CURABLE COMPOSITION, CURED FILM MANUFACTURED USING COMPOSITION, COLOR FILTER INCLUDING CURED FILM, AND DISPLAY DEVICE INCLUDING COLOR FILTER

Abstract

Disclosed are a curable composition, a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter. The curable composition includes (A) quantum dots; and (B) a curable monomer having a viscosity of less than 6.2 cps and a vapor pressure of 1?10.sup.?6 torr to 3?10.sup.?3 torr.

Claims

1. A curable composition, comprising (A) quantum dots; and (B) a curable monomer having a viscosity of less than 6.2 cps and a vapor pressure of 1?10.sup.?6 torr to 3?10.sup.?3 torr.

2. The curable composition of claim 1, wherein the curable monomer has a viscosity of greater than or equal to 3 cps and less than 6.2 cps.

3. The curable composition of claim 1, wherein the curable monomer has an asymmetric structure.

4. The curable composition of claim 1, wherein the curable monomer is represented by Chemical Formula 1: ##STR00035## wherein, in Chemical Formula 1, R.sup.a is a substituted or unsubstituted C1 to C20 alkyl group, and L.sup.a is an unsubstituted C1 to C8 alkylene group, a substituted or unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by Chemical Formula 2, ##STR00036## wherein, in Chemical Formula 2, L.sup.b and L.sup.c are each independently a substituted or unsubstituted C1 to C8 alkylene group, and n is an integer of 1 to 3.

5. The curable composition of claim 4, wherein in Chemical Formula 1, L.sup.1 is an unsubstituted C1 to C8 alkylene group, an unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by Chemical Formula 2, and in Chemical Formula 2, L.sup.2 and L.sup.3 are each independently unsubstituted C1 to C6 alkylene group.

6. The curable composition of claim 1, wherein the curable monomer represented by any one of Chemical Formula 1-1 to Chemical Formula 1-9: ##STR00037## ##STR00038##

7. The curable composition of claim 1, wherein the quantum dot is a quantum dot surface-modified with a ligand having a polar group.

8. The curable composition of claim 7, wherein the ligand having the polar group is represented by any one of Chemical Formula 3 to Chemical Formula 16: ##STR00039## wherein, in Chemical Formula 3 to Chemical Formula 8, R.sup.1 to R.sup.7 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, L.sup.1 to L.sup.16 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n1 to n7 are each independently an integer of 0 to 10, ##STR00040## wherein, in Chemical Formula 9 to Chemical Formula 11, R.sup.8 and R.sup.9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.17 to L.sup.23 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n8 to n10 are each independently an integer of 0 to 10, ##STR00041## wherein, in Chemical Formula 12 to Chemical Formula 15, R.sup.10 to R.sup.15 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L.sup.24 to L.sup.29 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n11 to n16 are each independently an integer of 0 to 10, ##STR00042## wherein, in Chemical Formula 16, R.sup.16 to R.sup.18 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.30 to L.sup.32 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n17 to n19 are each independently an integer of 0 to 10.

9. The curable composition of claim 1, wherein the curable composition is a solvent-free curable composition.

10. The curable composition of claim 9, wherein the solvent-free curable composition comprises, based on the total amount of the solvent-free curable composition, 5 wt % to 60 wt % of the quantum dots; and 40 wt % to 95 wt % of the polymerizable compound.

11. The curable composition of claim 1, wherein the curable composition further comprises a polymerizationinitiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

12. The curable composition of claim 11, wherein the light diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

13. The curable composition of claim 1, wherein the curable composition further comprises a solvent.

14. The curable composition of claim 13, wherein the curable composition comprises 1 wt % to 40 wt % of the quantum dots; 1 wt % to 20 wt % of the polymerizable compound; and 40 wt % to 80 wt % of the solvent based on the total weight of the curable composition.

15. The curable composition of claim 1, wherein the curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

16. A cured layer manufactured by using the curable composition of claim 1.

17. A color filter comprising the cured layer of claim 16.

18. A display device comprising the color filter of claim 17.

Description

PREPARATION EXAMPLE

[0199] After putting a magnetic bar in a 3-necked round-bottomed flask, green quantum dot dispersion solution (InP/ZnSe/ZnS, Hansol Chemical; quantum dot solid content of 23 wt %) was put therein. The compound represented by Chemical Formula Q (a ligand) was added thereto and then, stirred at 80? C. under a nitrogen atmosphere. When a reaction was completed, after decreasing the temperature down to room temperature (23? C.), the quantum dot reaction solution was added to cyclohexane, catching precipitates. The precipitates were separated from the cyclohexane through centrifugation and then, sufficiently dried in a vacuum oven for one day, obtaining surface-modified quantum dots.

[0200] (*Synthesis of Compound represented by Chemical Formula Q: 100 g of PH-4 (Hannong Chemical Inc.) was put in a 2-neck round-bottomed flask and then, sufficiently dissolved in 300 mL of THF. 15.4 g of NaOH and 100 mL of water were injected thereinto at 0? C. and then, sufficiently dissolved, until a clear solution was obtained. A solution obtained by dissolving 73 g of para-toluene sulfonic chloride in 100 mL of THF was slowly injected thereinto at 0? C. Injection was carried out for 1 hour, and the obtained mixture was stirred at room temperature for 12 hours. When a reaction was completed, an excessive amount of methylene chloride was added thereto and then, stirred, and a NaHCO.sub.3 saturated solution was added thereto, which was followed by extraction, titration, and water removal. After removing the solvent, the residue was dried in a dry oven for 24 hours. 50 g of the dried product was put in a 2 necked round-bottomed flask and sufficiently stirred in 300 mL of ethanol. Subsequently, 27 g of thiourea was added thereto and dispersed therein and then, refluxed at 80? C. for 12 hours. Then, an aqueous solution prepared by dissolving 4.4 g of NaOH in 20 mL of water was injected thereinto, while further stirred for 5 hours, an excessive amount of methylene chloride was added thereto, and then, a hydrochloric acid aqueous solution was added thereto, which was sequentially followed by extraction, titration, water removal, and solvent removal. The obtained product was dried in a vacuum oven for 24 hours, obtaining a compound represented by Chemical Formula Q.)

##STR00019##

(Preparation of Curable Compositions)

[0201] The curable compositions according to Examples 1 to 9 and Comparative Examples 1 to 6 were prepared based on each of the following components.

[0202] (A) Quantum Dots

[0203] Surface-modified green quantum dots prepared from the above preparation example

[0204] (B) Polymerizable Compound

[0205] (B-1) a compound represented by Chemical Formula 1-1 (viscosity: 4.3 cPs, vapor pressure: 2.9?10.sup.?3 torr)

##STR00020##

[0206] (B-2) a compound represented by Chemical Formula 1-2 (viscosity: 5.5 cPs, vapor pressure: 1?10.sup.?3 torr)

##STR00021##

[0207] (B-3) a compound represented by Chemical Formula 1-3 (viscosity: 6.15 cPs, vapor pressure: 3.6?10.sup.?4 torr)

##STR00022##

[0208] (B-4) a compound represented by Chemical Formula 1-4 (viscosity: 3.9 cPs, vapor pressure: 3?10.sup.?3 torr)

##STR00023##

[0209] (B-5) a compound represented by Chemical Formula 1-5 (viscosity: 4.5 cPs, vapor pressure: 1.9?10.sup.?3 torr)

##STR00024##

[0210] (B-6) a compound represented by Chemical Formula 1-6 (viscosity: 5.3 cPs, vapor pressure: 1.2?10.sup.?3 torr)

##STR00025##

[0211] (B-7) a compound represented by Chemical Formula 1-7 (viscosity: 4.1 cPs, vapor pressure: 7.8?10.sup.?4 torr)

##STR00026##

[0212] (B-8) a compound represented by Chemical Formula 1-8 (viscosity: 5.4 cPs, vapor pressure: 9.5?10.sup.?5 torr)

##STR00027##

[0213] (B-9) a compound represented by Chemical Formula 1-9 (viscosity: 6.1 cPs, vapor pressure: 5?10.sup.?6 torr)

##STR00028##

[0214] (B-10) a compound represented by Chemical Formula C-1 (viscosity: 6.2 cPs, vapor pressure: 1?10.sup.?3 torr)

##STR00029##

[0215] (B-11) a compound represented by Chemical Formula C-2 (viscosity: 4.5 cPs, vapor pressure: 8?10.sup.?3 torr)

##STR00030##

[0216] (B-12) a compound represented by Chemical Formula C-3 (viscosity: 5.4 cPs, vapor pressure: 2.85?10.sup.?3 torr)

##STR00031##

[0217] (B-13) a compound represented by Chemical Formula C-4 (viscosity: 4.45 cPs, vapor pressure: 1.85?10.sup.?3 torr)

##STR00032##

[0218] (B-14) a compound represented by Chemical Formula C-5 (viscosity: 5.27 cPs, vapor pressure: 3.7?10.sup.?4 torr)

##STR00033##

[0219] (B-15) a compound represented by Chemical Formula C-6 (viscosity: 6.4 cPs, vapor pressure: 1.3?10.sup.?4 torr)

##STR00034##

[0220] (C) Photopolymerization Initiator

[0221] TPO-L (Polynetron)

[0222] (D) Light Diffusing Aquent

[0223] Titanium dioxide dispersion (rutile type TiO.sub.2; D50 (180 nm))

[0224] (E) Polymerization Inhibitor

[0225] Methylhydroquinone (TOKYO CHEMICAL Co., Ltd.)

Examples 1 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3

[0226] Specifically, the surface-modified quantum dots prepared in the preparation example were mixed with a curable monomer in the same weight ratio and then, stirred for 12 hours. Herein, a polymerization inhibitor was added thereto and then, stirred for 5 minutes. Subsequently, a photoinitiator was added thereto, and then, a light diffusing agent was added thereto.

[0227] (Taking Example 1 as an example, 40 g of the surface-modified green quantum dots and 40 g of a compound represented by Chemical Formula 1-1 as the curable monomer were mixed and stirred to prepare quantum dot dispersion, 12.5 g of another curable monomer represented by Chemical Formula 1-1 and 0.5 g of the polymerization inhibitor were added thereto and then, stirred for 5 minutes, and subsequently, 3 g of the photoinitiator and 4 g of the light diffusing agent were added thereto and then, stirted, preparing a curable composition.)

[0228] Specific compositions are shown in Tables 1 and 2.

TABLE-US-00001 TABLE 1 (unit: wt %) Polymeri- Light Quantum Curable monomer zation Photo- diffusing dot B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 inhibitor initiator agent Ex. 1 40 52.5 0.5 3 4 Ex. 2 40 52.5 0.5 3 4 Ex. 3 40 52.5 0.5 3 4 Ex. 4 40 52.5 0.5 3 4 Ex. 5 40 52.5 0.5 3 4 Ex. 6 40 52.5 0.5 3 4 Ex. 7 40 52.5 0.5 3 4 Ex. 8 40 52.5 0.5 3 4 Ex. 9 40 52.5 0.5 3 4

TABLE-US-00002 TABLE 2 (unit: wt %) Polymeri- Light Quantum Curable monomer zation Photo- diffusing dot B-10 B-11 B-12 B-13 B-14 B-15 inhibitor initiator agent Comp. 40 52.5 0.5 3 4 Ex. 1 Comp. 40 52.5 0.5 3 4 Ex. 2 Comp. 40 52.5 0.5 3 4 Ex. 3 Ref. 40 52.5 0.5 3 4 Ex. 1 Ref. 40 52.5 0.5 3 4 Ex. 2 Ref. 40 52.5 0.5 3 4 Ex. 3

Evaluation 1: Evaluation of Ink Viscosity and Volatility

[0229] Each curable composition according to Examples 1 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 was measured with respect to viscosity at 25? C. by using a viscometer (RV-2 spins, 23 rpm, D-H made by Brookfield Engineering Laboratories, Inc.), and the results are shown in Table 3, and in addition, after ink-jetting each curable compositions in a pixel having barrier ribs, a thickness reduction rate of each single film was measured by using a 3D optical microscope (VK-9710 color 3D laser microscope, Keyence Corp.) to calculate a film residue ratio, and the results are shown in Table 3. In Table 3, the higher a film residue ratio, the lower volatility.

TABLE-US-00003 TABLE 3 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Viscosity (cPs) 20.3 23.2 25.3 23.6 24.2 25.1 25.3 25.8 26.5 Film residue 85 92 96 85 88 92 85 90 95 ratio (%) Comp. Comp. Comp. Ref. Ref. Ref. Ex. 1 Ex. 2 Ex. 3 Ex. 1 Ex. 2 Ex. 3 Viscosity (cPs) 25.5 21 26 23.4 21.8 23.6 Film residue 85 73 88 82 80 83 ratio (%)

[0230] Referring to Table 3, the curable compositions according to Examples 1 to 9, Reference Examples 1 to 3, and Comparative Examples 1 to 3 all had low viscosity, but when the curable compositions having similar viscosity were compared, the curable compositions according to Examples 1 to 9 exhibited a higher film residue ratio than those of the curable compositions according to Reference Examples 1 to 3 and Comparative Examples 1 to 3 and thus much improved volatility. In other words, the curable composition according to an embodiment had low viscosity and simultaneously, exhibited improved volatility.

[0231] While this invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the present invention in any way.