KR101895356B1 - Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same - Google Patents
Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same Download PDFInfo
- Publication number
- KR101895356B1 KR101895356B1 KR1020150040528A KR20150040528A KR101895356B1 KR 101895356 B1 KR101895356 B1 KR 101895356B1 KR 1020150040528 A KR1020150040528 A KR 1020150040528A KR 20150040528 A KR20150040528 A KR 20150040528A KR 101895356 B1 KR101895356 B1 KR 101895356B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- photosensitive resin
- resin composition
- self
- color filter
- Prior art date
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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention relates to a self-emitting photosensitive resin composition and an image display device including the color filter prepared therefrom, and more particularly, to a self-emitting photosensitive resin composition comprising an alkali-soluble binder resin containing a cationic binder resin, a quantum dot, a photopolymerizable compound, And a solvent, and an image display apparatus including the color filter manufactured from the self-luminous photosensitive resin composition.
The color filter including the above composition exhibits excellent color characteristics, durability and reliability by improving the degree of curing and chemical resistance of the formed film, and when introduced into an image display device, various color expressions are ensured to realize high quality and vivid image quality.
Description
The present invention relates to a self-emitting photosensitive resin composition capable of realizing high quality image quality by securing excellent color reproduction characteristics, improved surface hardness and chemical resistance, and a color filter and an image display device manufactured therefrom.
The display industry has undergone drastic changes from cathode-ray tubes (CRTs) to flat panel displays such as plasma display panels (PDPs), organic light-emitting diodes (OLEDs), and liquid-crystal displays (LCDs). Among them, LCD is thin and light, has excellent resolution and low power consumption, and is widely used as an image display device used in almost all industries.
In LCD, white light generated from a light source passes through a liquid crystal cell, and transmittance is controlled, and three primary colors that are transmitted through red, green, and blue color filters are mixed to realize a full color.
A color filter is a thin film-type optical component that extracts three colors of red, green, and blue in white light and makes it possible to make a fine pixel unit. The size of one pixel is several tens to several hundreds of micrometers. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between each pixel, and a plurality of colors (typically, red (R), green (G) And blue (B)) are arranged in a predetermined order.
Therefore, the color filter is a key component for expressing colors on an LCD, and has been adopted for a wide variety of applications such as a notebook PC, a monitor, and a portable terminal, along with the spread of a flat panel display. High color purity, high transmittance and low reflection type color filter fabrication techniques have been actively studied for realizing more vivid image quality and quality advantage with other displays.
Generally, a color filter is manufactured by coating three or more colors on a transparent substrate by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, a transfer method, an ink jet method or the like. In recent years, a pigment dispersion method using a pigment dispersion type photosensitive resin excellent in terms of quality, degree and performance has been mainstream.
In the pigment dispersion method, which is one of the methods of implementing a color filter, a photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives is coated on a transparent substrate provided with a black matrix, A method of forming a colored thin film by repeating a series of steps of exposing a pattern to be formed and removing an unexposed portion with a solvent to thermally cure the substrate, .
Because the pigments are not soluble in solvents and are present in fine particulate form, they have reached a limit to display more vivid and more diverse colors that are required in recent years. On the other hand, dyes have superior color properties to pigments and have been studied to replace pigments with dyes. However, since dyes are poor in durability against light or solvents, there are problems to be solved, such as solving them, and securing sufficient solubility for the solvent used in the production of color filters, although the dyes are dissolved in the solvent.
Further, when a dye or a pigment is used as a coloring agent, the transmission efficiency of the light source is lowered. As a result, the reduction of the transmission efficiency lowers the color reproducibility of the image display device, which makes it difficult to realize a high-quality image.
Accordingly, it has been proposed to use self-luminescent quantum dots instead of dyes or pigments in accordance with the demand for further improved performance such as high color brightness, high contrast ratio, as well as excellent color pattern representation and high color reproduction ratio.
The quantum dots can be self-emitted by the light source and used to generate light in the visible and infrared regions. The quantum dots are small crystals of II-VI, III-V, IV-VI materials typically having a diameter of 1 nm to 20 nm, which is smaller than the bulk exciton Bohr radius. Due to the quantum confinement effects, the energy differences between the electron states of the quantum dots are a function of both the composition and the physical size of the quantum dots. Thus, the optical and optoelectronic properties of a quantum dot can be tuned and adjusted by changing the physical size of the quantum dot. The quantum dots absorb wavelengths shorter than the onset wavelength and emit light at the absorption start wavelength. The bandwidth of the emission spectra of the quantum dots is related to temperature dependent Doppler broadening, the Heisenberg Uncertainty Principle and the size distribution of the quantum dots. For a given quantum dot, the emission band of the quantum dot can be controlled by varying the magnitude. Thus, quantum dots can produce ranges of unattainable colors using conventional dyes or pigments.
The photosensitive resin composition containing such a quantum dot is becoming more and more important as the usage of the LCD becomes more advanced and diversified. Accordingly, there is an increasing demand for productivity, chemical resistance and durability as well as excellent color reproduction characteristics.
Korean Patent Laid-Open Publication No. 2011-0068861 proposes the addition of basket-like silsesquioxane to improve the adhesion and solvent resistance of the radiation-sensitive composition for the production of color filters.
Korean Patent No. 10-0671106 discloses a photosensitive resin composition which is improved in sensitivity and excellent in heat resistance and chemical resistance by using a cadmium-based binder and a specific initiator.
These patents have attempted to improve the physical and chemical properties of the coating film through the use of additional additives or a specific binder resin and a photoinitiator, but the effect thereof is not sufficient and the use of a pigment as a coloring material and a black matrix application It is different.
As a result of various studies to secure high surface hardness and chemical resistance while maintaining excellent color characteristics, Applicant has found that the above problem can be solved when a cadmium binder resin is used as an alkali-soluble binder resin, Completed.
Accordingly, it is an object of the present invention to provide a self-luminescent photosensitive resin composition which can secure an excellent coating film hardenability, chemical resistance and color reproduction characteristics.
The present invention also provides an image display device having a color filter including the self-light-sensitive photosensitive resin composition and capable of realizing a high-quality and vivid image quality.
In order to attain the above object, the present invention provides a photocatalyst comprising a quantum dot, an alkali-soluble binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
The alkali-soluble binder resin includes a cationic binder resin.
Wherein the cadmium binder resin is a compound represented by the following general formula (1).
[Chemical Formula 1]
(Wherein R 1 to R 3 and n is as described in the specification.)
The present invention also provides a color filter made of the self-luminescent photosensitive resin composition and an image display device including the same.
The self-luminescent photosensitive resin composition according to the present invention can solve the problems of adhesion, durability and chemical resistance degradation.
The color filter using the self-luminescent photosensitive resin composition is excellent in adhesion, heat resistance, chemical resistance, strength and hardness, and the image display device incorporating the color filter can achieve a vivid image quality by maintaining high luminance and ensuring excellent color reproduction characteristics have.
The present invention provides a self-luminescent photosensitive resin composition usable in a color filter of an image display apparatus.
In particular, the present invention discloses a self-luminescent photosensitive resin composition using a cadmium-based binder resin as an alkali-soluble binder resin, wherein the cadmium-based binder resin has excellent hardness of a coating film formed by improving curing degree, And chemical resistance, and is excellent in adhesion to a substrate. In addition, by manufacturing the pixel pixel of the color filter with the self-emission photosensitive resin composition, it is possible to easily form the pattern.
In addition to the cationic binder resin, the self-luminescent photosensitive resin composition according to the present invention includes a quantum dot, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
Each composition will be described below.
The alkali-soluble binder resin has reactivity and alkali solubility due to the action of light or heat and acts as a binder resin for quantum dots described later. It should also have properties soluble in the alkaline developer used in the development step for the production of color filters.
In the present invention, the alkali-soluble binder resin is a cadmium-based binder resin and comprises a compound represented by the following formula (1).
(In the formula 1,
R 1 is -CO-, -SO 2 -, -C ( CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,
R 2 is a methacrylate group, a vinyl group or an acrylate group,
R 3 is a reactive residue derived from a monomer represented by the following formula (2)
R 6 is H, -C 2 H 5 , -C 2 H 4 Cl, -C 2 H 4 OH, -CH 2 CH = CH 2 or a phenyl group,
and n is an integer of 1 to 20)
In this case, R < 3 > The present invention provides a color filter exhibiting excellent heat resistance, chemical resistance, strength and hardness, and having excellent durability and reliability by including a reactive residue derived from a monomer represented by the following formula (2), thereby increasing the degree of curing and improving surface hardness.
(Wherein R < 4 > and R < 5 > are the same or different and independently of each other,
Specifically, the cationic binder resin represented by Formula 1 includes at least one selected from repeating units represented by the following Formulas (3) to (7), and is not limited to the following examples. Anything that is available is available.
(In the above formulas 3 to 7,
R 1 is -CO-, -SO 2 -, -C ( CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,
R 2 is a methacrylate group, a vinyl group or an acrylate group,
R 6 is H, -C 2 H 5 , -C 2 H 4 Cl, -C 2 H 4 OH, -CH 2 CH = CH 2 or a phenyl group,
and n is an integer of 1 to 20)
Preferably, in the alkali-soluble binder resin of the present invention, the repeating units of the above formulas (3) to (7) may be contained in an amount of 3 to 80 mol%, more preferably 5 to 70 mol% . When it is used in the above range, it exhibits excellent properties of solvent resistance and peeling of patterns during the development process because of its excellent sensitivity and adhesion.
Such an alkali-soluble binder resin may be contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight, based on 100% by weight of the total composition. When used within the above range, solubility in a developing solution is sufficient, pattern formation is easy, and reduction of the film thickness of the pixel portion of the exposed portion is prevented during development, so that the missing property of the non-pixel portion is improved.
The quantum dot in the present invention plays a role of generating three primary colors having excellent color purity by photoexcitation from a color filter to a backlight, and the quantum dots spontaneously emit light having color, so that the range of color purity and color expression can be greatly improved.
The quantum dot is a nano-sized semiconductor material. The atoms form molecules, and the molecules form a cluster of small molecules called clusters to form nanoparticles. These nanoparticles are called quantum dots, especially when they have semiconductor properties. The quantum dots emit energy according to the corresponding energy bandgap when they reach the excited state from the outside.
The quantum dot according to the present invention is not particularly limited as long as it is a quantum dot that can emit light by stimulation by light, for example, a II-VI semiconductor compound; III-V semiconductor compound; IV-VI semiconductor compound; Group IV elements or compounds containing them; And combinations thereof. These may be used alone or in combination of two or more.
Wherein the II-VI semiconductor compound is selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; Trivalent compounds selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; And a Group III-V semiconductor compound may be selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, , GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A trivalent compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; And a silicate compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, , The IV-VI semiconductor compound is selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; Ternary compounds selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And a silane compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof. The Group IV element or a compound containing the Group IV element may be selected from the group consisting of Si, Ge, ≪ / RTI > And these elemental compounds selected from the group consisting of SiC, SiGe, and mixtures thereof.
Further, the quantum dots may have a single homogeneous structure; A dual structure such as a core-shell, gradient structure or the like; Or a mixed structure thereof.
In the dual structure of the core-shell, the material forming each core and the shell may be made of the different semiconductor compounds mentioned above. For example, the core may include, but is not limited to, one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO. The shell may include, but is not limited to, one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe.
The quantum dots of the present invention are classified into quantum dots representing red, quantum dots representing green, and quantum dots representing blue such that the colored photosensitive resin composition used for producing a typical color filter contains red, green, and blue colorants for color implementation And the quantum dot according to the present invention may be one selected from the above-mentioned red, green, blue, and combinations thereof.
The quantum dot can be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process.
The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal is grown, the organic solvent naturally coordinates to the surface of the quantum dot crystal to serve as a dispersing agent to control crystal growth. Therefore, the metal organic chemical vapor deposition (MOCVD) or molecular molecular epitaxy (MBE) beam epitaxy), it is possible to control the growth of nanoparticles through an easier and less expensive process.
Such quantum dots may be contained in an amount of 3 to 80% by weight, preferably 5 to 70% by weight, in 100% by weight of the total composition. If the content is less than 3% by weight, the light emitting efficiency may be insufficient. If the content is more than 80% by weight, the content of the other composition is insufficient.
The quantum dot of the present invention may optionally further include a pigment as required. In particular, when a color filter is manufactured including quantum dots representing red and green, the color characteristics of the color filter can be further improved by further including pigments.
As the above-mentioned pigments, all known organic pigments and inorganic pigments can be used, and these pigments can be used singly or in combination of two or more kinds. Preferably organic pigments can be used.
For example, organic pigments are compounds classified as pigments in the color index (CI, published by The Society of Dyers and Colors, Inc.), specifically color indexes (CIs) such as: Quot; is given: "
C.I. Pigment red No. 1, C.I. Pigment red No. 2, C.I. Pigment red No. 5, C.I. Pigment red No. 9, C.I. Pigment red No. 17, C.I. Pigment red No. 31, C.I. Pigment red No. 32, C.I. Pigment red No. 41, C.I. Pigment red No. 97, C.I. Pigment red No. 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment red No. 144, C.I. Pigment red No. 149, C.I. Pigment Red 166, C.I. Pigment Red No. 168, C.I. Pigment red No. 170, C.I. Pigment Red 171, C.I. Pigment red No. 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment red No. 180, C.I. Pigment red No. 185, C.I. Pigment red No. 192, C.I. Pigment Red No. 194, C.I. Pigment red No. 202, C.I. Pigment red No. 206, C.I. Pigment red No. 207, C.I. Pigment red No. 208, C.I. Pigment red No. 209, C.I. Pigment Red 214, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment red No. 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red No. 264, C.I. Pigment red No. 265, C.I. Pigment red No. 272;
C.I. Pigment Green No. 7, C.I. Pigment green No. 36, C.I. Pigment green No. 58;
C.I. Pigment yellow No. 20, C.I. Pigment yellow No. 24, C.I. Pigment yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow No. 86, C.I. Pigment yellow 93, C.I. Pigment Yellow 94, C.I. Pigment yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment yellow No. 137, C.I. Pigment yellow 138, C.I. Pigment yellow No. 139, C.I. Pigment yellow No. 147, C.I. Pigment yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment yellow 153, C.I. Pigment yellow 154, C.I. Pigment yellow 166, C.I. Pigment yellow No. 173, C.I. Pigment Yellow No. 180 and C.I. Pigment yellow 185;
C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 31, C.I. Pigment orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment orange No. 43, C.I. Pigment orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment orange No. 64, C.I. Pigment orange No. 65, and C.I. Pigment orange No. 71;
C.I. Pigment white No. 4, C.I. Pigment white No. 6, C.I. Pigment White 22.
These organic pigments may be subjected to a surface treatment using a pigment derivative in which a rosin treatment, an acidic group or a basic group is introduced, a surface graft treatment using a polymer compound or the like, a fine particle treatment using sulfuric acid, Cleaning treatment or the like may be performed.
In addition to this, pigments for use in printing ink, ink jet, etc., and pigments for use in water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacreotide pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxins, anthraquinones, Anthanthrone, indanthrone, pravanthrone, pyranthrone pigments, and the like can be used.
The quantum dot can be used together with a dispersant, a dispersion aid, and a dispersion resin as necessary.
The dispersant is added to maintain the deagglomeration and stability of the quantum dots and further included pigments, and any of those generally used in the art can be used without limitation.
Examples of the dispersing agent include cationic, anionic, nonionic, amphoteric acrylic, polyester, and polyamine. These may be used alone or in combination of two or more.
Commonly used dispersants include butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) as an acrylic dispersant. Dispersing BYK-2000, DISPER BYK-2070, DISPER BYK-2150, BYK-LPN6919 and BYK-LPN21116 (manufactured by BYK), Solsperse 5000 (Manufactured by Lubrizol), and the like.
In addition to the above-mentioned acrylic dispersant, other types of dispersants include known resin type dispersants, in particular, polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids , Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl-substituted polycarboxylic acids and their modified products, free carboxyl groups (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid Water-soluble resins or water-soluble polymer compounds such as copolymers, polyvinyl alcohols, polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.
DISKER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184 (all manufactured by BYK); EFKA-44, EFKA-44, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA- 4400, EFKA-4406, EFKA-4510, EFKA-4800 (manufactured by BASF); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (manufactured by Lubrizol); Hinoact T-6000, Hinoact T-7000, Hinoact T-8000 (manufactured by Kawaken Fine Chemicals Co., Ltd.); AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 (manufactured by Ajinomoto Co., Ltd.); FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 (manufactured by Kyowa Chemical Industry Co., Ltd.).
The amount of the dispersant to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the quantum dot used. When the content is more than 60 parts by weight, the viscosity may be increased. When the content is less than 5 parts by weight, it may be difficult to atomize the pigment and gelation after dispersion.
Examples of the dispersion aid include pigment derivatives, specifically, copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.
The dispersion resin can be selectively added to the quantum dots and the pigment as the dispersion medium of the above-described quantum dots and the pigment, and it is possible to manufacture a pigment dispersion composition which is more excellent by mixing dispersing resins as compared with the use of a dispersant alone.
In the case of the dispersion resin, it is possible to use the dispersion resin as long as it can function as a dispersion medium. However, in view of the developability of the photosensitive resin composition, it is preferable to have an acid value in order to have solubility in an alkali developer.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.
In the case of the dispersion resin having an acid value, it is possible to copolymerize a compound having a carboxyl group and an unsaturated bond with a compound having an unsaturated bond capable of copolymerization with the carboxyl group.
Specific examples of the compound having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; and mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as ? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable. The compounds exemplified as the compound having a carboxylic acid group and an unsaturated bond may be used alone or in combination of two or more.
Specific examples of the compound having an unsaturated bond capable of copolymerizing with the compound having a carboxylic acid group and an unsaturated bond are as follows and are not necessarily limited thereto:
The copolymerizable monomer is selected from the group consisting of styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, Aromatic vinyl compounds such as ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether or p-vinyl benzyl glycidyl ether; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate or t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like Unsaturated oxetane compounds, and the like. The compounds exemplified as the compound (b2) may be used alone or in combination of two or more.
The amount of the dispersing resin used is preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the solid content of the quantum dot used. If the content exceeds 60 parts by weight, the viscosity can be increased by the dispersing resin. If the content is less than 5 parts by weight, the amount of the dispersing resin is insufficient, so that the pigment dispersed composition can not be obtained.
The photopolymerizable compound in the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers and other polyfunctional monomers, .
The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.
The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.
The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Such a photopolymerizable compound may be contained in an amount of 1 to 45% by weight, preferably 1 to 20% by weight, in 100% by weight of the total composition. If the content is less than the above range, the photosensitivity may be lowered. On the contrary, if the content is in excess of the above range, the photosensitive resin layer becomes excessively sticky, and the strength of the film is insufficient.
The photopolymerization initiator in the present invention is a compound for initiating the polymerization of the photopolymerizable compound described above and is not specifically limited in the present invention. However, the photopolymerization initiator is not limited to the acetophenone, benzophenone, triazine, thioxanthone, oxime, Based, anthraquinone-based, and nonimidazole-based compounds, which may be used alone or in combination of two or more.
Acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- (2- Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) Oligomers of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one is preferably usable.
Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, (Diethylamino) benzophenone, and the like.
Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1 -yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanedioxanthone.
Oximeimino-1-phenylpropan-1-one, and the like. Commercially available products include OXE-01, OXE-02 and OXE-03 manufactured by Ciba .
As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like can be used.
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 anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, and the like.
Examples of the nonimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) 4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2, 2'-bis (2-chlorophenyl) , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl groups in the 4,4', 5,5 ' Substituted imidazole compounds, and the like.
Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylchloroxylate, Compounds and the like can be used.
The content of the photopolymerization initiator is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on 100% by weight of the total composition. The content of the photopolymerization initiator is, Parts by weight, preferably 10 to 100 parts by weight.
When the content of the photopolymerization initiator is within the above range, the self-luminescent photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion and the smoothness on the surface of the pixel portion tend to be favorable. When the content of the photopolymerization initiator is within the above range, the sensitivity efficiency of the self-luminescent photosensitive resin composition is further increased, and the productivity of the color filter formed by using the composition tends to be improved.
In addition, when the photopolymerization initiator is used in combination with the photopolymerization initiator, the self-luminescent photosensitive resin composition containing the photopolymerization initiator becomes more sensitive and productivity is improved when a color filter is formed.
As the photopolymerization initiation auxiliary which can be used, one kind of compound selected from the group consisting of an amine compound, a carboxylic acid compound and a combination thereof can be preferably used.
Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone Amino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.
Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
Such a photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.
Any solvent may be used as long as it can dissolve or disperse the above-mentioned composition, and the solvent is not particularly limited in the present invention. Representative examples are alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, examples of the solvent include alkylene 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; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, Ryu; 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 glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; There deulsu the like cyclic esters such as -butyrolactone - γ.
Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C in the solvent is preferably used from the viewpoint of coatability and dryness, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents (E) may be used alone or in combination of two or more.
Such a solvent may be used as the remainder to satisfy 100 wt% of the total composition. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability).
In addition, the self-luminescent photosensitive resin composition according to the present invention may further include known additives for various purposes. As such additives, additives such as fillers, other polymer compounds, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents may be used in combination. These additives may be used alone or in combination of two or more, and it is preferable to use 1 wt% or less in the whole composition in consideration of light efficiency and the like.
Examples of the filler include glass, silica, and alumina. Other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester , And thermoplastic resins such as polyurethane.
Specific examples of other polymer compounds include curable resins such as epoxy resin and maleimide resin, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane have.
The curing agent is used for enhancing deep curing and mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.
The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like.
The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of commercially available epoxy resin curing agents include trade name (ADEKA HARDONA EH-700) (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (Manufactured by Shin-Etsu Chemical Co., Ltd.).
The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane and the like.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Specific examples of the anti-aggregation agent include sodium polyacrylate .
Specific examples of the anti-aggregation agent include sodium polyacrylate.
The self-luminescent photosensitive resin composition according to the present invention can produce a color filter by wet coating. In this case, the wet coating method can be applied to a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) A coating apparatus such as an inkjet can be used.
The present invention provides a color filter made of the self-luminous photosensitive resin composition described above.
When the color filter of the present invention is applied to an image display apparatus, the surface hardness of a coated film formed by using a cadmium binder resin is improved and the chemical stability is improved due to excellent heat resistance and solvent resistance, thereby improving reliability and durability . In addition, the quantum dot emits light by the light source itself, and emits light having a color, so that the color reproducibility is excellent.
The color filter includes a substrate and a pattern layer formed on the substrate.
The substrate may be a substrate of a color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. For example, glass, silicon (Si), silicon oxide (SiO x ), or a polymer substrate can be used. Specifically, the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).
The pattern layer may be a layer containing the self-luminescent photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminescent photosensitive resin composition and exposing, developing and thermally curing the self-luminescent photosensitive resin composition in a predetermined pattern.
According to one embodiment of the present invention, the pattern layer formed of the self-luminescent photosensitive resin composition may have a red pattern layer containing red quantum dots, a green pattern layer containing green quantum dots, and a blue pattern layer containing blue quantum dots have. During the light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.
In such a case, the emitted light of the light source is not particularly limited when applied to an image display apparatus, but a light source that emits blue light in terms of better color reproducibility can be used.
According to another embodiment of the present invention, the pattern layer may include only a pattern layer of two colors, that is, a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer may further include a transparent pattern layer not containing a quantum dot.
In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In such a case, the red quantum dot emits red light and the green quantum dot emits green light, and the transparent pattern layer transmits blue light as it is and exhibits blue color.
The color filter including the substrate and the pattern layer described above may further include a partition wall formed between each pattern, and may further include a black matrix. Further, it may further comprise a protective film formed on the pattern layer of the color filter.
The present invention also provides an image display device including the color filter.
As the image display apparatus, various image display apparatuses such as an electroluminescence display apparatus, a plasma display apparatus, and a field emission display apparatus can be used as well as a normal liquid crystal display apparatus.
The image display apparatus according to the present invention is excellent in light efficiency, exhibits high luminance, excellent in color reproducibility, and has a wide viewing angle.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Production Example 1. Synthesis of Qdot A of CdSe (core) / ZnS (shell) structure
CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 ml) were added to the reactor together with 1-Octadecene (20 ml) and heated to 150 ° C. Lt; / RTI > The reaction was then left under vacuum at 100 mTorr for 20 minutes to remove the acetic acid formed by the displacement of oleic acid into zinc.
Then, a transparent mixture was obtained by applying heat at 310 DEG C, and after maintaining the temperature at 310 DEG C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine Se and S solutions were rapidly injected into a reactor containing Cd (OA) 2 and Zn (OA) 2 solutions. The resulting mixture was grown at 310 ° C for 5 minutes, and growth was stopped using an ice bath.
Then, the precipitate was precipitated with ethanol, and the quantum dots were separated using a centrifugal separator. The excess impurities were washed with chloroform and ethanol to obtain a product having a core particle size and shell thickness summed to 3 to 5 nm And a quantum dot A of a CdSe (core) / ZnS (shell) structure in which particles are distributed.
Production Example 2. Preparation of quantum dot dispersion A-1
25.0 parts by weight of Quantum Point A in Production Example 1, 6 parts by weight of Ajisera PB-821 as a dispersant and 69 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare Quantum Point Dispersion A-1 Respectively.
Production Example 3. Preparation of quantum dot dispersion A-2
10.0 parts by weight of Quantum Point A in Production Example 1, 15.0 parts by weight of a titanium oxide pigment (R-102, manufactured by Dupont) as a CI pigment white color No. 6, 6 parts by weight of Ajisera PB-821 as a dispersing agent and 6 parts by weight of propylene glycol monomethyl ether acetate Were mixed and dispersed by a bead mill for 12 hours to prepare a quantum dot dispersion A-2.
Production Example 4. Preparation of alkali-soluble binder resin B-1
(4,4'- (9H-fluorene-9,9-dicarboxylic acid) bis (4,1-phenylene)) bis (oxyacetic acid) was added to a 1000 ml flask equipped with a stirrer, a thermometer and a reflux condenser. ) 10 parts by weight of bis (methylene) dioxane, 30 parts by weight of acrylic acid, and 10 parts by weight of propylene glycol monomethyl ether acetate were gradually added and the temperature of the flask was gradually raised to 100 DEG C while stirring.
Then, 0.3 part by weight of tetramethylammonium chloride and 0.01 part by weight of a polymerization inhibitor were added, followed by stirring at the same temperature for 3 hours. When the reaction was completed, the temperature was gradually lowered to room temperature and distilled water was added to precipitate the precipitate. After filtering, the precipitate was washed with distilled water 2-3 times and then dried.
10 parts by weight of the thus obtained precipitate was added to a 1000 ml flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then 3 parts by weight of tetramethylammonium chloride, 50 parts by weight of propylene glycol monomethyl ether acetate, And 5 parts by weight of phthalic anhydride were placed and replaced with nitrogen.
Thereafter, the reaction solution was stirred, the temperature was raised to 110 DEG C, and the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 5,5 '- (perfluoropropane-2,2-dile) dibenzo [de] isochromene-1,3-dione was added and reacted for an additional 6 hours. An alkali-soluble binder resin B-1 having a solid content of 123 mgKOH / g after purification and a weight-average molecular weight of 12,300 as measured by GPC was obtained.
Production Example 5. Preparation of alkali-soluble binder resin B-2
(4,4'- (9H-fluorene-9,9-dicarboxylic acid) bis (4,1-phenylene)) bis (oxyacetic acid) was added to a 1000 ml flask equipped with a stirrer, a thermometer and a reflux condenser. ) 10 parts by weight of bis (methylene) dioxane, 30 parts by weight of acrylic acid, and 10 parts by weight of propylene glycol monomethyl ether acetate were gradually added and the temperature of the flask was gradually raised to 100 DEG C while stirring.
Then, 0.3 part by weight of tetramethylammonium chloride and 0.01 part by weight of a polymerization inhibitor were added, followed by stirring at the same temperature for 3 hours. When the reaction was completed, the temperature was gradually lowered to room temperature and distilled water was added to precipitate the precipitate. After filtering, the precipitate was washed with distilled water 2-3 times and then dried.
10 parts by weight of the thus obtained precipitate was added to a 1000 ml flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then 3 parts by weight of tetramethylammonium chloride, 50 parts by weight of propylene glycol monomethyl ether acetate, And 5 parts by weight of tallic anhydride were placed and replaced with nitrogen.
Thereafter, the reaction solution was stirred, the temperature was raised to 110 DEG C, and the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 5,5 '- (perfluoropropane-2,2-dile) bis (hexahydroisobenzofuran-1,3-dione) was added and the mixture was reacted for 6 hours. An alkali-soluble binder resin B-2 having a solid content of 130 mgKOH / g after purification and a weight-average molecular weight of 12,000 as measured by GPC was obtained.
Production Example 6. Preparation of alkali-soluble binder resin B-3
(4,4'- (9H-fluorene-9,9-dicarboxylic acid) bis (4,1-phenylene)) bis (oxyacetic acid) was added to a 1000 ml flask equipped with a stirrer, a thermometer and a reflux condenser. ) 10 parts by weight of bis (methylene) dioxane, 30 parts by weight of acrylic acid, and 10 parts by weight of propylene glycol monomethyl ether acetate were gradually added and the temperature of the flask was gradually raised to 100 DEG C while stirring.
Then, 0.3 part by weight of tetramethylammonium chloride and 0.01 part by weight of a polymerization inhibitor were added, followed by stirring at the same temperature for 3 hours. When the reaction was completed, the temperature was gradually lowered to room temperature and distilled water was added to precipitate the precipitate. After filtering, the precipitate was washed with distilled water 2-3 times and then dried.
10 parts by weight of the thus obtained precipitate was added to a 1000 ml flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then 3 parts by weight of tetramethylammonium chloride, 50 parts by weight of propylene glycol monomethyl ether acetate, And 5 parts by weight of tallic anhydride were placed and replaced with nitrogen.
Thereafter, the reaction solution was stirred, the temperature was raised to 110 DEG C, and the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 4,4 '- (hexafluoroisopropylidene) diphthalic was added and reacted for an additional 6 hours. After the purification, the alkali-soluble binder resin B-3 having a solid content of 120 mgKOH / g and a weight-average molecular weight of 12,100 as measured by GPC was obtained.
Examples 1 to 6 and Comparative Examples 1 to 3: Preparation of self-luminescent photosensitive resin composition
The self-luminescent photosensitive resin composition was prepared using the components and contents shown in Table 1 below.
2) The quantum dot dispersion prepared in Production Example 3
3) Cathode binder resin prepared in Production Example 4
4) Cathode binder resin prepared in Production Example 5
5) Cathode binder resin prepared in Production Example 6
6) Acrylic binder resin (SPCY-1L, manufactured by Showa Highpolymer Co., Ltd.)
7) Acrylic binder resin (SPCY-6L, manufactured by Showa Highpolymer Co., Ltd.)
8) Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
9) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369;
10) 4,4'-di (N, N'-dimethylamino) -benzophenone (manufactured by Hodogaya Kagaku Co., Ltd.)
11) Irgacure OXE01 (manufactured by Ciba Specialty Chemical)
12) Irgacure OXE03 (manufactured by Ciba Specialty Chemical)
13) Propylene glycol monomethyl ether acetate
Experimental Example 1. Evaluation
A color filter was prepared from the self-luminescent photosensitive resin compositions prepared in the above Examples and Comparative Examples. That is, each of the self-luminescent photosensitive resin compositions was coated on a glass substrate by spin coating, then placed on a heating plate, and maintained at a temperature of 100 ° C for 2 minutes to form a thin film.
Subsequently, a test photomask having a pattern changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 50 탆 was placed on the thin film, and the distance between the test photomask and the test photomask was set to 50 탆. Respectively.
At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kw high pressure mercury lamp containing g, h and i lines. No special optical filter was used at this time.
The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter pattern. The thickness of the self-emission color pattern prepared above was 3.0 mu m.
(1) Surface hardness
The hardness of the films obtained in the above Examples and Comparative Examples was measured using a hardness meter (HM500; Fischer). The results obtained are shown in Table 2 below.
The surface hardness was evaluated by the following criteria.
<Standard>
?: Surface hardness of 30 or more
DELTA: Surface hardness less than 10 to 30
X: surface hardness less than 10
(2) Solvent resistance
The membranes obtained in Examples and Comparative Examples were evaluated for solvent resistance to NMP (n-methyl-2-pyrrolidone) solvent. The membranes were cut into 3 × 3 cm size and placed in 5 g of NMP, left in an oven at 100 ° C. for 30 minutes , The NMP solvent was recovered and measured using the absorbance of the coloring material extracted in the NMP solvent using a UV-vis spectrometer (UV-2550, manufactured by Shimatzu). The obtained results are shown in Table 2 below.
The reliability was evaluated by the following criteria.
<Standard>
○: absorbance less than 1
?: Absorbance 1 to less than 3
X: Absorbance of 3 or more
Referring to Table 2, in Examples 1 to 6 using the self-luminescent photosensitive resin composition according to the present invention, it was confirmed that the formed film had better hardness and solvent resistance than Comparative Examples 1 and 2 using acrylic binder resin .
The self-luminescent photosensitive resin composition according to the present invention is introduced into a color filter of an image display device to maintain excellent durability and chemical resistance, thereby realizing a high-quality and vivid image quality.
Claims (7)
Wherein the quantum dots comprise 3 to 80% by weight and the alkali-soluble binder resin comprises 5 to 20% by weight in 100% by weight of the total composition,
Wherein the alkali-soluble binder resin is a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
(In the formula 1,
R 1 is -CO-, -SO 2 -, -C ( CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,
R 2 is a methacrylate group, a vinyl group or an acrylate group,
R 3 is a reactive residue derived from a monomer represented by the following formula (2)
R 6 is H, -C 2 H 5 , -C 2 H 4 Cl, -C 2 H 4 OH, -CH 2 CH = CH 2 or a phenyl group,
and n is an integer of 1 to 20)
(2)
(Wherein R < 4 > and R < 5 > are the same or different and independently of each other,
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
(In the above formulas 3 to 7,
R 1 is -CO-, -SO 2 -, -C ( CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,
R 2 is a methacrylate group, a vinyl group or an acrylate group,
R 6 is H, -C 2 H 5 , -C 2 H 4 Cl, -C 2 H 4 OH, -CH 2 CH = CH 2 or a phenyl group,
and n is an integer of 1 to 20)
3 to 80% by weight of a quantum dot,
5 to 20% by weight of an alkali-soluble resin,
1 to 45% by weight of photopolymerizable compound and
And 0.1 to 20% by weight of a photopolymerization initiator, and the remainder is made of a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150040528A KR101895356B1 (en) | 2015-03-24 | 2015-03-24 | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150040528A KR101895356B1 (en) | 2015-03-24 | 2015-03-24 | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160114292A KR20160114292A (en) | 2016-10-05 |
| KR101895356B1 true KR101895356B1 (en) | 2018-09-05 |
Family
ID=57153923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150040528A KR101895356B1 (en) | 2015-03-24 | 2015-03-24 | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101895356B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067243A (en) * | 2016-12-12 | 2018-06-20 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using same and color filter |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10712483B2 (en) * | 2015-08-24 | 2020-07-14 | Samsung Electronics Co., Ltd. | Photosensitive compositions, quantum dot polymer composite pattern prepared therefrom, and electronic devices including the same |
| KR101840347B1 (en) * | 2016-10-26 | 2018-03-20 | 동우 화인켐 주식회사 | Self emission type photosensitive resin composition, color filter and image display device produced using the same |
| KR101974841B1 (en) * | 2016-12-07 | 2019-05-03 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
| KR101998732B1 (en) * | 2016-12-07 | 2019-07-10 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
| KR102601648B1 (en) * | 2017-02-20 | 2023-11-14 | 삼성전자주식회사 | Photosensitive compositions, preparation methods thereof, and quantum dot polymer composite pattern produced therefrom |
| JP6876823B2 (en) * | 2017-03-30 | 2021-05-26 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Blue photosensitive resin composition, color filter and image display device manufactured using this |
| KR101998775B1 (en) * | 2017-03-30 | 2019-07-10 | 동우 화인켐 주식회사 | A blue colored photosensitive resin composition, color filter and image display device produced using the same |
| WO2018182186A1 (en) * | 2017-03-30 | 2018-10-04 | 동우화인켐 주식회사 | Blue photosensitive resin composition, and color filter and image display device manufactured by using same |
| JP7011055B2 (en) | 2017-10-27 | 2022-01-26 | サムスン エスディアイ カンパニー，リミテッド | Quantum dot-containing composition, quantum dot manufacturing method and color filter |
| KR102387414B1 (en) * | 2017-11-07 | 2022-04-15 | 동우 화인켐 주식회사 | A binder resin, a colored photo resist composition, a color filter comprising the same and a display device comprising the same |
| KR102464914B1 (en) * | 2017-11-22 | 2022-11-09 | 동우 화인켐 주식회사 | A light converting resin composition, a light converting unit and a display device using the same |
| CN110297391B (en) * | 2018-03-21 | 2022-12-20 | 东友精细化工有限公司 | Light conversion resin composition, light conversion laminated substrate, and image display device |
| KR102284582B1 (en) * | 2018-04-04 | 2021-08-02 | 삼성에스디아이 주식회사 | Red photosensitive resin composition, photosensitive resin layer using the same and color filter |
| KR102519941B1 (en) * | 2018-10-18 | 2023-04-07 | 동우 화인켐 주식회사 | Light Conversion Resin Composition, Light Conversion Sheet and Display Device |
| KR102296792B1 (en) | 2019-02-01 | 2021-08-31 | 삼성에스디아이 주식회사 | Non-solvent type curable composition, curing layer using the same, color filter including the curing layer, display device and manufacturing method of the curing layer |
| KR102360987B1 (en) | 2019-04-24 | 2022-02-08 | 삼성에스디아이 주식회사 | Curable composition including quantum dot, resin layer using the same and display device |
| KR102504790B1 (en) | 2019-07-26 | 2023-02-27 | 삼성에스디아이 주식회사 | Quantum dot, curable composition comprising the same, curing layer using the composition, color filter including the curing layer, display device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100574318B1 (en) * | 1999-02-04 | 2006-04-26 | 제일모직주식회사 | Photosensitive resin composition and color filter |
| KR100671106B1 (en) | 2004-12-29 | 2007-01-17 | 제일모직주식회사 | High photosensitive resin composition and black matrix thereof |
| WO2006103908A1 (en) * | 2005-03-28 | 2006-10-05 | Idemitsu Kosan Co., Ltd. | Organic ligands for semiconductor nanocrystals |
| KR101266295B1 (en) * | 2009-09-09 | 2013-05-23 | 제일모직주식회사 | Black photosensitive resin composition and black matrix manufactured by using the same |
| JP5515714B2 (en) | 2009-12-16 | 2014-06-11 | Ｊｓｒ株式会社 | Coloring composition, color filter and color liquid crystal display element |
| KR20130003892A (en) * | 2011-07-01 | 2013-01-09 | 동우 화인켐 주식회사 | Cardo type resin, black photosensitive resin composition including the same, color filter and liquid crystal display device using the composition |
-
2015
- 2015-03-24 KR KR1020150040528A patent/KR101895356B1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067243A (en) * | 2016-12-12 | 2018-06-20 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using same and color filter |
| KR101976659B1 (en) | 2016-12-12 | 2019-05-09 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using same and color filter |
| US10915020B2 (en) | 2016-12-12 | 2021-02-09 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, photosensitive resin layer using same and color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160114292A (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101895356B1 (en) | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| KR101879016B1 (en) | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| KR101840347B1 (en) | Self emission type photosensitive resin composition, color filter and image display device produced using the same | |
| KR102418601B1 (en) | Self emission type photosensitive resin composition, color filter using thereof and image display device having the same | |
| KR102431437B1 (en) | Color filter, method for producing the same and image display device employing color filter | |
| KR102413603B1 (en) | Color filter comprising dichroic mirror and image display device having the same | |
| CN106569389B (en) | Self-luminous photosensitive resin composition, color filter and display device including the same | |
| CN105988291B (en) | Self-luminous photosensitive resin composition, color filter and image display device | |
| KR101941573B1 (en) | Self emission type photosensitive resin composition, color filter and image display device produced using the same | |
| CN110291431B (en) | Color filter and image display device | |
| KR102554277B1 (en) | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| KR20160112499A (en) | Yellow curable resin composition, and color filter comprising thereof and display device comprising of the same | |
| KR20160091708A (en) | Color filter and image display device using the same | |
| KR101932221B1 (en) | Yellow curable resin composition, and color filter and display device comprising the same | |
| KR20160114362A (en) | Color filter and display dece comprising thereof | |
| CN110099954B (en) | Yellow curable resin composition, color filter produced using same, and image display device | |
| KR20170109762A (en) | Photosensitive resin composition, color filter and image display device produced using the same | |
| TWI815801B (en) | Yellow curable resin composition, and color filter and image display device comprising the same | |
| KR102206910B1 (en) | Self emission type photosensitive resin composition, and color filter comprising thereof and display device comprising of the same | |
| KR102174182B1 (en) | A self-light emitting photosensitive resin composition, color filter and display device comprising the same | |
| KR102297066B1 (en) | Yellow curable resin composition, and color filter comprising thereof and display device comprising of the same | |
| KR102376959B1 (en) | Yellow curableresin composition, color filter and display device having the same | |
| KR20190108781A (en) | Yellow curableresin composition, color filter and display device having the same | |
| KR20170017544A (en) | Self emission type photosensitive resin composition, color filter using thereof and image display device having the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| A302 | Request for accelerated examination | ||
| E902 | Notification of reason for refusal | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |