KR20210021664A - New quantum dot ligand - Google Patents
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 61
- 239000003446 ligand Substances 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 17
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 abstract description 18
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 28
- 125000003396 thiol group Chemical group [H]S* 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 disulfide compound Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/30—Monomers containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/04—Luminescent, e.g. electroluminescent, chemiluminescent materials containing natural or artificial radioactive elements or unspecified radioactive elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/015—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on semiconductor elements having potential barriers, e.g. having a PN or PIN junction
- G02F1/017—Structures with periodic or quasi periodic potential variation, e.g. superlattices, quantum wells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/015—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on semiconductor elements having potential barriers, e.g. having a PN or PIN junction
- G02F1/017—Structures with periodic or quasi periodic potential variation, e.g. superlattices, quantum wells
- G02F1/01791—Quantum boxes or quantum dots
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
Description
본 발명은 양자점의 표면개질은 통한 양자점의 분산성 및 안정성을 향상시키기 위한 양자점 표면개질용 리간드 화합물 및 해당 리간드가 코팅된 양자점 및 해당 양자점을 함유하는 감광성 수지 조성물 및 해당 조성물을 이용하여 제조된 컬러필터에 관한 것이다.The present invention is to improve the dispersibility and stability of the quantum dot through the surface modification of the quantum dot, a ligand compound for modifying the surface of a quantum dot, a quantum dot coated with the ligand, a photosensitive resin composition containing the quantum dot, and a color prepared using the composition It's about the filter.
일반적으로 디스플레이에 적용하는 컬러필터는 감광성 레지스트 조성을 사용하여 포토마스크를 적용한 노광 공정을 통해 원하는 패턴을 형성하고, 현상 공정을 통해 비노광부를 용해시켜 제거하는 패터닝 공정을 통해 컬러 필터를 형성한다. 컬러필터용 소재는 알칼리 가용성이며 높은 감도, 기판에 대한 부착력, 내화학성, 내열성 등이 요구된다. 그런데 통상적으로 노광 공정만으로 경화반응이 충분하지 못하기 때문에 요구되는 특성들을 얻기 위해서는 200℃ 이상의 고온에서 일정시간 열경화 시켜주는 단계가 필요하다. 따라서 전자종이, OLED 등 저온 공정이 필요한 응용에는 한계가 있다.한편, 전자종이, OLED 등 비교적 저온 공정 적용이 필요한 컬러 필터용 감광성 수지 조성물을 개발하기 위해, 조성물 내에 추가적인 화합물, 예컨대 에폭시드 및 과산화물 등을 첨가하여 부족한 경화특성을 보완하려는 노력이 있었으나, 경화도가 충분하지 않아, 신뢰성이 낮다는 문제점이 있다.In general, a color filter applied to a display forms a desired pattern through an exposure process in which a photomask is applied using a photosensitive resist composition, and a color filter is formed through a patterning process in which an unexposed part is dissolved and removed through a development process. The color filter material is alkali-soluble and requires high sensitivity, adhesion to the substrate, chemical resistance, and heat resistance. However, since the curing reaction is not normally sufficient only by the exposure process, a step of thermally curing at a high temperature of 200°C or higher for a certain period of time is required to obtain the required properties. Therefore, there is a limit to applications requiring low-temperature processing such as e-paper and OLED. Meanwhile, in order to develop a photosensitive resin composition for color filters that require relatively low-temperature processing such as electronic paper and OLED, additional compounds such as epoxides and peroxides in the composition are developed. Efforts have been made to compensate for the insufficient curing characteristics by adding, but there is a problem in that the degree of curing is insufficient and reliability is low.
상기 문제점은 안료 또는 염료 등의 색재료가 광중합 개시제와 광에너지를 경쟁적으로 흡수하기 때문에 나타나는 현상이며, 또한 안료 및 염료가 생성된 라디칼을 제거하는 작용을 하기 때문에 충분한 개시효율을 얻기 어렵고, 따라서 광중합성 단량체의 경화율이 색재료를 사용하지 않은 경우보다 감소하게 되게 되는 것이다.The above problem is a phenomenon that occurs because color materials such as pigments or dyes absorb light energy competitively with the photopolymerization initiator, and it is difficult to obtain sufficient initiation efficiency because the pigments and dyes act to remove the generated radicals. The curing rate of the synthetic monomer decreases compared to the case where no color material is used.
따라서, 기존의 염료 혹은 안료 등의 색재료 대신 다른 물질을 사용함으로써 내화학성, 내열성 등의 신뢰성을 현저히 향상시킬 수 있는, 감광성 수지 조성물을 개발하려는 노력이 계속되고 있다.일 구현예는 컬러필터 제조 공정을 거친 후에도 높은 광변환율을 유지하는 양자점 함유 감광성 수지 조성물을 제공하기 위한 것이다.Accordingly, efforts have been made to develop a photosensitive resin composition that can significantly improve reliability such as chemical resistance and heat resistance by using other materials instead of color materials such as dyes or pigments. It is to provide a photosensitive resin composition containing quantum dots that maintains a high light conversion rate even after passing through the process.
다른 일 구현예는 컬러필터 등 디스플레이 공정에 유리한 용매에 분산 가능한 표면 개질된 양자점 제조방법을 제공하기 위한 것이다. Another embodiment is to provide a method for manufacturing a surface-modified quantum dot capable of dispersing in a solvent advantageous for a display process such as a color filter.
또 다른 일 구현예는 Another embodiment is
상기 감광성 수지 조성물을 이용하여 제조된 컬러필터를 제공하기 위한 것이다.노광, 현상, 경화 등의 공정을 포함하는 컬러필터 제조 공정에서 사용되는 용매에 분산이 가능하도록 표면 개질된 양자점을 사용하여, 감광성 수지 조성물 내 양자점의 절대 양자효율 저하를 최소화하여, 높은 광변환율을 유지하는 것을 기술적 과제로 한다.It is to provide a color filter manufactured using the photosensitive resin composition. By using quantum dots whose surface has been modified so that they can be dispersed in a solvent used in a color filter manufacturing process including processes such as exposure, development, and curing, It is a technical task to maintain a high light conversion rate by minimizing the reduction in absolute quantum efficiency of the quantum dots in the resin composition.
또한, 표면개질된 양자점이 노광공정에서 표면에 경화피막이 형성되어, 신뢰성의 향상시키는 것을 기술적 과제로 한다.In addition, a cured film is formed on the surface of the surface-modified quantum dots in the exposure process, making it a technical task to improve reliability.
1. 본 발명은 하기 화학식 1의 화합물을 제공한다.One. The present invention provides a compound represented by the following formula (1).
[화학식 1] [Formula 1]
n은 0~10의 정수이고, X는 직접연결, C1~C10의 지방족탄화수소,페닐, 벤질이고, Y는 CH2 또는 C=O이다.n is an integer from 0 to 10, X is a direct link, C1 to C10 aliphatic hydrocarbon, phenyl, benzyl, and Y is CH2 or C=O.
2. 본 발명은 상기 1의 화합물이 구체적으로 하기 화합물군 A중에서 선택되어지는 화합물을 제공한다.2. The present invention provides a compound in which the compound of 1 is specifically selected from the following compound group A.
<화합물군 A><Compound group A>
3. 본 발명은 하기 반응식 1로 대표되는 반응에 의해서 제조되는 상기 청구항 1~2의 화합물을 제공한다.3. The present invention provides the compounds of claims 1 to 2 prepared by a reaction represented by the following Scheme 1.
<반응식 1> 디설파이드의 환원반응 <Reaction Scheme 1> Reduction of disulfide
[화학식 2] [화학식 1] [Formula 2] [Formula 1]
4. 본 발명은 상기 1~2의 화합물이 피복된 양자점을 제공한다.4. The present invention provides a quantum dot coated with the compounds of 1 to 2.
5. 본 발명은 상기 4의 양자점을 포함하는 컬러레지스트 조성물을 제공한다.5. The present invention provides a color resist composition comprising the quantum dots of 4.
6. 본 발명은 상기 5의 컬러제지스트 조성물을 이용하여 제조되는 디스플레이를 제공한다.6. The present invention provides a display manufactured by using the color paper composition of the 5 above.
노광, 현상, 경화 등의 공정을 포함하는 컬러필터 제조 공정에서 사용되는 용매에 분산이 가능하도록 표면 개질된 양자점을 사용하여, 감광성 수지 조성물 내 양자점의 절대 양자효율 저하를 최소화하여, 높은 광변환율을 유지할 수 있다.By using quantum dots that have been surface-modified so that they can be dispersed in a solvent used in the color filter manufacturing process including processes such as exposure, development, and curing, the reduction in absolute quantum efficiency of the quantum dots in the photosensitive resin composition is minimized, resulting in a high light conversion rate. I can keep it.
또한, 표면개질된 양자점이 노광공정에서 표면에 경화피막이 형성되어, 신뢰성의 향상을 확보할수 있다.In addition, since the surface-modified quantum dot is formed with a cured film on the surface in the exposure process, it is possible to secure an improvement in reliability.
일 구현예에 따른 감광성 수지 조성물은 (A) 바인더 수지; (B) 광중합성 단량체; (C) 광중합 개시제; (D) 말단한쪽에 하나의 티올기를 가지고, 다른 말단 한쪽에 라디컬경화성 비닐기를 가지며, 양 말단을 연결하는 링커부분이 에틸렌옥사이드기를 가지는 화합물로 표면 개질된 양자점; 및 (E) 용매를 포함한다.The photosensitive resin composition according to an embodiment includes (A) a binder resin; (B) photopolymerizable monomer; (C) a photoinitiator; (D) a quantum dot having one thiol group at one end, a radically curable vinyl group at one end of the other end, and a linker portion connecting both ends thereof surface-modified with a compound having an ethylene oxide group; And (E) a solvent.
양자점 함유 감광성 수지 조성물은 종래의 감광성 수지 조성물과 같이 광중합성 단량체, 바인더 수지, 광중합개시제, 용매, 첨가제 등으로 구성되나, 안료나 염료 대신 양자점(및 확산제)이 포함되어 단막 형성 후 입사되는 청색광을 변환시키는 기능을 갖는다. 청색광 변환에 핵심적인 기능을 하는 양자점은 소수성 리간드(hydrophobic ligand)로 둘러싸여 있으며, 상기 리간드에 비해친수성(hydrophilic)을 갖는 용매가 적용된 조성물 조액 내에서 양자점의 안정적인 분산을 위해서는 조성물을 구성하는 각 성분들의 밸런스를 맞추는 일이 필요하다. 이 과정에서 양자점의 표면에 어떤 조성물이 직접적으로 결합하느냐에 따라 조성물 조액 내 양자점의 발광효율이 결정된다. 뿐만 아니라 양자점 표면에 직접 결합하는 리간드 혹은 조성물의 성분에 따라 조액 이후 패턴 형성 과정(열공정, 노광 공정)에서 손실되는 발광효율이 달라지게 되므로 양자점의 표면을 안정적으로 패시베이션(passivation)할 수 있는 리간드 혹은 조성물 도입은 높은 광변환 효율을 갖는 양자점 함유 감광성 수지조성물의 구현을 위해 꼭 필요한 상황이다.The photosensitive resin composition containing quantum dots is composed of a photopolymerizable monomer, a binder resin, a photopolymerization initiator, a solvent, and an additive, as in a conventional photosensitive resin composition. It has the function of converting. Quantum dots, which play a key function in blue light conversion, are surrounded by a hydrophobic ligand, and for stable dispersion of quantum dots in a composition solution to which a solvent having hydrophilic properties is applied compared to the ligand, It needs to be balanced. In this process, the luminous efficiency of the quantum dots in the composition solution is determined depending on which composition is directly bonded to the surface of the quantum dots. In addition, a ligand that can stably passivation the surface of a quantum dot because the luminous efficiency that is lost in the pattern formation process (thermal process, exposure process) after liquid preparation varies depending on the ligand or composition of the composition that is directly bonded to the surface of the quantum dot. Or the introduction of the composition is a necessary situation for the realization of a photosensitive resin composition containing quantum dots having high light conversion efficiency.
양자점 함유 감광성 수지 조성물을 적용한 패널은 포토레지스트 공정 이후 여러 단계를 거치며 만들어지며 때로는 매우 가혹 조건에서 이루어진다. 이 과정에서 양자점 함유 감광성 수지 조성물층은 산소나 수분, 열 등에 의하여 손상을 입어 시간이 지남에 따라 혹은 공정이 진행됨에 따라 광변환 기능이 급격히 감소하게 된다. 초기 합성을 거쳐 수득한 양자점의 절대 양자효율은 80% 내지 90% 이상이나 컬러 필터 제작 시 각 단계에 따라 그 효율은 감소하여 30% 내지 40% 수준에 이르는 실정이고, 이후 열공정이 반복됨에 따라 5% 내지 20%까지 감소하게 된다. 따라서, 모든 제작 공정을 거친 후에도 높은 절대 양자효율(PLQY)를 유지시키는 것이 양자점 적용 컬러Panels to which the photosensitive resin composition containing quantum dots is applied are made through several steps after the photoresist process, and are sometimes made under very harsh conditions. In this process, the photosensitive resin composition layer containing quantum dots is damaged by oxygen, moisture, heat, etc., and the photoconversion function rapidly decreases over time or as the process proceeds. The absolute quantum efficiency of the quantum dots obtained through the initial synthesis is 80% to 90% or more, but the efficiency decreases according to each step when manufacturing the color filter, reaching the level of 30% to 40%. % To 20%. Therefore, maintaining high absolute quantum efficiency (PLQY) even after going through all manufacturing processes is the color applied to quantum dots.
필터 기술의 핵심이라 할 수 있겠다.It can be said to be the core of filter technology.
양자점 함유 감광성 수지 조성물의 광변환 효율 및 공정 유지율을 증가시키는 방법 중의 하나로 양자점과 강한binding affinity를 갖는 티올(thiol)계 유기물을 첨가하는 방법이 있다. 그러나, 단순히 티올(thiol)계 첨가제를 조성물 내에 혼합(mixing)하는 경우 단분자인 첨가제는 양자점 함유 감광성 수지 조성물 조액 상태에서 양자점 표면으로부터 이탈, 재결합을 반복하는 일종의 평형상태를 이루며, 이 과정에서 양자효율의 감소가 일어난다. 이후 pre-bake의 열공정을 거치며 티올(thiol)계 첨가제가 양자점의 표면으로부터 이탈, 재결합하는 속도는 증가하게 되고 이에 따른 양자효율 감소도 증가하여, 결국 광변환율의 저하를 야기하기에 이른다. 뿐만아니라 티올(thiol)과 아크릴레이트 계열의 단량체와의 반응으로 결국 패턴형성 공정이 진행됨에 따라, 양자점One of the methods of increasing the photo-conversion efficiency and process retention of the photosensitive resin composition containing quantum dots is a method of adding a thiol-based organic material having strong binding affinity to quantum dots. However, when a thiol-based additive is simply mixed into the composition, the monomolecular additive forms a kind of equilibrium in which the quantum dot-containing photosensitive resin composition is separated from the surface of the quantum dot and recombined repeatedly in a crude liquid state. A decrease in efficiency occurs. Subsequently, through a pre-bake thermal process, the rate at which the thiol-based additive detaches and recombines from the surface of the quantum dot increases, and the quantum efficiency decreases accordingly, leading to a decrease in the light conversion rate. In addition, as the pattern formation process eventually proceeds due to the reaction of thiol and acrylate-based monomers, quantum dots
표면으로부터 리간드의 물리적 손실이 증가하여 최종 post-bake 후의 광변환율이 낮아지게 된다.이외에도 광변환율 및 공정유지율 증가를 위해 양자점 함유 감광성 수지 조성물 조액 내 특정 기능기가 부여된 단량체나 바인더 수지를 적용하는 시도가 있다. 그러나 대부분 단분자 상태로 조액에 혼합 적용하고 있으며 양자점 표면과의 리간드 이탈을 근본적으로 차단하지는 못하는 실정이다. 이를 해결하고자 다관능 티올(multidentate thiol) 작용기를 가진 올리고머나 폴리머를 적용하여 양자점 표면을 더욱 단단히 패시베이션하고자 하는 시도가 있었으나, 역시 광변환율 저하를 억제하기에는 역부족이었다.The physical loss of the ligand from the surface increases and the photoconversion rate after the final post-bake decreases. In addition, an attempt to apply a monomer or a binder resin with a specific functional group in the photosensitive resin composition containing quantum dots to increase the photoconversion rate and process maintenance rate. There is. However, most of them are mixed and applied to the crude liquid in the state of a single molecule, and the situation cannot fundamentally block the release of the ligand from the surface of the quantum dot. To solve this problem, there have been attempts to more tightly passivate the surface of the quantum dot by applying an oligomer or polymer having a multidentate thiol functional group, but it was also insufficient to suppress the reduction of the photoconversion rate.
한편, 일 구현예에 따른 감광성 수지 조성물은, 말단한쪽에 하나의 티올기를 가지고, 다른 말단 한쪽에 라디컬경화성 비닐기를 가지며, 양 말단을 연결하는 링커부분이 에틸렌옥사이드기를 가지는 화합물로 표면 개질된 양자점을 사용함으로써, 광변환율 저하를 최소화할 수 있다.On the other hand, the photosensitive resin composition according to an embodiment has one thiol group at one end, a radically curable vinyl group at the other end, and the linker portion connecting both ends is surface-modified with a compound having an ethylene oxide group. By using, it is possible to minimize the decrease in the light conversion rate.
이하에서 각 성분에 대하여 구체적으로 설명한다.Hereinafter, each component will be described in detail.
(D) 표면 개질된 양자점기존 양자점 합성법에 의해 합성된 양자점은 필연적으로 소수성(hydrophobic)을 가지는 긴 알킬사슬(alkyl chain)과 친수성(hydrophlic)을 가지는 머리기(head group; carboxylic aicd, phosphine, amine, phosphineoxide 등)로 이루어진 리간드 시스템(ligand system)을 가지고 있다. 이러한 리간드는 양자점 표면의 댕글링 본드(dangling bond)를 안정화시켜 양자점 자체의 안정성을 부여함과 동시에 소수성(hydrophobic)을 가지는 용매에 무기 입자인 양자점의 분산성을 부여하게 된다.(D) Surface-modified quantum dots Quantum dots synthesized by the conventional quantum dot synthesis method inevitably have a hydrophobic long alkyl chain and a hydrophlic head group (carboxylic aicd, phosphine, amine). , phosphineoxide, etc.). These ligands stabilize dangling bonds on the surface of the quantum dots, thereby imparting stability of the quantum dots, and at the same time imparting dispersibility of quantum dots, which are inorganic particles, to a solvent having hydrophobic properties.
하지만 양자점 합성 조건에 의한 리간드 시스템을 원하는 대로 변경하지 못함으로써, 소수성을 가지는 비극성 용매에서만 양자점 분산이 이루어짐으로써, 양자점을 디스플레이 공정 상에 적용시키는 데 상당한 제약이 되고 있다. 현재 InP계 양자점의 리간드는 대부분 올레산(oleic acid), 트리옥틸아민(trioctylamine), 트리옥틸포스핀(-옥사이드)(trioctylphosphine(-oxide)) 등으로 이루어져 있고, 분산 가능한 용매가 hexane, cyclohexane, chloroform, toluene 등이 있으나, 이들 모두 디스플레이 공정 상에서 인체 독성 문제로 금지물질로 지정되어 있고, 공정 상 필요한 물성(녹는점, 끓는점, 증기압, 다른 용매와의 상용성 등) 또한 맞지 않다.However, since the ligand system according to the conditions for synthesizing the quantum dots cannot be changed as desired, quantum dots are dispersed only in a non-polar solvent having hydrophobicity, which is a significant limitation in applying the quantum dots to the display process. Currently, the ligands of InP-based quantum dots are mostly composed of oleic acid, trioctylamine, trioctylphosphine (-oxide), etc., and dispersible solvents are hexane, cyclohexane, and chloroform. , toluene, etc., but all of them are designated as prohibited substances due to toxicity to the human body in the display process, and the physical properties required for the process (melting point, boiling point, vapor pressure, compatibility with other solvents, etc.) are also not appropriate.
이러한 관점에서 양자점을 잘 분산시키고, 장기간 우수한 분산성 및 광변환 효율을 유지시킬 수 있는 양자점 분산 기술이 필요로 하게 되었으며, 결국 말단한쪽에 하나의 티올기를 가지고, 다른 말단 한쪽에 라디컬경화성 비닐기를 가지며, 양 말단을 연결하는 링커부분이 에틸렌옥사이드기를 가지는 화합물로 양자점을 표면 개질하는 기술을 개발하게 되었다.From this point of view, a quantum dot dispersion technology that can well disperse quantum dots and maintain excellent dispersibility and light conversion efficiency for a long period of time is required. Eventually, it has one thiol group at one end and a radical curable vinyl group at the other end. And a linker portion connecting both ends to develop a technology for surface modification of quantum dots with a compound having an ethylene oxide group.
양자점 표면과의 친화성(affinity)이 좋은 티올기(thiol group)를 이용하여 양자점 표면의 올레산을 치환(ligand exchange)하되, 상기 티올기 함유 화합물 중간에 에틸렌옥사이드 기를 도입하여,Using a thiol group having good affinity with the surface of the quantum dot, oleic acid on the surface of the quantum dot is substituted (ligand exchange), but an ethylene oxide group is introduced in the middle of the thiol group-containing compound,
디스플레이 공정에 유리한 용매(소수성을 가지는 극성 용매)에 대한 분산성을 극대화시켰다. 또한, 말단에 경화성 비닐기를 도입하여 노광시에 양자점 표면에 고분자 피막을 형성하여 신뢰성을 더욱 향상시킬 수 있다.Dispersibility in a solvent (polar solvent having hydrophobicity) that is advantageous for the display process was maximized. In addition, by introducing a curable vinyl group at the end, a polymer film is formed on the surface of the quantum dot during exposure, thereby further improving reliability.
상기 리간드는 하기 화학식 1로 표시되는 화합물이며, 구체적으로는 하기 화합물군 A에서 선택되어 질수 있다.The ligand is a compound represented by the following formula (1), and specifically, may be selected from the following compound group A.
[화학식 1] [Formula 1]
n은 0~10의 정수이고, X는 직접연결, C1~C10의 지방족탄화수소,페닐, 벤질이고, Y는 CH2 또는 C=O이다.n is an integer from 0 to 10, X is a direct link, C1 to C10 aliphatic hydrocarbon, phenyl, benzyl, and Y is CH2 or C=O.
<화합물군 A><Compound group A>
상기 화합식 1로 표현되는 화합물은 하기 반응식 1과 같이 디설파이드화합물의 환원반응을 통하여 얻어질수 있다.The compound represented by Formula 1 may be obtained through a reduction reaction of a disulfide compound as shown in Scheme 1 below.
<반응식 1> 디설파이드의 환원반응 <Reaction Scheme 1> Reduction of disulfide
[화학식 2] [화학식 1] [Formula 2] [Formula 1]
이는 일반적인 티올의 친핵성 치환반응으로는 비닐기 함유 화합물은 수율높게 제조하기 어렵기 때문이다.This is because it is difficult to prepare a vinyl group-containing compound in high yield by a general nucleophilic substitution reaction of thiol.
이는 하기 반응식 2에서 구체적으로 볼수 있다.This can be seen in detail in Scheme 2 below.
<반응식 2><Reaction Scheme 2>
본 발명은 화학식 1의 화합물을 상기 반응식 2와 같은 부반응없이 제조할수 있는 제조방법을 특징으로 하기도 한다.The present invention is also characterized by a manufacturing method capable of preparing the compound of Formula 1 without side reactions such as in Scheme 2.
Claims (6)
[화학식 1]
n은 0~10의 정수이고, X는 직접연결, C1~C10의 지방족탄화수소,페닐, 벤질이고, Y는 CH2 또는 C=O이다.
A compound of formula 1 below.
[Formula 1]
n is an integer from 0 to 10, X is a direct link, C1 to C10 aliphatic hydrocarbon, phenyl, benzyl, and Y is CH2 or C=O.
<화합물군 A>
<Compound group A>
<반응식 1> 디설파이드의 환원반응
[화학식 2] [화학식 1]
The compounds of claims 1 to 2 prepared by a reaction represented by the following Scheme 1.
<Reaction Scheme 1> Reduction of disulfide
[Formula 2] [Formula 1]
Quantum dots coated with the compounds of claims 1 to 2.
Color resist composition comprising the quantum dots of claim 4
A display manufactured using the color paper composition of claim 5.
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| WO2023054923A1 (en) * | 2021-09-30 | 2023-04-06 | 삼성에스디아이 주식회사 | Curable composition, cured film manufactured using composition, color filter including cured film, and display device including color filter |
| WO2023054922A1 (en) * | 2021-09-30 | 2023-04-06 | 삼성에스디아이 주식회사 | Curable composition, cured layer prepared using the composition, color filter including the cured layer, and display device including the color filter |
| KR20230088235A (en) * | 2021-12-09 | 2023-06-19 | 한인정밀화학(주) | Quantum composition, curable pattern formed from the same, and image display including the curable pattern |
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|---|---|---|---|---|
| WO2023054923A1 (en) * | 2021-09-30 | 2023-04-06 | 삼성에스디아이 주식회사 | Curable composition, cured film manufactured using composition, color filter including cured film, and display device including color filter |
| WO2023054922A1 (en) * | 2021-09-30 | 2023-04-06 | 삼성에스디아이 주식회사 | Curable composition, cured layer prepared using the composition, color filter including the cured layer, and display device including the color filter |
| KR20230088235A (en) * | 2021-12-09 | 2023-06-19 | 한인정밀화학(주) | Quantum composition, curable pattern formed from the same, and image display including the curable pattern |
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