TWI679269B - Quantum dot dispersion, self emission type photosensitive resin composition comprising the same, color filter and image display device manufactured using the same - Google Patents

Abstract

The present invention relates to a quantum dot dispersion and a self-luminous photosensitive resin composition containing the same, and a color filter and an image display device manufactured using the self-luminous photosensitive resin composition. More specifically, the present invention The quantum dot dispersion includes photoluminescent quantum dot particles, a dispersant, and a solvent, and the dispersant is a compound having a carboxylic acid and an unsaturated double bond in one molecule. In addition, the present invention is characterized by a color filter manufactured from a self-luminous photosensitive resin composition including the quantum dot dispersion and an image display device including the color filter.

Description

Quantum dot dispersion, self-luminous photosensitive resin composition containing the same, and color filter and image display device manufactured using the self-luminous photosensitive resin composition

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

The color filter is a thin film film type optical component that can extract three colors of red, green, and blue from white light to form a fine pixel unit. The size of one pixel is about tens to hundreds of microns. This type of color filter has a black matrix layer formed by a predetermined pattern on a transparent substrate in order to shield the boundary portion between each pixel, and a plurality of colors (typically red (R), green ( G) and blue (B) 3 primary colors). Generally speaking, a color filter can be manufactured by coating three or more colors on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, or a pigment dispersion method. Recently, pigments using a pigment-dispersed photosensitive resin have been used. Decentralized methods have become mainstream.

One of the methods for realizing a color filter is a pigment dispersion method in which a transparent substrate provided with a black matrix is coated with a colorant and an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, Photosensitive resin composition of solvent and other additives, After the pattern to be formed is exposed, the non-exposed parts are removed with a solvent, thermally cured, and a series of processes are repeated to form a colored film method, which is actively used in the manufacture of portable phones and notebook computers. , Monitor, TV, etc. LCD. In recent years, the actual situation is that for a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics are required, but also high color reproduction rate, high brightness, and high contrast are required. efficacy.

However, the color reproduction is realized by the light transmitted from the light source through the color filter, but in the process, a part of the light is absorbed by the color filter, so the light efficiency is reduced. In addition, there are pigment characteristics due to the color filter. And such fundamental limitation that makes perfect color reproduction insufficient.

As a solution to this problem, there is a method for manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots. The use of quantum dots can reduce the light emission waveform, and has high color realization capabilities that cannot be achieved by pigments, and thus has excellent brightness characteristics.

However, quantum dots have a problem that they become susceptible to oxidation due to oxygen in the air. Under normal circumstances, quantum dots are dispersed in non-polar solvents such as toluene and chloroform for storage and use. However, when such quantum dots dispersed in a non-polar solvent are used in a photosensitive resin composition, foreign matter is precipitated due to compatibility problems with the polar solvent in the photosensitive resin composition. The problem of reduced luminous characteristics. Therefore, in order to improve compatibility with a polar solvent-based photosensitive resin composition and maintain luminous efficiency of quantum dots, additional development is necessary.

Korean Patent Publication No. 10-2013-0000506 discloses a technology related to a display device including a light source and a display panel into which light emitted from the light source is incident, and the display panel includes a plurality of color conversion sections. The color conversion unit includes a plurality of wavelength conversion particles that convert the wavelength of the light, and a plurality of color filter particles that absorb light in a predetermined wavelength band in the light.

However, although the above-mentioned prior art is similar in terms of including quantum dots, The content of the photosensitive resin composition is not specifically described, and only a display device having a high color reproduction rate and brightness is disclosed. Therefore, additional development of the photosensitive resin composition is required.

Prior art literature Patent literature

Patent Document 1: Korean Patent Publication No. 10-2013-0000506

The present invention has been made in order to solve the problems as described above, and an object thereof is to provide a dispersant as a compound having a carboxylic acid and an unsaturated double bond in one molecule, thereby providing no decrease in light efficiency and occurrence of foreign matter precipitation. A quantum dot dispersion that can maintain luminous efficiency.

Another object of the present invention is to provide a color filter manufactured from a self-luminous photosensitive resin composition containing the quantum dot dispersion as described above, and an image display device including the color filter.

The quantum dot dispersion according to the present invention for achieving the above object includes photoluminescent quantum dot particles, a dispersant, and a solvent, and the dispersant is a compound having a carboxylic acid and an unsaturated double bond in one molecule.

In addition, the present invention is characterized by a color filter manufactured from a self-luminous photosensitive resin composition including the above-mentioned quantum dot dispersion, and an image display device including the color filter.

Since the quantum dot dispersion according to the present invention contains a dispersant having a carboxylic acid and an unsaturated double bond, foreign matter caused by precipitation is not generated. Therefore, it is possible to provide the formation based on unsaturated double bonds during the exposure process of the color filter manufacturing process A high-quality photosensitive resin composition that protects a film and has excellent light retention characteristics.

In addition, the present invention has a self-luminous type which can provide the quantum dot dispersion Effects of a color filter made of a photosensitive resin composition and an image display device including the color filter.

The quantum dot dispersion according to the present invention includes photoluminescent quantum dot particles, a dispersant, and a solvent, and the dispersant is a compound having a carboxylic acid and an unsaturated double bond in one molecule.

Hereinafter, the present invention will be described in detail.

<Quantum dot dispersion> Photoluminescence quantum dot particle

The quantum dot dispersion of the present invention includes photoluminescent quantum dot particles.

Quantum dots are nanometer-sized semiconductor materials. Atoms form molecules. Molecules form clusters of small molecules to form nano particles. Such nano particles are called quantum dots especially when they have semiconductor characteristics. Quantum dots, if they receive energy from the outside and become excited, will automatically release energy in accordance with the corresponding energy band gap.

The quantum dot dispersion of the present invention contains such photoluminescent quantum dot particles, and a color filter manufactured therefrom can emit light (photoluminescence) by irradiation of light.

The photoluminescent quantum dot particles involved in the present invention are not particularly limited as long as they are quantum dot particles that can emit light by the stimulation of light, and can be selected from, for example, group II-VI semiconductor compounds; group III-V semiconductor compounds; IV- Group VI semiconductor compounds; Group IV elements or compounds containing Group IV elements; and groups of combinations thereof. These can be used alone or in combination of two or more.

The above II-VI semiconductor compounds may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof. Compound; selected from CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and a mixture of three-element compounds selected from the group consisting of CdZnSe , Four-element compounds of the group consisting of CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. The above-mentioned group III-V semiconductor compounds can be selected from the group consisting of GaN and GaP , GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and a mixture of two-element compounds; selected from the group consisting of GaNP, GaAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and a mixture of three-element compounds; and selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, A group of four-element compounds consisting of a mixture of GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and the like, and the aforementioned Group IV-VI semiconductor compounds Selected from the group consisting of: two-element compounds selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, A three-element compound consisting of a mixture of SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and a four-element compound selected from a group consisting of a mixture of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof, the above-mentioned Group IV elements or the above-mentioned Group IV The compound of the element may be selected from the group consisting of: an elemental compound selected from the group consisting of a mixture of Si, Ge, and the like; and a two-element compound selected from the group consisting of a mixture of SiC, SiGe, and the like .

The quantum dot particles may be a homogeneous single structure; a dual structure such as a core-shell, a gradient structure, or the like; or a mixed structure thereof.

Core-shell (core-shell) dual structures that form cores and shells, respectively Can be formed from semiconductor compounds different from each other as mentioned above. For example, the core may include one or more substances 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 substances selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

The coloring photosensitive resin composition used in the manufacture of general color filters includes red, green, and blue coloring agents. In the same way, photoluminescent quantum dot particles can be classified into red quantum dot particles. , Green quantum dot particles and blue quantum dot particles, the quantum dot particles involved in the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.

Quantum dot particles can be synthesized by a wet chemical process, an organic metal chemical vapor deposition process, or a molecular beam epitaxy process. The wet chemical process is a method in which a precursor substance is added to an organic solvent to grow particles. During crystal growth, organic solvents naturally coordinate to the surface of the quantum dot crystals, and act as a dispersant to regulate the growth of crystals. Therefore, they are used in combination with metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy, etc. Compared with the vapor deposition method (MBE, molecular beam epitaxy), the growth of nano particles can be controlled by an easier and cheaper process.

The content of the photoluminescent quantum dot particles according to the present invention is not particularly limited, for example, it is preferably 10 to 90% by weight, and more preferably 15 to 80% by weight in the total weight of the solid content of the quantum dot dispersion. If the content of the photoluminescent quantum dot particles is less than 10% by weight, when used in a self-luminous photosensitive resin composition, the content of the dispersant is larger than the content of the quantum dots, which causes a problem in the photosensitive characteristics. If the content of the particles exceeds 90% by weight, the content of the dispersant that can be used is insufficient, and the dispersion of quantum dots may cause problems.

Dispersant

The dispersant is used to impart a de-aggregation effect to the quantum dots and to suppress the appearance of a phenomenon caused by a difference in polarity when used in a self-luminous photosensitive resin composition. It is used as a protective layer for the quantum dot during the manufacturing process.

According to the present invention, when a compound containing a carboxylic acid and an unsaturated double bond is used in the dispersant described above, dispersion of quantum dots is facilitated, and a quantum having excellent compatibility with a self-luminous photosensitive resin composition can be produced. Point dispersion.

In this case, examples of the compound containing a carboxylic acid and an unsaturated double bond include acrylics such as acrylic acid and methacrylic acid, dipentaerythritol pentaacrylate, succinic acid monoester (TO-1382, Toa Synthesis Corporation), and pentaerythritol. Triacrylate succinate monoester (TO-756, Toa Synthetic Corporation), dipentaerythritol pentaacrylate modified succinic acid (DPE6A-MS, Kyoei Corporation), pentaerythritol triacrylate succinic acid modified (PE3A-MS , Gongrong Company), dipentaerythritol pentaacrylate phthalate modification (DPE6A-MP, Gongrong company), pentaerythritol acrylate phthalate modification (PE3A-MP), The copolymer is a polymer compound obtained by introducing an unsaturated double bond group and polyaddition with a glycidyl methacrylate or the like.

The exemplified dispersant containing a carboxylic acid and an unsaturated double bond can be used alone or in combination of two or more kinds.

In addition to the above-mentioned compounds having a carboxylic acid and an unsaturated double bond, the dispersant according to the present invention may be used in combination with a resin-based dispersant to disperse a pigment. Examples of the resin-based pigment dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc., which are acrylic dispersants produced using a living control method. In addition, as other resin-based pigment dispersants, well-known resin-based pigment dispersants may be included, in particular, polycarboxylates represented by polyurethanes, polyacrylates, unsaturated polyamines, polycarboxylic acids, and polycarboxylic acids. (Partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxy-polycarboxylic acid-containing esters, and the like Modified products, or oily dispersants such as amidine or a salt thereof formed by the reaction of a polyester having a free carboxyl group with poly (lower alkyleneimine); such as (a Base) acrylic-styrene copolymer, (meth) propylene Water-soluble resins or polymer compounds of acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone; polyesters; modified polyacrylates ; Ethylene oxide / propylene oxide addition products and phosphate esters.

As a commercially available product of the above-mentioned resin-based pigment dispersant, examples of the cationic resin dispersant include the trade names of BYK (Chemie Corporation): DISPER BYK-160, DISPER BYK-161, DISPER BYK- 162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Trade names of BASF: EFKA-44, EFKA-46, EFKA -47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510 EFKA-4800; Trade names of Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Trade names of Chuanyan Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; trade names of Ajinomoto: AJISPER PB-821, AJISPER PB-822, AJISPER PB-823; trade names of Kyoeisha Chemical Company: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33 , FLORENE DOPA-44, etc.

The weight average molecular weight of the dispersant is 200 to 6,000, and more preferably 300 to 5,000. If the weight average molecular weight is less than the above range, it becomes difficult to maintain the light efficiency of the quantum dots. If the weight average molecular weight exceeds the above range, there is a problem that it is difficult to disperse the quantum dots.

Solvent

The solvent involved in the present invention is not particularly limited, and may be an organic solvent generally used in this technology.

Specific examples include non-polar solvents such as chloroform and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. alkyl Ethers; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl cellosolve B Acid esters, ethyl cellosolve acetates, and other ethylene glycol alkyl ether acetates; propylene glycol monomethyl ethers, such as propylene glycol alkyl ethers; propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate and other alkylene glycol alkyl ether acetates; methyl ethyl ketone, acetone, methyl Ketones such as methylpentyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; 3-ethyl Esters such as ethyl oxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; etc. These can be used alone or in combination of two or more.

The content of the solvent according to the present invention is not particularly limited as long as it can disperse the quantum dots and maintain compatibility with the photosensitive resin composition. For example, it is 5 to 600 masses based on 100 mass parts of the solid content of the quantum dots. Parts, more preferably in the range of 10 to 500 parts by mass. If the amount of the dispersant used exceeds 600 parts by mass based on the above-mentioned basis, the viscosity may sometimes become high. In the case of less than 5 parts by mass, the dispersion of the quantum dots is difficult, or compatibility problems may be caused.

<Self-light-emitting photosensitive resin composition>

The self-luminous photosensitive resin composition of the present invention includes the quantum dot dispersion, a photopolymerizable monomer, a photopolymerization initiator, an alkali-soluble resin, and a solvent, and can form a fine pattern with excellent light emission characteristics and pattern characteristics and high brightness.

The quantum dot dispersion and the solvent contained in the self-luminous photosensitive resin composition of the present invention are as described above in the description.

The photopolymerizable monomer contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include a monofunctional monomer, a difunctional monomer, Other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2- Hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like.

Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, bis (propylene ethoxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate and the like. Among them, it is preferred to use a difunctional or more polyfunctional monomer.

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention is not limited, but is one selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, and an oxime compound. The above compounds. The self-luminous photosensitive resin composition containing the above-mentioned photopolymerization initiator is highly sensitive, and a pixel formed by using the composition will improve the strength and patternability of the pixel portion. In addition, when a photopolymerization initiator is used in combination with a photopolymerization initiator, the self-luminous photosensitive resin composition containing the photopolymerization initiator is further highly sensitive, and productivity is improved when a color filter is formed by using the composition. Better.

The alkali-soluble resin contained in the self-luminous photosensitive resin composition of the present invention is obtained by polymerizing a substance containing an ethylenically unsaturated monomer having a carboxyl group. It is a component which imparts solubility to the alkaline developing solution used in the developing process process at the time of pattern formation.

The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and the like Anhydrides; mono (meth) acrylates such as ω-carboxy polycaprolactone mono (meth) acrylate, and polymers having carboxyl and hydroxyl groups at both ends, and the like are preferably acrylic acid and methacrylic acid. These can be used alone or in combination of two or more.

<Color filter>

When the color filter of the present invention is applied to an image display device, it emits light by the light of the light source of the display device, so that it can achieve more excellent light efficiency. In addition, since light having color is released, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, so that the viewing angle can also be improved.

The color filter includes a substrate and a pattern layer formed on the substrate.

Regarding the substrate, the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like, 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 containing the photosensitive resin composition of the present invention, and may be a layer formed by coating the photosensitive resin composition and exposing, developing, and thermal curing with 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. When illuminated by light, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

In such cases, when applied to an image display device, the light emitted from the light source is not particularly limited, but a light source that emits blue light may be used in terms of excellent color reproducibility.

According to another embodiment of the present invention, the pattern layer may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer further includes a transparent pattern layer that does not contain quantum dot particles.

In the case where the pattern layer has only two colors, a light source that emits light of a wavelength that does not include the remaining colors can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In such cases, the red quantum dots The electrons emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to display blue.

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

<Image display device>

The present invention also provides an image display device including the color filter.

The color filter of the present invention can be applied not only to ordinary liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.

The image display device 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 cases, when applied to an image display device, the light emitted from the light source is not particularly limited, but in terms of more excellent color reproducibility, a light source that emits blue light is preferably used.

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

In the case where the pattern layer has only two colors, a light source that emits light of a wavelength that does not include the remaining colors can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In such cases, red quantum dot particles emit red light, green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to show blue.

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

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified or changed by those skilled in the art within the scope of the present invention.

Manufacturing Example 1. Synthesis of Photoluminescence Green Quantum Dot Particles A with CdSe (Core) / ZnS (Shell) Structure

Add CdO (0.4mmol), zinc acetate (4mmol), oleic acid (5.5mL) and 1-octadecene (20mL) to the reactor, and heat It was allowed to react to 150 ° C. Then, in order to remove the acetic acid generated by replacing oleic acid with zinc, the above reaction was placed under a vacuum of 100 mTorr for 20 minutes. Then, heat was applied at 310 ° C to obtain a transparent mixture. After maintaining the mixture at 310 ° C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. The obtained Se and S solutions were quickly injected into a reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions. After the thus-obtained mixture was allowed to grow at 310 ° C for 5 minutes, the growth was interrupted using an ice bath. Then, it was precipitated with ethanol, and the quantum dots were separated using a centrifugal separator. The extraneous impurities were washed with chloroform and ethanol, and dried in a drying oven at 80 ° C. for 6 hours to obtain a nucleus distributed with oleic acid. Quantum dot powder A having a CdSe (core) / ZnS (shell) structure with a particle size and a shell thickness of 3 to 5 nm and the like.

Production Example 2-1: Synthesis of Dispersant (B1)

In a flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 100 parts by weight of propylene glycol monomethyl ether acetate, 100 parts by weight of propylene glycol monomethyl ether, 8 parts by weight of AIBN, 2- 21.4 parts by weight of ethylhexyl acrylate, 1.5 parts by weight of 4-methylstyrene, 46 parts by weight of glycidyl methacrylate, and 3 parts by weight of n-dodecyl mercaptan were purged with nitrogen. Then, the temperature of the reaction liquid was raised to 80 ° C while stirring, and the reaction was carried out for 4 hours.

Next, the temperature of the reaction solution was reduced to normal temperature, and the atmosphere of the flask was replaced with nitrogen. After air-forming, 0.2 parts by weight of triethylamine, 0.1 parts by weight of 4-methoxyphenol, and 23.3 parts by weight of acrylic acid were charged, and reacted at 100 ° C for 6 hours. Then, the temperature of the reaction liquid was lowered to normal temperature, 12.5 parts by weight of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours. The acid value of the solid content of the alkali-soluble resin thus synthesized was 69 mgKOH / g, and a dispersant (B1) having a weight average molecular weight (MW) of 2980 measured by GPC was obtained.

Production Examples 2-2 to 2-4: Synthesis of Dispersants (B2 to B4)

The content and ratio of the comonomer in the above Production Example 2-1 were fixed, and the content of AIBN was changed to 1 to 6 parts by weight to make the acid values the same, and the weight average molecular weights were 5,800 (dispersant B2) and 7,400 (dispersion, respectively). Agent B3), 9,800 (dispersant B4) dispersant (B2 ~ B4).

Production Example 3: Synthesis of alkali-soluble resin (D ')

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube was prepared. On the other hand, 35 parts by weight of N-benzyl cis butylene diimide and tricyclodecyl methacrylate 10 were charged. Parts by weight, 55 parts by weight of acrylic acid, 4 parts by weight of m-third butyl peroxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), propylene glycol mono After 20 parts by weight of methyl ether, the mixture was stirred and mixed to prepare a monomer dropping funnel. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added, and the mixture was stirred and mixed to prepare a chain transfer agent dropping funnel.

Then, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was replaced with air from nitrogen, and then the temperature of the flask was raised to 90 ° C while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. During the dropwise addition, each was maintained for 2 hours while maintaining the temperature at 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Then, the gas introduction tube was introduced to start mixing of oxygen / nitrogen = 5/95 (v / v). Bubbling of gas. Next, 50 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were put into the flask. The reaction was continued at 110 ° C for 8 hours, and then, it was cooled to room temperature, and at the same time, a solid content of 30.0% by weight and a weight average molecular weight were obtained. Alkali-soluble resin D 'having an acid value of 15,000, an acid value of 60 mgKOH / g, and an equivalent of propylene group of 435 g / eq.

In this case, the measurement methods of molecular weight, solid content, and acid value are as follows.

Molecular weight evaluation

The weight-average molecular weight (Mw) of each of the alkali-soluble resins produced as described above was measured using the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (connected in series)

Column temperature: 40 ° C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μL

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Calibration Standards: TSK Standard Polystyrene (Standard Polystyrene) F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Solid content

About 1 g of the polymer solution was weighed and put into an aluminum cup, and about 3 g of acetone was added to dissolve it, and then naturally dried at normal temperature. Then, a hot-air dryer (manufactured by espec Corporation, trade name: PHH-101) was used, dried at 160 ° C for 3 hours under vacuum, and then allowed to cool in a dryer to measure the weight. The solid content of the polymer solution was calculated from the weight reduction.

Acid value

Precisely weigh 3g of the resin solution, dissolve it in a mixed solvent of 90g of acetone / 10g of water, use thymol blue as an indicator, and use a 0.1N KOH aqueous solution as a titration solution. An automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd.) , Trade name: COM-555) Determine the acid value of the polymer solution, and determine the acid per 1 g of the solid content from the acid value of the solution and the solid content of the solution. value.

Manufacturing Example 4: Manufacturing of quantum dot dispersion

After mixing the components described in Tables 1 to 2 below, that is, quantum dots (A), dispersants (B), and solvents (C), mixed with 1.0 mm zirconia beads of the same volume, using a paint shaker DAS- 200 (Lau hemmer company), disperse for 3 hours at a rate of 600 cycles / minute to produce a quantum dot dispersion 4-1 to 4-15. Regarding Production Example 4-15 without dispersant, in order to match Production Example 4- The weight percentage of quantum dots from 1 to 4-14 is the same. It is manufactured by adding chloroform.

Example 1: Production of a self-luminous photosensitive resin composition

Photopolymerization initiators (B ') and photopolymerization monomers (C') other than the quantum dot dispersion (A ') among the components described in Tables 3 and 4 below as self-emitting photosensitive resin components After the alkali-soluble resin (D ') and the solvent (E') are mixed first, Production Examples 4-1 to 4-15 are introduced to produce Examples 1 to 8 and Comparative Examples 1 to 7.

Experimental Example 1: Dispersibility of quantum dot dispersion and compatibility evaluation with self-luminous photosensitive resin composition (1) Dispersion evaluation of quantum dot dispersion

Regarding the dispersibility of the manufactured quantum dot dispersion, the level of transparency of the dispersion liquid was visually observed, and when it was opaque, it could be judged as poor dispersion.

The dispersion results of Production Examples 4-1 to 15 are shown in Table 5.

(2) Evaluation of compatibility with self-luminous photosensitive resin composition

Similar to Examples 1 to 8 and Comparative Examples 1 to 7, the quantum dot dispersion and the photosensitive resin The presence or absence of foreign matter precipitated during the mixing of the ingredients is visually shown in Table 5.

Experimental example 2: Manufacturing and evaluation of color filters (1) Manufacturing of color filters

The self-luminous photosensitive resin composition produced in the above-mentioned Examples 1 to 8 and Comparative Examples 1 and 7 was used to produce a color filter.

That is, each of the above self-luminous photosensitive resin compositions was coated on a glass substrate by a spin coating method, then placed on a hot plate, and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Next, a test mask having a transmission pattern of a horizontal × 20 mm × 20 mm regular quadrangle and a line / gap pattern of 1 μm to 100 μm was placed on the film, and ultraviolet rays were irradiated at a distance of 100 μm from the test mask.

At this time, the ultraviolet light source was irradiated with an ultrahigh-pressure mercury lamp (trade name USH-250D) manufactured by Shiyo Electric Co., Ltd. under the atmosphere at an exposure amount (365 nm) of 200 mJ / cm ² without using a special optical filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution at pH 10.5 for 80 seconds for development. The glass plate to which the film was applied was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to produce a color filter pattern.

The thickness of the film of the self-luminous color filter pattern manufactured in the above was 5.0 μm.

(2) Measurement of luminous intensity

The area where the light was converted was measured using a 365nm tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT) in the pattern portion formed in a 20mm × 20mm regular quadrangle pattern among the color filters forming the self-emitting pixels. The light emission intensities of Examples 1 to 8 and Comparative Examples 1 to 7 were measured using a spectroscope (manufactured by Ocean Optics) in the 550 nm region.

It can be determined that the higher the measured luminous intensity is, the more excellent the self-luminescence characteristics are exhibited. The measurement results of the luminous intensity are shown in Table 5 below.

At this time, the color filter was subjected to hard baking at 230 ° C for 60 minutes, and the hard baking was measured. The luminous intensity before and after confirms the level of maintaining luminous efficiency. Table 5 shows the luminous intensity maintaining rate.

With reference to Table 5 above, it can be seen that the dispersion characteristics of quantum dots in Examples 1 to 8 in which quantum dot dispersions are manufactured using the dispersant having a carboxylic acid and an unsaturated double bond having a weight average molecular weight of 300 to 5,000 according to the present invention are used. It has excellent compatibility with the photosensitive resin composition, excellent light emission characteristics and light retention of a color filter using the photosensitive resin composition.

However, as in Comparative Examples 5 and 6, when the molecular weight of the dispersant is 300 or less, although the dispersion characteristics of the quantum dots are good, the compatibility and light emitting characteristics with the photosensitive resin composition are poor, as in Comparative Examples 1 and 2. When the molecular weight of the dispersant is 5,000 or more, sufficient dispersion characteristics of the quantum dots cannot be obtained. Further, in Comparative Example 3 in which a urethane-based dispersant was used, a result was obtained in which the dispersibility of the quantum dots and the compatibility with the photosensitive resin composition were excellent, but the light emitting characteristics were very weak. In addition, in the case of Comparative Example 4 to which a propylene-based dispersant was applied and Comparative Example 7 to which a dispersant was not applied, the Since the precipitation phenomenon occurs during mixing of the resin composition, the results of poor light emission characteristics can be confirmed.

Claims (7)

A self-luminous photosensitive resin composition includes a quantum dot dispersion, a photopolymerization monomer, a photopolymerization initiator, an alkali-soluble resin, and a solvent, and does not contain a hydrocarbon-based solvent; wherein the quantum dot dispersion includes a photoluminescent quantum Dot particles, a dispersant, and a solvent. The dispersant is a compound having a carboxylic acid and an unsaturated double bond in one molecule. For example, the self-luminous photosensitive resin composition of claim 1, wherein the weight average molecular weight of the dispersant is 300 to 5,000. The self-luminous photosensitive resin composition according to claim 1, wherein the photoluminescent quantum dot particles are red quantum dot particles, green quantum dot particles, or blue quantum dot particles. For example, the self-luminous photosensitive resin composition of claim 1, wherein the content of the photoluminescent quantum dot particles is 100 parts by mass, and the dispersant is 10 to 500 parts by mass. The self-luminous photosensitive resin composition according to claim 1, wherein the compound having a carboxylic acid and an unsaturated double bond is selected from the group consisting of acrylic acid, methacrylic acid, dipentaerythritol pentaacrylate succinate monoester, Pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaerythritol phthalate modified product, pentaerythritol acrylate phthalate A modified product and a polymer compound obtained by addition polymerization of glycidyl methacrylate to introduce an unsaturated double bond group into a copolymer containing acrylic acid or methacrylic acid. A color filter made of a self-luminous photosensitive resin composition according to any one of claims 1 to 5. An image display device includes a color filter as claimed in claim 6.