WO2018093028A1 - Self-luminescent photosensitive resin composition, color filter prepared by using same, and image display device - Google Patents

Abstract

The present invention relates to a self-luminescent photosensitive resin composition and, more specifically, to a self-luminescent photosensitive resin composition comprising scattering particles and an alkali soluble resin, wherein the alkali soluble resin has an acrylic equivalent of 300 to 2,000g/eq. Therefore, the self-luminescent photosensitive resin composition can provide a high-quality color filter, showing excellent luminance, without the problem of degraded light efficiency and poor photosensitive properties during hard baking.

Description

Self-luminous photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a self-luminous photosensitive resin composition, a color filter manufactured using the same, and an image display device.

The display industry has undergone rapid changes from cathode-ray tubes (CRTs) to flat panel displays represented by plasma display panels (PDPs), organic light-emitting diodes (OLEDs), liquid-crystal displays (LCDs), and the like. Among them, LCD is thin and light, and has excellent resolution and low power consumption, so it is widely used as an image display device used in almost all industries, and a large market is expected to expand in the future.

In the LCD, as the white light generated from the light source passes through the liquid crystal cell, the transmittance is controlled, and the three primary colors transmitted through the red, green, and blue color filters are mixed to realize full color.

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and enables the unit of fine pixels, and the size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate for shielding the boundary between each pixel, and a plurality of colors (typically, red (R) and green (G) to form each pixel. And a pixel portion in which three primary colors of blue (B) are arranged in a predetermined order.

Therefore, color filters have been adopted for a wide range of applications, such as notebook PCs, monitors, and mobile terminals, with the spread of flat panel displays as a key component to express colors in LCDs. In order to realize more vivid image quality and superior quality with other displays, high color purity, high transmissivity, and low reflection type color filter manufacturing technologies are actively researched.

In general, color filters are manufactured by coating three or more colors on a transparent substrate by a pigment dispersion method, electrodeposition method, printing method, dyeing method, transfer method, inkjet method, or the like. Recently, the pigment dispersion method using the pigment dispersion type photosensitive resin which is excellent in quality, precision, and performance is mainstream.

The pigment dispersion method, which is one of the methods for implementing the color filter, coats the photosensitive resin composition including alkali soluble resin, photopolymerization monomer, photoinitiator, epoxy resin, solvent, and other additives on a transparent substrate provided with a black matrix, After exposing the pattern of the form to be formed, it is a method of forming a colored thin film by repeating a series of processes of removing the non-exposed areas with a solvent and thermally curing, and is active in manufacturing LCDs of mobile phones, laptops, monitors, and TVs. Is being applied.

Because pigments do not dissolve in solvents and exist as fine particles, they have recently reached a limit to display the sharper and more diverse colors required. On the other hand, since dyes have better color characteristics than pigments, studies have been conducted to replace pigments with dyes. However, dyes also suffer from problems such as improving durability because they are less resistant to light and solvents, and ensuring sufficient solubility in solvents used in the production of color filters, although dyes are dissolved in solvents.

Moreover, when using a dye or a pigment as a coloring agent, the problem of reducing the transmission efficiency of a light source arises. As a result, the decrease in the transmission efficiency lowers the color reproducibility of the image display device, which makes it difficult to realize a high quality screen.

The use of quantum dots that emits light instead of dyes or pigments has been proposed, as well as excellent color characteristics, higher color reproducibility, and improved performance such as high brightness and high contrast ratio.

Quantum dots emit light by themselves and can be used to generate light in the visible and infrared regions. Quantum dots are small crystals of II-VI, III-V, IV-VI materials that typically have a diameter of 1 nm to 20 nm, smaller than the bulk exciton Bohr radius. Due to quantum confinement effects, the energy differences between the electronic states of a quantum dot are a function of both the composition and physical size of the quantum dot. Thus, the optical and optoelectronic properties of quantum dots can be tuned and adjusted by changing the physical size of the quantum dots. The quantum dots absorb wavelengths shorter than the onset wavelength and emit light at the initiation wavelength. The bandwidth of luminescence spectra of quantum dots is related to temperature dependent Doppler broadening, Heisenberg Uncertainty Principle and size distribution of 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 a range of unattainable colors using conventional dyes or pigments.

But quantum dots are essentially non-scattering particles because of their nanoscale size. Thus, when light passes through a color filter containing quantum dots, it has a much shorter optical path than other dyes or pigments. Most of the light is absorbed by the quantum dots unless the thickness of the color filter is sufficient. Therefore, a method of controlling the thickness of the color filter, increasing the concentration of quantum dots, or introducing scattering particles has been proposed. Among these, problems in terms of color uniformity occur when adjusting thickness or concentration.

In the method of introducing scattering particles into the color filter, Korean Patent Laid-Open No. 10-2016-0060904 relates to an image display device including a self-luminous photosensitive resin composition and a color filter manufactured therefrom. And a self-luminous photosensitive resin composition comprising a scattering particle, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin and a solvent, and a color filter prepared therefrom.

In addition, Korean Patent Laid-Open No. 10-2016-0091708 relates to a color filter and an image display apparatus using the same; A first pixel layer including a quantum dot formed on the substrate; And a second pixel layer including scattering particles formed on the first pixel layer has a laminated structure.

In the case of the preceding documents, it is described that the light efficiency reduction including the quantum dots and alkali-soluble resin is described, but it can be seen that the point of preventing the settling of the scattering material in the color filter pattern is not recognized.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Republic of Korea Patent Publication No. 10-2016-0060904 (2016.05.31.Dongwoo Fine Chem Co., Ltd.)

(Patent Document 2) Republic of Korea Patent Publication No. 10-2016-0091708 (December 2016. Dongwoo Fine-Chem Co., Ltd.)

The present invention has been made to solve the above problems, by including a specific alkali-soluble resin and scattering particles together, the scattering material in the color filter pattern does not settle, and excellent color filter without the problem of lowering brightness and poor light retention rate It aims at providing the photosensitive resin composition which can be manufactured.

In addition, an object of the present invention is to provide a color filter made of the self-luminous photosensitive resin composition and an image display device including the same.

The self-luminous photosensitive resin composition according to an embodiment of the present invention for achieving the above object comprises scattering particles and an alkali-soluble resin, the alkali-soluble resin has a weight average molecular weight of 3000 to 15000 in terms of polystyrene, acrylic equivalent of 300 To 2000 g / eq.

In addition, the present invention is characterized by a color filter made of the self-luminous photosensitive resin composition and an image display device including the same.

As described above, the self-luminous photosensitive resin composition according to the present invention includes scattering particles and scattering in a color filter pattern by containing an alkali soluble resin having a weight average molecular weight of 3000 to 15000 in terms of polystyrene and an acrylic equivalent of 300 to 2000 g / eq. It is possible to manufacture an excellent color filter without the problem of lowering luminance and poor light retention rate without the sieve settling.

FIG. 1 is a diagram illustrating sedimentation by measuring TiO ₂ sedimentation properties of a lower part of a pattern.

2 is a view showing that the sedimentation did not appear by measuring the TiO ₂ sedimentability of the lower part of the pattern.

The self-luminous photosensitive resin composition of the present invention comprises scattering particles and an alkali-soluble resin, wherein the alkali-soluble resin has a weight average molecular weight of 3000 to 15000 in terms of polystyrene, and an acrylic equivalent of 300 to 2000 g / eq.

Hereinafter, the self-luminous photosensitive resin composition will be described in detail.

Alkali soluble resin

Alkali-soluble resin contained in the self-luminous photosensitive resin composition of this invention makes the non-exposed part of the photosensitive resin layer alkali-soluble, and can remove it, and serves to remain an exposure area | region. In addition, the alkali-soluble resin of the present invention has a polymerizable unsaturated bond to effectively form a protective layer around the surface of the quantum dot in the exposure step, to maintain the high brightness by excluding the effects of high temperature and oxygen radicals in the POB process as much as possible Can be.

The alkali-soluble resin preferably has a weight average molecular weight of 3000 to 15000 in terms of polystyrene, and when the weight average molecular weight of the alkali-soluble resin is in the above range, it is possible to reduce the settling properties of the scattering body.

In addition, the alkali-soluble resin is preferably an acrylic equivalent of 300 to 2000 g / eq, more preferably 500 to 1000 g / eq. When the alkali-soluble resin acrylic equivalent is within the above range, it is possible to prevent the quenching phenomenon during the color filter process. On the other hand, when the acrylic equivalent of the alkali-soluble resin exceeds the above range, the ability to effectively protect the quantum dot is insufficient, and it is not suitable because it is difficult to prevent the scattering body from settling, and when the acrylic equivalent is less than the above range, the luminous efficiency And it is good in the sedimentation surface, but there is a problem that does not dissolve during development, peeling.

In particular, the alkali-soluble resin according to the present invention by adjusting the weight average molecular weight and the acrylic equivalent as described above, evenly distributed composition in the pattern of the self-luminous photosensitive resin composition, so that light scattering effectively occurs, preventing the problem of scattering body settling In addition, there is an effect that can prevent the lowering of the luminance and poor light retention.

The acid value of the alkali-soluble resin may be in the range of 30 to 150mgKOH / g. The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the acrylic polymer and is involved in solubility. When the acid value of the alkali-soluble resin is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development, thereby improving the film remaining ratio. There is this. If the acid value of the alkali-soluble resin is less than the above range, the solubility in the alkaline developer is low and there is a risk of leaving a residue on the substrate, if the acid value exceeds the above range may be more likely to break the pattern.

It is preferable that it is 1.0-6.0, and, as for the molecular weight distribution of the said alkali-soluble resin, it is more preferable that it is 1.5-4.0. Developability is excellent in the molecular weight distribution of the said alkali-soluble resin being in the said range.

In the case of the self-luminous photosensitive resin composition including the alkali-soluble resin satisfying the above conditions, not only the protective layer is effectively formed on the surface of the quantum dot during the exposure step, but also the scattering body does not settle under the pattern as the degree of curing in the matrix is increased. Help to distribute the quantum dots evenly.

The alkali-soluble resin is not particularly limited as long as it has a polymerizable unsaturated bond, but specific examples of the monomer that can be used include 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and 2-methoxy- 3-propy-2-noyloxy-propyl) -2-methyl-2-propinoate, (2-oxydanyl-3-propy-2-noyloxy-propyl) -2-butinoate, 1,3- Propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,4-phenyline di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, 2-propinoyloxymethyl-2-propinoate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1 , 6-hectanediol di (meth) acrylate, 1,12-dodecanediol di (meth) arc Relate, trimethylloyl propane tri (meth) acrylate, bisphenol A di (meth) acrylate, a diurethane di (meth) acrylate, neopentyl glycol diacrylate, etc. are mentioned.

In particular, when the alkali-soluble resin includes a repeating unit represented by the following formula (1), it is possible to more effectively control the sedimentation.

[Formula 1]

An alkyloxy group or C ₁ to C ₃₀ alkyloxycarbonylaminoalkyl group, the alkyl group, alkyloxy group or alkyloxycarbonylaminoalkyl group is C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxy group, an aralkyl group of C ₁ to C _20, C ₆ to C ₂₀ aryl group, C ₁ to an acyloxy group of C _20, C ₁ to C ₂₀ acyl group, C ₁ to C ₂₀ alkoxycarbonyl group, C ₆ to the C ₂₀ arylcarbonyl group, C ₁ to C ₂₀ dialkylamino group, C ₁ to C ₂₀ alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfuryl group, Import of C ₁ to C ₂₀ alkylthio, trimethylsilyl group, and a trifluoromethyl group, a carboxyl group, a thienyl group, a mole Poly group, or Dimorpholino Reno carbonyl groups can be substituted,

R ₃ is represented by -R ₅ -R ₆ -COOH,

R ₅ is -OC (= O)-,

R ₆ is C ₁ to C ₃₀ alkylene, C ₂ to C ₃₀ alkenylene, -R ₇ -C (= 0) -R _8- , -R ₉ -C (= 0) -OR ₁₀ -,- R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N- (R ₁₄ R ₁₅ )-, -RC (= O) -NR ₁₆ -C (= O) R _17- , -R _18- C (= O) -N (R ₁₉ ) (C (= O))-R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O)- R _24- , -CH = CH-OCR _25- , -CH = CH-OC (= O) -N (R ₂₆ ) (R ₂₇ )-, an arylene group of C ₆ to C ₃₀ , C ₅ to C ₃₀ A heteroarylene group, a C ₆ to C ₃₀ cycloalkylene group,

R ₇ to R ₂₇ are the same as or different from each other, and are each independently hydrogen, C ₁ to C ₃₀ alkylene, C ₆ to C ₃₀ arylene group, or C ₆ to C ₃₀ cycloalkylene group,

R ₄ is a C ₁ to C ₂₀ alkyl (meth) acrylate group.

In this case, R ₂ is preferably a C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkyloxy group, or C ₁ to C ₂₀ alkyloxycarbonylaminoalkyl group, methyl, ethyl, propylene, butyl Group, ethyleneoxy group, diethyleneoxy group, triethyleneoxy group, ethyloxycarbonylaminoethyl group are more preferable, and these are functional groups of a trivalent form.

In this case, the R ₄ is an alkyl (meth) acrylate group is preferable, and an acrylate or methylacrylate group of C ₁ to C ₁₂ is more preferable.

In this case, R ₆ is C ₁ to C ₂₀ alkylene, C ₂ to C ₂₀ alkenylene, C ₆ to C ₂₀ arylene group, or C ₆ to C ₂₀ cycloalkylene group, these are substituted with a carboxyl group or It is preferred to be unsubstituted. R ₆ is a methylene group, an ethylene group, a propylene group, isopropylene, pentylene, ethenylene, 2-methyl-ethenylene, dimethylpropylene group, butylene group, cyclohexylene group, 4-cyclohexynyl group, It is more preferable that they are a bicyclo [4.4.0] decylene group, a bicyclo [2.2.1] -2-heptinylene group, a phenylene group, a carboxyphenylene, or a naphthalenyl group.

As used herein, an "alkyl group" includes straight or branched forms, for example methyl, ethyl, n-propyl, i-propylene, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl , n-octyl, n-decyl and the like, alkylene means a divalent form of alkyl.

As used herein, an "aryl group" includes phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, and the like, and arylene means a divalent form of aryl.

As used herein, a "cycloalkyl group" refers to cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, bornyl, norbornyl and norbornenyl and their condensed forms of dicyclopentyl, dicyclohexyl, dicycloheptyl , Diadamantyl, dibornyl, dinorbornyl or dinorbornenyl, and the like, cycloalkylene means a divalent form of cycloalkyl.

The alkali-soluble resin may be a homopolymer, or may be used in the form of a copolymer with another unsaturated monomer or a blend with a polymer polymerized with another unsaturated monomer. In this case, the copolymer may be in the form of an alternating copolymer, a random copolymer or a block copolymer, and is not particularly limited in the present invention.

The kind of the copolymerizable monomer is not particularly limited, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and amino. Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as ethyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Containing alicyclic substituents such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate and tricyclodecyl methacrylate Unsaturated carboxylic ester compounds; Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Vinyl cyanide compounds such as carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, (meth) acrylonitrile and? -Chloroacrylonitrile; Maleimide compounds, such as N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide, etc. are mentioned.

The content of the alkali-soluble resin is preferably contained in 5 to 80% by weight, more preferably in 10 to 70% by weight relative to 100% by weight of the self-luminous photosensitive resin composition. When the content of the alkali-soluble resin is included within the above range, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is improved.

Scattering particles

The scattering particles are used to increase the light efficiency of the color filter. The light irradiated from the light source is incident on the color filter at a critical angle, and the spontaneous emission light spontaneously emitted by the incident light or the quantum dots meets the scattering particles and increases the light emission intensity due to the increase in the light path. Increasing the light efficiency. The scattering particles may be any conventional inorganic material, preferably a metal oxide.

The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, An oxide comprising one metal selected from the group consisting of Ce, Ta, In and combinations thereof is possible.

Specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, MgO and One selected from the group consisting of a combination of these is possible. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

The scattering particles limit the average particle diameter and the content in the entire composition so as to sufficiently improve the emission intensity of the color filter. The scattering particles preferably have an average particle diameter of 10 to 1000 nm, and have an average particle diameter of 50 to 500 nm. It is more preferable. If the scattering particle size is too small, a sufficient scattering effect of the light emitted from the quantum dots cannot be expected, and on the contrary, if the scattering particle size is too large, the surface of the self-luminous layer having a uniform quality or submerging cannot be obtained.

In addition, the scattering particles may be used from 0.1 to 50% by weight within 100% by weight of the self-luminous photosensitive resin composition, preferably from 0.5 to 30% by weight. If the content of the scattering particles is less than the above range can not secure the luminescence intensity to be obtained, if it exceeds the above range, the effect of further increasing the luminescence intensity is insufficient, and the stability of the composition may occur.

The self-luminous photosensitive resin composition according to the present invention includes a scattering particle which is a metal oxide in the alkali-soluble resin, so that the scattering particle can be prevented from settling over time.

Quantum dots

The photosensitive resin composition of this invention contains a quantum dot particle. Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are semiconducting.

When the quantum dot reaches the excited state from the outside, the quantum dot emits energy according to the corresponding energy band gap.

The photosensitive resin composition of this invention contains such a quantum dot particle, and the color filter manufactured from this can emit light (photoluminescence) by light irradiation.

In a typical image display apparatus including a color filter, white light is transmitted through the color filter to implement color. In this process, a part of the light is absorbed by the color filter, thereby degrading light efficiency.

However, in the case of including the color filter made of the photosensitive resin composition of the present invention, since the color filter emits light by the light of the light source, more excellent light efficiency can be realized. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.

The quantum dot particle is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation by light, for example, a group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; And combinations thereof may be selected from the group. These can be used individually or in mixture of 2 or more types. The II-VI semiconductor compound may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. The group III-V semiconductor compound Binary elements selected from the group consisting of GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds 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 an elemental compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The group IV-VI semiconductor compound is a binary element selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and an elemental compound selected from the group consisting of a mixture thereof, and the group IV element or the compound comprising the same is Si, Ge, and a mixture thereof. An element compound selected from; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The quantum dot particles are homogeneous single structure; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.

In the dual structure of the core-shell, the material forming each core and shell may be made of the above-mentioned different semiconductor compounds. For example, the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

As the colored photosensitive resin composition used in the manufacture of conventional color filters includes colorants of red, green, and blue for color realization, photoluminescence quantum dot particles may be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. In addition, the quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.

The quantum dot particles may 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. As the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant, thereby controlling the growth of the crystal. Therefore, organic metal chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE) It is easier and cheaper to control nanoparticle growth than vapor deposition such as epitaxy.

The content of the quantum dot particles according to the present invention is not particularly limited. For example, the content of the quantum dot particles is preferably included in 3 to 80% by weight of the total weight of the solid content of the self-luminous photosensitive resin composition, and more preferably included in 5 to 70% by weight. desirable. If the content of the quantum dot is less than the above range, the luminous efficiency may be insignificant, and if the content of the quantum dot exceeds the above range, there is a problem that it is difficult to form a pixel pattern due to the lack of a relatively different content of composition.

Photopolymerizable  compound

The photopolymerizable compound contained in the quantum dot photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound is preferably contained 5 to 70% by weight, more preferably 7 to 65% by weight relative to the total weight percent solids of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included in the above range, the intensity or smoothness of the pixel portion may be good.

Photopolymerization Initiator

Although the photoinitiator which concerns on this invention is not restrict | limited, It is more preferable to include 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound.

The self-luminous photosensitive resin composition containing the photopolymerization initiator is highly sensitive, and the pixel pixels formed using the composition may have good strength and patternability of the pixel portion.

Moreover, when a photoinitiation adjuvant is used together with the said photoinitiator, since the self-luminous photosensitive resin composition containing them becomes more sensitive and productivity at the time of forming a color filter using this composition is preferable, it is preferable.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl 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] propane- 1-one oligomer etc. are mentioned. Moreover, the compound represented by following formula (2) is mentioned.

[Formula 2]

In Formula 2, R ₂₈ to R ₃₁ are each independently the same as or different from each other, and are substituted with a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an unsubstituted phenyl group and an alkyl group having 1 to 12 carbon atoms. Or an unsubstituted benzyl group or a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 2 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole can be preferably used.

As said oxime compound, the compound of the following general formula is mentioned.

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

In addition, in the present invention, as the photopolymerization initiator that can be used in combination with the photopolymerization initiator, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and the like may be preferably used.

Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoic acid. , 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4 ' Aromatic amine compounds, such as -bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiator of the present invention is preferably included in 0.1 to 20% by weight, more preferably in 1 to 10% by weight of the total weight percent solids of the self-luminous photosensitive resin composition. When the content of the photopolymerization initiator is included in the above range, the self-luminous photosensitive resin composition may be highly sensitive, so that the intensity of the pixel portion or the smoothness on the surface of the pixel portion may be good.

In addition, the photopolymerization initiation aid of the present invention is preferably included in 0.1 to 2% by weight, more preferably in 1 to 10% by weight of the total weight percent solids of the self-luminous photosensitive resin composition. When the amount of the photopolymerization initiation aid used is in the above range, the sensitivity efficiency of the self-luminous photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition can be improved.

solvent

The solvent according to the present invention is not particularly limited and may be an organic solvent commonly used in the art.

Specific examples 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; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl 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 glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters such as? -Butyrolactone; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

The content of the solvent according to the present invention is not particularly limited, for example, it is preferably included in 60 to 90% by weight of the total weight percent of the photosensitive resin composition, it is preferably included in 70 to 85% by weight. When the content of the solvent is within the above range may be good coating properties.

<Color filter>

In addition, the present invention provides a color filter made of the photosensitive resin composition.

When the color filter of the present invention is applied to an image display device, since the light is emitted by the light of the display device light source, it is possible to implement more excellent light efficiency. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.

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 positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer including the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern.

The pattern layer formed of the photosensitive resin composition may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In 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 emission light of the light source is not particularly limited when applied to the image display device, but a light source that emits blue light may be used in view of better color reproducibility.

According to another embodiment of the present invention, the pattern layer may include only the pattern layer of two colors of red pattern layer, green pattern layer, and blue pattern layer. In such a case, the pattern layer further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included can be used. For example, when including a red pattern layer and a green pattern layer, the light source which emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light as it is transmitted.

The color filter including the substrate and the pattern layer as described above may further include a partition formed between each pattern, and may further include a black matrix. In addition, a protective film formed on the pattern layer of the color filter may be further included.

<Image display device>

In addition, the present invention provides an image display device including the color filter.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

The image display apparatus of the present invention may include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In such a case, the emission light of the light source is not particularly limited when applied to the image display device, but in view of better color reproducibility, a light source that emits blue light may be preferably used.

According to another embodiment of the present invention, the image display device of the present invention may include a color filter including only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer. In such a case, the color filter further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included can be used. For example, when including a red pattern layer and a green pattern layer, the light source which emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light as it is transmitted.

The image display device of the present invention is excellent in light efficiency, exhibits high luminance, is excellent in color reproducibility, and has a wide viewing angle.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production Example  One. CdSe (core)/ ZnS Synthesis of Photoluminescent Green Quantum Dot Particle A with (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 (1-Octadecene) (20 mL) and heated to 150 ° C. for reaction. . Thereafter, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr to remove acetic acid produced by substitution of oleic acid with zinc. Then, 310 ° C. heat was applied to obtain a transparent mixture, which was then maintained at 310 ° C. for 20 minutes, and 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. And S solution was rapidly injected into the reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C. for 5 minutes and then stopped using an ice bath. Then, precipitated with ethanol to separate the quantum dots using a centrifuge and the excess impurities washed with chloroform and ethanol, stabilized with oleic acid, the core particle diameter and the sum of the shell thickness of 3 to 5nm A quantum dot particle A having a CdSe (core) / ZnS (shell) structure in which they were distributed was obtained.

Production Example  2- 1.alkali  Synthesis of Soluble Resin (E-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 50 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether, and then stir-mixed the monomer dropping lot 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto, followed by stirring and mixing to prepare a dropping chain of a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90, and after 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours. Then, the solid content was cooled to room temperature and the solid content was 29.1 wt% and the weight average molecular weight 10,000 was 10,000 mgKOH / g. Phosphorus resin E-1 was obtained.

Production Example  2-2: Synthesis of Alkali-Soluble Resin (E-2)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 50 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether, and then stir-mixed the monomer dropping lot 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto, followed by stirring and mixing to prepare a dropping chain of a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started. Subsequently, 5 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were added to the flask to react at 110 to 8 hours. Then, resin E-2 whose solid content was 29.1 weight%, the weight average molecular weight 10,000, the acid value was 130 mgKOH / g, and the acrylic equivalent was 4300 g / eq was cooled to room temperature after that.

Production Example  2- 3: alkaline  Synthesis of Soluble Resin (E-3)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 50 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether, and then stir-mixed the monomer dropping lot 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto, followed by stirring and mixing to prepare a dropping chain of a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started. Subsequently, 15 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. The reaction was continued and then cooled to room temperature to obtain Resin E-3 having a solid content of 29.1 wt%, a weight average molecular weight of 10,000, an acid value of 110 mgKOH / g, and an acrylic equivalent of 1450 g / eq.

Production Example  2- 4: alkaline  Synthesis of Soluble Resin (E-4)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 50 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether, and then stir-mixed the monomer dropping lot 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto, followed by stirring and mixing to prepare a dropping chain of a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started. Subsequently, 30 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. The reaction was continued, and then cooled to room temperature to obtain Resin E-4 having a solid content of 29.1 wt%, a weight average molecular weight of 10,000, an acid value of 85 mgKOH / g, and an acrylic equivalent of 725 g / eq.

Production Example  2- 5: alkaline  Synthesis of Soluble Resin (E-5)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 35 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 55 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and 20 parts by weight of propylene glycol monomethyl ether were added, followed by stirring and mixing to add a monomer. Lots were prepared, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added, followed by stirring and mixing to prepare a lot of chain transfer agent dropping lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started. Subsequently, 50 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. The reaction was continued and then cooled to room temperature to obtain Resin E-5 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 60 mgKOH / g, and an acrylic equivalent of 435 g / eq.

Production Example  2- 6: alkali  Synthesis of Soluble Resin (E-6)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 35 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 55 parts by weight of acrylic acid, and meta-t- 2 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") and 20 parts by weight of propylene glycol monomethyl ether, and then stirred and mixed to add monomer Lots were prepared, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added, followed by stirring and mixing to prepare a lot of chain transfer agent dropping lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started. Subsequently, 50 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. Reaction was continued, and the resin E-6 of 29.1 weight% of solid content, the weight average molecular weight of 30,000, the acid value of 65 mgKOH / g, and the acrylic equivalent of 435 g / eq was obtained after cooling to room temperature after that.

Production Example  2-7. Synthesis of Alkali Soluble Resin (E-7)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide, 10 parts by weight of tricyclodecyl methacrylate, 50 parts by weight of acrylic acid, and meta-t- 4 parts by weight of butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether, and then stir-mixed the monomer dropping lot 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto, followed by stirring and mixing to prepare a dropping chain of a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was started. Subsequently, 30 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. The reaction was continued. Thereafter, the reaction solution temperature was lowered to room temperature, 6.0 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C for 6 hours. After cooling to room temperature, Resin E-7 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 85 mgKOH / g, and an acrylic equivalent of 720g / eq was obtained.

Example  1 to 8 and Comparative example  1 to 5: Self-luminescence  Preparation of Photosensitive Resin Composition

After mixing each component as shown in following Table 1, it diluted with propylene glycol monomethyl ether acetate so that total solid content might be 20 weight%, and fully stirred, and obtained the self-luminous photosensitive resin composition.

In this case, the polystyrene reduced weight average molecular weight and the acrylic equivalent of the total alkali-soluble resins included in the examples and the comparison are shown in Table 2 below.

Quantum dots Scattering particles Photopolymerizable compound Photopolymerization Initiator Alkali-soluble resin E-1 E-2 E-3 E-4 E-5 E-6 E-7 Example 1 30 5 30 5 - - 30 - - - - Example 2 30 5 30 5 - - - 30 - - - Example 3 30 5 30 5 - - - - 30 - - Example 4 30 5 30 5 - - - - - - 30 Example 5 30 5 30 5 5 - 25 - - - - Example 6 30 5 30 5 - 5 25 - - - - Example 7 30 5 30 5 - - 25 - - 5 - Example 8 30 5 30 5 - - 25 - - - 5 Comparative Example 1 30 5 30 5 30 - - - - - - Comparative Example 2 30 5 30 5 - 30 - - - - - Comparative Example 3 30 5 30 5 - - - - - 30 - Comparative Example 4 30 5 30 5 - - 5 - - 25 - Comparative Example 5 30 5 30 5 25 - 5 - - - - 1) Quantum dot A-1: CdSe (core) / ZnS (shell) structure of Preparation Example 1 A-12) Scattering particle: TiO2 (TR-88, manufactured by Huntsman) 3) Photopolymerizable compound: dipentaerythritol penta Acrylate amber monoester (carboxylic acid-containing 5-functional photopolymerizable compound) (TO-1382, manufactured by Dong-A Synthesis) 4) Photopolymerization initiator: Irgacure-907 (manufactured by BASF) 5) Alkali-soluble resin: Alkali-soluble resin of Preparation Example 2

Polystyrene equivalent weight average molecular weight Acrylic equivalent (g / eq) Example 1 10,000 1450 Example 2 10,000 725 Example 3 10,000 435 Example 4 10,000 720 Example 5 10,000 1740 Example 6 10,000 1630 Example 7 13,330 1044 Example 8 10,000 1240 Comparative Example 1 10,000 - Comparative Example 2 10,000 4300 Comparative Example 3 30,000 435 Comparative Example 4 26,670 429 Comparative Example 5 10,000 8700

Color filter Glass substrate ) Production Example

Color filters were prepared using the self-luminous photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 5. That is, each of the self-luminous 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 3 minutes to form a thin film. Subsequently, a test photomask having a transmissive pattern of 20 mm x 20 mm square and a line / space pattern of 1 µm to 100 µm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 µm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern. The film thickness of the self-luminous color pattern prepared above was 3.0 μm.

Intensity Measurement

The light-converted area was measured by a 365nm tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) on a pattern formed of a 20mm x 20mm square pattern among the color filters in which the self-luminous pixels were formed. 8 to 8 and Comparative Examples 1 to 5 measured the light intensity (Intensity) in the 550nm region using a Spectrum meter (manufactured by Ocean Optics). It can be determined that the higher the measured light intensity (Intensity) is to exhibit an excellent self-luminous characteristics, the emission intensity (Intensity) measurement results are shown in Table 3 below. In addition, the hard bake was carried out at 230 ° C. for 60 minutes, and the emission intensity before and after the hard bake was measured, and the level at which the luminous efficiency was maintained was confirmed.

TiO ₂ Sedimentation Measurement

Using the energy-dispersive X-ray spectroscopy (EDX) equipment, the color pattern substrate prepared above was used to check the distribution of titanium (Ti) elements in the substrate, and thereby the degree of TiO ₂ sedimentation under the pattern. This can be confirmed through Figs. 1 and 2.

<Evaluation Criteria>

◎: No TiO ₂ sedimentation.

(Circle): TiO ₂ sedimented only a part of area inside a pattern.

△: TiO ₂ settled to half level in the pattern

Ⅹ: TiO ₂ is completely settled under the pattern

Luminous intensity Luminous intensity retention Sedimentation strength Example 1 52654 51.2% ○ Example 2 51241 52.3% ○ Example 3 55246 53.6% ○ Example 4 60152 59.1% ◎ Example 5 57245 52.2% ○ Example 6 52476 54.1% ○ Example 7 52444 53.1% ○ Example 8 58658 56.9% ◎ Comparative Example 1 20124 20.3% Ⅹ Comparative Example 2 22101 22.5% Ⅹ Comparative Example 3 52330 52.8% △ Comparative Example 4 50079 50.9% △ Comparative Example 5 21285 21.1% △

As can be seen from Table 3, when using alkali-soluble resin having a double bond equivalent and molecular weight within the claims in Examples 1 to 8, not only the luminescence intensity and retention is high, but also the sedimentation resistance in the pattern is suppressed. You can see that you can. In particular, Example 4 and Example 8 using an alkali-soluble resin containing a monomer of the formula (1) it can be seen that the TiO ₂ sedimentation in the pattern can be completely controlled.

On the other hand, referring to Comparative Examples 1, 2, and 5, when the double bond equivalent is 2000 g / eq or more, it can be confirmed that TiO ₂ is precipitated at the bottom of the pattern as well as the luminescence intensity and retention is low. Referring to 4, when the weight average molecular weight is 15000 or more, the luminescence intensity and retention are maintained high, but it can be confirmed that sedimentation cannot be suppressed.

Claims (12)

Including scattering particles and alkali-soluble resin, The alkali-soluble resin is a self-luminous photosensitive resin composition, characterized in that the weight average molecular weight in terms of polystyrene is 3000 to 15000, and the acrylic equivalent is 300 to 2000 g / eq. The method of claim 1, The self-luminous photosensitive resin composition A self-luminous photosensitive resin composition further comprising at least one component selected from a quantum dot, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The method of claim 1, The alkali soluble resin is A self-luminous photosensitive resin composition comprising a repeating unit represented by Formula 1 below: [Formula 1]

(In Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is a C ₁ to C ₃₀ alkyl group, C ₁ to C ₃₀ alkyloxy group, or C ₁ to C ₃₀ alkyloxycarbonylaminoalkyl group, the alkyl group, alkyloxy group or alkyloxycarbonylaminoalkyl group C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ aralkyl group, C ₆ to C ₂₀ aryl group, C ₁ to C ₂₀ acyloxy group, C ₁ to C ₂₀ Acyl group, C ₁ to C ₂₀ alkoxycarbonyl group, C ₆ to C ₂₀ arylcarbonyl group, C ₁ to C ₂₀ dialkylamino group, C ₁ to C ₂₀ alkylamino group, halogen atom, cyano group, fu Aryl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfuryl group, C ₁ to C ₂₀ alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, or morpholinocarbono It can be substituted by a nil group, R ₃ is represented by -R ₅ -R ₆ -COOH, R ₅ is -OC (= O)-, R ₆ is C ₁ to C ₃₀ alkylene, C ₂ to C ₃₀ alkenylene, -R ₇ -C (= 0) -R _8- , -R ₉ -C (= 0) -OR ₁₀ -,- R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N- (R ₁₄ R ₁₅ )-, -RC (= O) -NR ₁₆ -C (= O) R _17- , -R _18- C (= O) -N (R ₁₉ ) (C (= O))-R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O)- R _24- , -CH = CH-OCR _25- , -CH = CH-OC (= O) -N (R ₂₆ ) (R ₂₇ )-, an arylene group of C ₆ to C ₃₀ , C ₅ to C ₃₀ A heteroarylene group, a C ₆ to C ₃₀ cycloalkylene group, R ₇ to R ₂₇ are the same as or different from each other, and are each independently hydrogen, C ₁ to C ₃₀ alkylene, C ₆ to C ₃₀ arylene group, or C ₆ to C ₃₀ cycloalkylene group, R ₄ is a C ₁ to C ₂₀ alkyl (meth) acrylate group). The method of claim 1, The alkali soluble resin is An acid value of 30 to 150 mgKOH / g, self-luminous photosensitive resin composition, characterized in that. The method of claim 1, The alkali soluble resin is The molecular weight distribution is 1.0 to 6.0, self-luminous photosensitive resin composition. The method of claim 1, The alkali soluble resin is To 100% by weight of the self-luminous photosensitive resin composition, A self-luminous photosensitive resin composition comprising 5 to 80% by weight. The method of claim 1, The scattering particles An average particle diameter is 10-1000 nm, The self-luminous photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The scattering particles An average particle diameter is 10-1000 nm, The self-luminous photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The scattering particles Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, Self-luminous photosensitive resin composition, characterized in that the metal oxide containing one metal selected from the group consisting of In and combinations thereof. The method of claim 9, The metal oxide is Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, A self-luminous photosensitive resin composition comprising one selected from the group consisting of MgO and combinations thereof. The color filter containing the hardened | cured material of the self-luminous photosensitive resin composition of any one of Claims 1-10. An image display apparatus comprising the color filter of claim 11.

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