Curable composition comprising quantum dot, resin layer using the same, and display device
阅读说明：本技术 包含量子点的可固化组合物、使用其的树脂层及显示装置 (Curable composition comprising quantum dot, resin layer using the same, and display device ) 是由 尹振燮 朴民志 柳允堤 李范珍 郑知英 崔锺奎 于 2019-01-02 设计创作，主要内容包括：本发明公开一种可固化组合物、使用所述可固化组合物制造的树脂层以及包括所述树脂层的显示装置,所述可固化组合物包含(A)量子点；(B)粘合剂树脂,包含由化学式1-1表示的结构单元、由化学式1-2表示的结构单元及由化学式1-3表示的结构单元,且包含由化学式2表示的结构单元；以及(C)溶剂。在所述化学式中,每一取代基与在说明书中所定义的相同。(Disclosed are a curable composition, a resin layer manufactured using the curable composition, and a display device including the resin layer, the curable composition including (A) quantum dots; (B) a binder resin including a structural unit represented by chemical formula 1-1, a structural unit represented by chemical formula 1-2, and a structural unit represented by chemical formula 1-3, and including a structural unit represented by chemical formula 2; and (C) a solvent. In the formula, each substituent is the same as defined in the specification.)
1. A curable composition, comprising:
(A) quantum dots;
(B) a binder resin including a structural unit represented by chemical formula 1-1, a structural unit represented by chemical formula 1-2, and a structural unit represented by chemical formula 1-3, and including a structural unit represented by chemical formula 2; and
(C) solvent:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formula 2]
Wherein, in chemical formula 1-1, chemical formula 1-2, chemical formula 1-3 and chemical formula 2,
R1is a substituted or unsubstituted acrylate group,
R2is a substituted or unsubstituted C6 to C20 thioaryl group,
R3and R4Independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical, and
X2is a substituted or unsubstituted divalent organic radical.
2. The curable composition of claim 1, wherein the acrylate group is represented by chemical formula 3:
[ chemical formula 3]
Wherein, in chemical formula 3,
R5to R7Independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
3. The curable composition of claim 1, wherein the binder resin satisfies equation 1:
[ equation 1]
0.1≤a/a+b≤0.5
Wherein, in the equation 1,
a represents the number of acrylate groups in the binder resin, and
b represents the number of thioaryl groups in the binder resin.
4. The curable composition according to claim 1, characterized in that the curable composition further comprises a binder resin containing a structural unit represented by chemical formula 1 to 3 and a structural unit represented by chemical formula 2 at both ends:
[ chemical formulas 1-3]
[ chemical formula 2]
Wherein, in chemical formulas 1-3 and 2,
R2to R4Independently a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical, and
X2is a substituted or unsubstituted divalent organic radical.
5. The curable composition of claim 1, wherein X is1Is represented by one of chemical formulas X-1 to X-3:
[ chemical formula X-1]
[ chemical formula X-2]
[ chemical formula X-3]
Wherein, in the chemical formula X-1,
L1is a single bond, an oxygen atom, a sulfur atom, — C (═ O) -, or — CRa1Ra2-, wherein Ra1And Ra2Independently a halogen substituted or unsubstituted C1 to C10 alkyl group.
6. The curable composition of claim 1, wherein X is2Is represented by one of chemical formulae X-4 to X-10:
[ chemical formula X-4]
Wherein, in the chemical formula X-4, RbAnd RcIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl, ester or ether group,
[ chemical formula X-5]
[ chemical formula X-6]
[ chemical formula X-7]
[ chemical formula X-8]
Wherein, in the chemical formula X-8, RdO, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino,
[ chemical formula X-9]
[ chemical formula X-10]
7. The curable composition of claim 1, wherein the binder resin has a weight average molecular weight of 2,000g/mol to 12,000 g/mol.
8. The curable composition according to claim 1, wherein the quantum dot is a quantum dot that absorbs light in 360nm to 780nm and emits fluorescence having a wavelength of 500nm to 700 nm.
9. The curable composition of claim 1, wherein the quantum dots comprise green quantum dots and red quantum dots.
10. The curable composition of claim 1, wherein the solvent comprises propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethylacetamide, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ -butyrolactone, or a combination thereof.
11. The curable composition of claim 1, further comprising a reactive unsaturated compound.
12. The curable composition of claim 1, further comprising a dispersing agent.
13. The curable composition according to claim 12, characterized in that the diffusing agent is contained in an amount of 0.1 to 20% by weight based on the total amount of the curable composition.
14. The curable composition of claim 12, wherein the diffusant comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or combinations thereof.
15. The curable composition of claim 1, further comprising a thiol-based additive.
16. The curable composition of claim 15, wherein the thiol-based additive comprises at least two functional groups at the terminal end represented by formula 4:
[ chemical formula 4]
Wherein, in chemical formula 4,
L7and L8Independently a single bond, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a substituted or unsubstituted C2 to C20 heteroarylene.
17. The curable composition of claim 1, wherein the curable composition comprises 1 to 40 wt.% of the quantum dots, 1 to 40 wt.% of the binder resin, and the balance of the solvent, based on the total amount of the curable composition.
18. The curable composition of claim 1, further comprising malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; leveling agent; a fluorine-based surfactant; or a combination thereof.
19. A resin layer produced using the curable composition according to any one of claims 1 to 18.
20. A display device comprising the resin layer according to claim 19.
21. The display device according to claim 20,
the display device also comprises a color filter and a liquid crystal layer,
the color filter is disposed at one side of the liquid crystal layer, and
the resin layer is disposed at the other side of the liquid crystal layer.
Technical Field
The present disclosure relates to a curable composition including quantum dots, a resin layer using the same, and a display device including the resin layer.
Background
Color filters are used for Liquid Crystal Displays (LCDs), filters for cameras, and the like. The color filter may be manufactured by coating fine regions having three or more colors on a charge coupled device or a transparent substrate. The colored film is produced by a method such as dyeing, printing, pigment dispersion, ink-jet printing, or the like.
Dyeing involves forming a colored film by: an image is formed on a substrate using a coloring agent such as a natural photosensitive resin (e.g., gelatin, etc.), an amine-modified polyvinyl alcohol, an amine-modified acrylic resin, etc., and then the image is dyed using a direct dye. In the dyeing process, a commonly used dye and resin have transparency and good dispersibility by themselves, but may reduce light resistance, water resistance and heat resistance.
Printing involves forming a colored film by: an ink prepared by dispersing a pigment in a heat-curable or light-curable resin is printed, and the ink is cured with heat or light. This method can reduce material costs compared to other methods, but it is difficult to form a precise and accurate image.
The pigment dispersion method is to form a colored film by repeating a series of processes such as coating, exposing, developing and curing a photopolymerizable composition including a colorant on a transparent substrate having a black matrix (black matrix). The pigment dispersion method can improve the heat resistance and durability of the color filter and uniformly maintain the thickness of the film. In addition, since the pigment dispersion method is not only easy to apply but also can realize a precise pattern, such a method is generally employed. For example, Korean patent laid-open Nos. 1992-.
However, such a pigment dispersion method has difficulty in controlling the yield because each of red (R), green (G), and blue (B) colors requires coating, exposure, development, and curing, respectively, to form pixels, which makes the entire production line longer and increases the control factor between processes.
Therefore, such conventional pigment dispersion methods have recently been replaced with several new methods. Including typically ink jet printing processes. The inkjet printing method involves forming an opaque layer such as a black matrix on a glass substrate and implanting ink in the pixel spaces. Such an inkjet printing method does not require processes such as coating, exposure, development, and the like, and thus can reduce the amount of materials required for the processes and simplify the entire production line.
When such an inkjet is used to manufacture a color filter, at least two pigments are often mixed to ensure desired color characteristics. Specifically, when manufacturing a red filter, the main pigment includes a diketopyrrolopyrrole (diketopyrrolopyrrole) system red pigment, for example, color index (c.i.) pigment No. 254. In addition, an anthraquinone-based red pigment (e.g., c.i. pigment red 177) may be added as an auxiliary pigment, or an isoindolinone-based yellow pigment (e.g., c.i. pigment yellow 139) may be added. Other yellow pigments or orange pigments, such as c.i. pigment yellow 138, c.i. pigment yellow 150, c.i. pigment orange 38, and the like, may also be added as necessary. The above pigments are generally used as color filter materials because of their excellent color characteristics, light resistance and heat resistance; however, as the application field of the color filter of the liquid crystal display increases, the required physical properties become higher and higher. Therefore, research into pulverization and fine dispersion of pigments has been advanced to improve color characteristics such as brightness and color purity in transmission, but expression of color characteristics of a color filter by combining only these pigments is limited.
Disclosure of Invention
An embodiment provides a curable composition including quantum dots capable of minimizing curing shrinkage during a thermal process and improving brightness.
Another embodiment provides a resin layer manufactured using the curable composition.
Another embodiment provides a display device including the resin layer.
An embodiment provides a curable composition comprising (a) quantum dots; (B) a binder resin including a structural unit represented by chemical formula 1-1, a structural unit represented by chemical formula 1-2, and a structural unit represented by chemical formula 1-3, and including a structural unit represented by chemical formula 2 at a terminal; and (C) a solvent.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formula 2]
In chemical formula 1-1, chemical formula 1-2, chemical formula 1-3, and chemical formula 2,
R1is a substituted or unsubstituted acrylate group (acrylate group),
R2is a substituted or unsubstituted C6 to C20 thioaryl group,
R3and R4Independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical (quaternary organic group), and
X2is a substituted or unsubstituted divalent organic group.
The acrylate group may be represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the first and second,
R5to R7Independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
The binder resin may satisfy equation 1.
[ equation 1]
0.1≤a/a+b≤0.5
In the case of the equation 1, the,
a represents the number of acrylate groups in the binder resin, and
b represents the number of thioaryl groups in the binder resin.
The curable composition may further include a binder resin including structural units represented by chemical formulas 1 to 3 and structural units represented by chemical formula 2 at both ends.
[ chemical formulas 1-3]
[ chemical formula 2]
In chemical formulas 1 to 3 and 2,
R2to R4Independently a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical, and
X2is a substituted or unsubstituted divalent organic radical.
X1May be represented by one of chemical formulas X-1 to X-3.
[ chemical formula X-1]
[ chemical formula X-2]
[ chemical formula X-3]
In the chemical formula X-1, the compound,
L1is a single bond, an oxygen atom, a sulfur atom, — C (═ O) -, or — CRa1Ra2- (wherein R)a1And Ra2Independently a halogen substituted or unsubstituted C1 to C10 alkyl).
X2May be represented by one of chemical formula X-4 through chemical formula X-10.
[ chemical formula X-4]
In the chemical formula X-4, RbAnd RcIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.
[ chemical formula X-5]
[ chemical formula X-6]
[ chemical formula X-7]
[ chemical formula X-8]
In the chemical formula X-8, RdO, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.
[ chemical formula X-9]
[ chemical formula X-10]
The weight average molecular weight of the binder resin may be from about 2,000g/mol to about 12,000 g/mol.
The quantum dots may be quantum dots that absorb light in about 360nm to about 780nm and emit fluorescence having a wavelength of about 500nm to about 700 nm.
The quantum dots may include green quantum dots and red quantum dots.
The solvent may include propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate), dipropylene glycol methyl ether acetate (dipropylene glycol methyl ether acetate), cyclohexyl acetate (cyclohexyl acetate), ethanol (ethanol), ethylene glycol dimethyl ether (ethylene glycol dimethyl ether), ethylene glycol diethyl ether (ethylene glycol dimethyl ether), diethylene glycol dimethyl ether (ethylene glycol dimethyl ether), dimethylacetamide (dimethyl acetate), 2-butoxyethanol (2-butoxyethanol), N-methylpyrrolidine (N-methylpyrrolidine), N-ethylpyrrolidine (N-ethylpyrrolidine), propylene carbonate (propylene carbonate), γ -butyrolactone (γ -butyrolactone), or a combination thereof.
The curable composition may further comprise a reactive unsaturated compound.
The curable composition may further comprise a dispersing agent.
The dispersing agent may be included in an amount of about 0.1 wt% to about 20 wt% based on the total amount of the curable composition.
The dispersing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or combinations thereof.
The curable composition may further comprise a thiol-based additive.
The thiol-based additive may include at least two functional groups represented by chemical formula 4 at the terminal.
[ chemical formula 4]
In the chemical formula 4, the first and second organic solvents,
L7and L8Independently a single bond, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a substituted or unsubstituted C2 to C20 heteroarylene.
The curable composition may include the quantum dots in an amount of about 1 wt% to about 40 wt%, the binder resin in an amount of about 1 wt% to about 40 wt%, and the balance solvent, based on the total amount of the curable composition.
The curable composition may further comprise malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; leveling agent; a fluorine-based surfactant; or a combination thereof.
Another embodiment provides a resin layer manufactured using the curable composition.
Another embodiment provides a display device including the resin layer.
The display device may further include a color filter and a liquid crystal layer, and herein, the color filter may be disposed on one side of the liquid crystal layer, and the resin layer may be disposed on the other side of the liquid crystal layer.
Other embodiments of the invention are included in the following detailed description.
The conventional acrylic or epoxy adhesive resin has a high curing shrinkage rate during a thermal process, and thus causes surface omission (surface emission) or cracks when a thermally curable composition including the above adhesive resin is formed into a cured layer (resin layer), but the curable composition according to the embodiment uses an adhesive resin having a structure different from that of the conventional adhesive resin and minimizes the curing shrinkage rate during the thermal process, and thus can prevent surface omission or cracks and additionally improve quantum efficiency and improve dispersion of quantum dots and thus can improve brightness.
Drawings
Fig. 1 is a schematic view illustrating a display device (LCD) having a resin layer formed of a curable composition according to an embodiment.
Description of the symbols
1: light guide
2: resin layer
3: liquid crystal layer
4: overcoat layer
5: glass
6: color resist layer
7: color resist layer
8: color resist layer
9: quantum dots
10: quantum dots
Detailed Description
Hereinafter, examples of the present invention are explained in detail. These embodiments are exemplary, however, and the invention is not limited thereto and is defined by the scope of the claims.
When a specific definition is not otherwise provided, "alkyl" as used herein refers to C1 to C20 alkyl, "alkenyl" refers to C2 to C20 alkenyl, "cycloalkenyl" refers to C3 to C20 cycloalkenyl, "heterocycloalkenyl" refers to C3 to C20 heterocycloalkenyl, "aryl" refers to C6 to C20 aryl, "arylalkyl" refers to C6 to C20 arylalkyl, "alkylene" refers to C1 to C20 alkylene, "arylene" refers to C6 to C20 arylene, "alkylarylene" refers to C6 to C20 alkylarylene, "heteroarylene" refers to C3 to C20 heteroarylene, and "alkyleneoxy" refers to C1 to C20 alkyleneoxy.
As used herein, "substituted" when a specific definition is not otherwise provided, refers to the replacement of at least one hydrogen with a substituent: halogen atoms (F, Cl, Br, or I), hydroxyl groups, C1 to C20 alkoxy groups, nitro groups, cyano groups, amine groups, imino groups, azido groups, amidino groups, hydrazine groups, hydrazone groups, carbonyl groups, carbamoyl groups, thiol groups (thiol groups), ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl groups, C6 to C20 aryl groups, C3 to C20 cycloalkyl groups, C3 to C20 cycloalkenyl groups, C3 to C20 cycloalkynyl groups, C2 to C20 heterocycloalkyl groups, C2 to C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.
As used herein, "hetero" refers to substitution in the chemical formula by at least one heteroatom of N, O, S and P, when no specific definition is otherwise provided.
When a specific definition is not otherwise provided, "(meth) acrylate" used herein means both "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid".
When a specific definition is not otherwise provided, "combination" as used herein means mixing or copolymerization.
Unless a specific definition is provided otherwise, as used herein, a hydrogen atom is bonded at a position when a chemical bond is not drawn at the position that should be given.
As used herein, an "x" denotes a point connecting the same or different atoms or chemical formulae, when a specific definition is not otherwise provided.
A curable composition according to an embodiment includes (a) quantum dots; (B) a binder resin including a structural unit represented by chemical formula 1-1, a structural unit represented by chemical formula 1-2, and a structural unit represented by chemical formula 1-3, and including a structural unit represented by chemical formula 2; and (C) a solvent.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formula 2]
In chemical formula 1-1, chemical formula 1-2, chemical formula 1-3, and chemical formula 2,
R1is a substituted or unsubstituted acrylate group,
R2is a substituted or unsubstituted C6 to C20 thioaryl group,
R3and R4Independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical, and
X2is a substituted or unsubstituted divalent organic radical.
One embodiment relates to a curable composition (e.g., a thermally curable composition) comprising quantum dots, which has been recognized as a new technological trend in the display field. The curable composition including quantum dots applied to a display device includes a binder resin, a colorant (colorant), a solvent, an additive, etc. as in the conventional curable composition, and quantum dots are used instead of the colorant such as a pigment/dye as a material for realizing color characteristics, and may further include a light diffuser, etc. in addition.
The quantum dots may be representatively CdSe, InP, or the like, and a synthesis method of the quantum dots has been rapidly developed in terms of luminous efficiency (quantum yield), and luminous efficiency close to 100% is achieved. For example, quantum dot Ultra High Definition Television (QD SUHDTV) manufactured by applying quantum dot chips is currently commercially available. In addition, QD TVs are being developed by including sub-dots (containing no pigment and/or dye) in a color resist layer of a conventional light-emitting diode (LED) TV as a self-luminous version rather than a filtered version in the color resist layer. Such development of a television by applying a quantum dot-containing resin composition is critically dependent on maintaining the patterning property of the composition and the light efficiency of the quantum dot and well realizing the patterning property in a process of a thermal process (prebaking), exposure-development-washing-deposition-another thermal process (postbaking), and the like.
However, a method of including a quantum dot in a color resist layer of a conventional LED television so that the color resist layer is self-luminous is costly and has a limitation in minimizing a shrinkage rate during a thermal process, but recently, a method including the following steps has been studied: the quantum dot sheet is inserted as a separate layer in the color resist layer without including a quantum dot-containing resin layer, blue light (light source) is made incident into the quantum dot sheet, and the blue light is converted into white light. Herein, in order to convert blue light into white light, the quantum dot sheet should include both green and red quantum dots.
Quantum dots that play a key function in converting blue light are surrounded by hydrophobic ligands, and herein, when such hydrophobic quantum dots are added to a hydrophilic composition (e.g., and a curable composition containing an epoxy-based binder resin, etc.), there is a problem of deterioration in dispersibility, and thus to solve such a dispersibility problem, ligand substitution and passivation on the surface of the quantum dots are being actively studied. However, the patterning process of the curable composition including the quantum dot may drastically deteriorate sensitivity, and thus it is difficult to ensure patterning properties.
In addition, since the curable composition including the quantum dot includes a large amount of inorganic particles and thus includes a relatively small amount of organic material, processability is deteriorated. Therefore, it is very difficult to form a pattern in a forward direction (forward direction) due to deterioration of melting characteristics of the pattern and deterioration of developability particularly during a post-baking process.
Conventionally, undercut (undercut) of photoresist has been improved by: a binder resin having a low melting point as that of a cardo-based binder resin is applied to the composition to post-bake the undercut after development, or an epoxy group is introduced into the binder resin to enhance a close contact force during a pre-bake process. However, since the curable composition including the quantum dot includes a large amount of inorganic material as described above, improvement of undercut is limited because melting characteristics cannot be exhibited by applying only carduon binder resin (the curable composition including the quantum dot includes a large amount of inorganic material and thus cannot exhibit melting characteristics after post-baking), and the binder resin including an epoxy group has a problem that residual characteristics are greatly deteriorated. In addition, since the acrylic binder resin is one cause of deterioration in the efficiency of quantum dots in the composition, it is difficult to use the conventionally known acrylic binder resin itself.
In addition, the acrylic or epoxy-based binder resin, which has been conventionally used as a binder resin in a curable composition including quantum dots, exhibits a curing shrinkage of about 15% to about 20% in a post-baking step during a thermal curing process, a curing shrinkage of about 5% in an additional thermal process step after the post-baking, thus having a problem of surface omission in a resin layer, and even if there is no surface omission, a problem of causing cracks in the resin layer. With respect to the epoxy-based adhesive resin, the above-mentioned problems are caused by deterioration of quantum efficiency or dispersibility of the quantum dots due to an epoxy curing mechanism and an epoxy structure (as described above, the surface of the quantum dots is hydrophobic, but a network formed of the epoxy structure is hydrophilic), and with respect to the acrylic-based adhesive resin, the acrylic-based adhesive resin has compatibility with the quantum dots and thus the acrylic-based adhesive resin does not deteriorate the quantum efficiency, but the above-mentioned problems are caused by too large free volume (free volume) between molecules during curing.
However, the curable composition including quantum dots according to the embodiment uses cardmultisystem binder resin as a binder resin and thus solves the conventional problems (surface omission, cracks, etc.) by the following means: a carden multi-series adhesive resin comprising structural units containing both acrylate groups and thioaryl groups as functional groups is applied to minimize intermolecular free volume caused by pi-pi stacking of fluorene (fluoroene) compounds and thus minimize shrinkage upon curing.
Hereinafter, each component is specifically described.
(A) Quantum dots
The quantum dots can absorb light in a wavelength region of about 360nm to about 780nm, such as about 400nm to about 780nm, and emit fluorescence in a wavelength region of about 500nm to about 700nm, such as about 500nm to about 580nm or about 600nm to about 680 nm. That is, the quantum dot may have a maximum fluorescence wavelength (fluorescence λ) among wavelengths of about 500nm to about 680nmem)。
The quantum dots can independently have a full width at half maximum (FWHM) in a range of about 20nm to about 100nm, e.g., about 20nm to about 50 nm. When the quantum dots have a full width at half maximum (FWHM) within these ranges, the quantum dots have high color purity and thus have an effect of increasing color reproducibility when used as a color material in a color filter.
The quantum dots may independently be organic materials, inorganic materials, or a hybrid (or mixture) of organic and inorganic materials.
The quantum dot may independently include a core and a shell surrounding the core, and herein, the core and the shell may have a structure such as a core, a core/shell, a core/first shell/second shell, an alloy/shell, etc., independently including groups II-IV, III-V, etc., but is not limited thereto.
For example, the core may include at least one material selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell surrounding the core may comprise at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.
In the embodiment, since the interest in the environment has been greatly increased worldwide and the regulation of toxic materials has been strengthened recently, a non-cadmium-based luminescent material (InP/ZnS) having a slightly low quantum efficiency (quantum yield) but being environmentally friendly is used instead of the luminescent material having a cadmium-based core, but is not necessarily limited thereto.
The structure of the quantum dot is not particularly limited, but in the case of a quantum dot of a core/shell structure, the overall size of the quantum dot may include a shell of (average particle diameter) about 1nm to about 15nm, for example about 5nm to about 15 nm.
For example, the quantum dots may comprise red quantum dots, green quantum dots, or a combination thereof. For example, quantum dots may include both green and red quantum dots. Herein, a larger amount of green quantum dots may be included compared to red quantum dots. The red quantum dots may have an average particle size of about 10nm to about 15 nm. The green quantum dots may have an average particle size of about 5nm to about 8 nm.
On the other hand, the curable composition according to the embodiment may further include a dispersant due to dispersion stability of the quantum dot. The dispersant contributes to uniform dispersibility of the light conversion material such as quantum dots in the curable composition, and may include a nonionic dispersant, an anionic dispersant, or a cationic dispersant. Specifically, the dispersant may be a polyalkylene glycol or an ester thereof, a polyoxyalkylene, a polyol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate, a carboxylic ester, a carboxylic salt, an alkylamide alkylene oxide addition product, an alkylamine, or the like, and these dispersants may be used alone or as a mixture of two or more thereof. The dispersant may be used in an amount of about 0.1 wt% to about 100 wt%, for example about 10 wt% to about 20 wt%, based on the solid content of the light conversion material, such as quantum dots.
The quantum dots may be included in an amount of about 1 wt% to about 40 wt%, for example about 1 wt% to about 10 wt%, based on the total amount of the curable composition according to an embodiment. When the quantum dot is included within these ranges, the light conversion ratio is improved, and excellent processability can be provided by not reducing the pattern characteristics and the developing characteristics.
(B) Adhesive resin
The binder resin includes a structural unit represented by chemical formula 1-1, a structural unit represented by chemical formula 1-2, and a structural unit represented by chemical formula 1-3 and includes a structural unit represented by chemical formula 2 at a terminal.
The binder resin structurally includes both vinyl and thioaryl groups in the curable acrylate group, and thus can solve the above undercut problem while improving the development margin.
When no thioaryl group is present in the structure of the binder resin, optical characteristics (i.e., light maintenance rate) are greatly deteriorated, and when no acrylate group is present in the binder resin, pattern properties may be greatly deteriorated due to the generation of undercut.
For example, the acrylate group may be represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the first and second,
R5to R7Independently is a hydrogen atom or a hydrogen atomSubstituted or unsubstituted C1 to C20 alkyl.
For example, the vinyl group in the acrylate group is the cure site, and the acrylate group may be present in an amount of about 10% to about 50%, such as about 20% to about 30%, based on the total amount of acrylate groups and thioaryl groups in the adhesive resin (100%). Acrylate groups in the range may facilitate curing of the bottom during uv curing, and thus solve the undercut problem and also improve patterning ability.
For example, the binder resin may satisfy equation 1.
[ equation 1]
0.1≤a/a+b≤0.5
In the case of the equation 1, the,
a represents the number of the acrylate groups in the binder resin, and
b represents the number of the thioaryl groups in the binder resin.
The curable composition may further include a binder resin including structural units represented by chemical formulas 1 to 3 and structural units represented by chemical formula 2 at both ends.
[ chemical formulas 1-3]
[ chemical formula 2]
In chemical formulas 1 to 3 and 2,
R2to R4Independently a substituted or unsubstituted C6 to C20 thioaryl group,
X1is a substituted or unsubstituted tetravalent organic radical, and
X2is a substituted or unsubstituted divalent organic radical.
In chemical formulae 1-1 to 1-3, X1Can be represented by the chemical formula X-1One of X-3.
[ chemical formula X-1]
[ chemical formula X-2]
[ chemical formula X-3]
In the chemical formula X-1, the compound,
L1is a single bond, an oxygen atom, a sulfur atom, — C (═ O) -, or — CRa1Ra2- (wherein R)a1And Ra2Independently a halogen substituted or unsubstituted C1 to C10 alkyl).
For example, in the formula X-1, L1May be a sulfur atom.
In chemical formula 2, X2May be represented by one of chemical formula X-4 through chemical formula X-10.
[ chemical formula X-4]
In the chemical formula X-4, RbAnd RcIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.
[ chemical formula X-5]
[ chemical formula X-6]
[ chemical formula X-7]
[ chemical formula X-8]
In the chemical formula X-8, RdO, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.
[ chemical formula X-9]
[ chemical formula X-10]
The weight average molecular weight of the binder resin may be from about 2,000g/mol to about 12,000 g/mol. When the weight average molecular weight of the binder resin is within the range, a pattern may be well formed without residue, and in addition, the pattern may be satisfactory and there is no thickness loss during development. Specifically, when the weight average molecular weight of the binder resin is less than about 2,000g/mol, the polymer may not be formed, and when the weight average molecular weight of the binder resin is greater than about 12,000g/mol, the binder resin is dissolved in a peel-off type (peel type) during KOH development and thus impurities may be generated.
The binder resin may be included in an amount of about 1 wt% to about 40 wt%, for example about 5 wt% to about 20 wt%, based on the total amount of the curable composition. When the binder resin is included within the range, excellent sensitivity, developability, resolution, and linearity of the pattern may be obtained.
(C) Solvent(s)
The curable composition according to the embodiment may include, as a solvent: alcohols such as methanol, ethanol, etc.; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether and the like; cellosolve acetate such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactates such as methyl lactate, ethyl lactate, and the like; alkyl glycolates such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, and the like; alkyl 3-hydroxypropionates such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and the like; alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, and the like; or ketoesters such as ethyl pyruvate, etc., and in addition, N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate, cyclohexyl acetate, etc., but not limited thereto.
For example, the solvent may desirably be a glycol ether, such as ethylene glycol monoethyl ether, or the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as ethyl 2-hydroxypropionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; alcohols such as ethanol and the like; cyclohexyl acetate or a combination thereof.
For example, the solvent can be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethylacetamide, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ -butyrolactone, or combinations thereof.
The balance, e.g., from about 20 wt% to about 80 wt%, e.g., from about 35 wt% to about 80 wt%, of the solvent may be included based on the total amount of the curable composition. When the solvent is in the range, the curable composition has an appropriate viscosity, and thus may have excellent coating properties when coated over a large area by spin coating and slit coating.
Reactive unsaturated compound
The reactive unsaturated compound may be mixed with monomers or oligomers commonly used in conventional curable compositions.
The reactive unsaturated compound may be an acrylate-based compound. For example, the reactive unsaturated compound may be at least one selected from the group consisting of: ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol a diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, and the like, which may be used alone or as a mixture of two or more.
The reactive unsaturated compound may be treated with an anhydride to improve developability.
The reactive unsaturated compound may be included in an amount of from about 1 wt% to about 10 wt%, for example from about 1 wt% to about 5 wt%, based on the total amount of the curable composition. When the reactive unsaturated compound is included within the range, the reactive unsaturated compound is sufficiently cured during exposure in the pattern forming process, and thus reliability may be improved, and heat resistance, light resistance, chemical resistance, resolution, and close contact property of the pattern may be improved.
Dispersing agent (or dispersing agent dispersion)
The curable composition according to the embodiment may further include a diffusing agent.
For example, the diffusant may comprise barium sulfate (BaSO)4) Calcium carbonate (CaCO)3) Titanium dioxide (TiO)2) Zirconium oxide (ZrO)2) Or a combination thereof.
The diffusing agent reflects light that is not absorbed in the above quantum dots so that the reflected light can be absorbed again in the quantum dots. In other words, the diffusing agent increases the dose of light absorbed in the quantum dots, and thus, the light conversion efficiency of the curable composition is improved.
The diffuser can have an average particle size (e.g., D) of about 150nm to about 250nm, such as about 180nm to about 230nm50). When the diffusing agent has an average particle diameter within the range, more excellent light scattering effect can be obtained, and light can be enhancedThe conversion efficiency.
The dispersing agent may be included in an amount of from about 0.1 wt% to about 20 wt%, for example from about 1 wt% to about 15 wt%, based on total solids of the curable composition. When the diffuser is included in an amount of less than about 0.1 wt% based on the total weight of the curable composition, it may be difficult to achieve an improvement in light conversion efficiency, and when the diffuser is included in an amount of more than about 20 wt%, pattern characteristics may be deteriorated.
Other additives
In order to improve the stability and dispersibility of the quantum dot, the curable composition according to the embodiment may further include a thiol-based additive.
The thiol-based additive may replace the shell surface of the quantum dot, and may improve dispersion stability of the quantum dot in a solvent and may stabilize the quantum dot.
The thiol-based additive has 2 to 10, for example, 2 to 4 thiol groups (-SH) at the terminal end according to its structure.
For example, the thiol-based additive may include at least two functional groups represented by chemical formula 4 at the end.
[ chemical formula 4]
In the chemical formula 4, the first and second organic solvents,
L7and L8Independently a single bond, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a substituted or unsubstituted C2 to C20 heteroarylene.
For example, the thiol-based additive may be represented by chemical formula 5.
[ chemical formula 5]
In the chemical formula 5, the first and second organic solvents,
L7and L8Independently a single bond,A substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a substituted or unsubstituted C2 to C20 heteroarylene, and
u1 and u2 are independently integers of 0 or 1.
For example, in chemical formulas 4 and 5, L7And L8May independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
Specific examples of the thiol-based additive may be selected from pentaerythritol tetrakis (3-mercaptopropionate) represented by chemical formula 4a, trimethylolpropane tris (3-mercaptopropionate) represented by chemical formula 4b, pentaerythritol tetrakis (mercaptoacetate) represented by chemical formula 4c, trimethylolpropane tris (2-mercaptoacetate) represented by chemical formula 4d, glycol di-3-mercaptopropionate represented by chemical formula 4e, and combinations thereof.
[ chemical formula 4a ]
[ chemical formula 4b ]
[ chemical formula 4c ]
[ chemical formula 4d ]
[ chemical formula 4e ]
The thiol-based additive may be included in an amount of about 0.1 wt% to about 10 wt%, for example about 0.1 wt% to about 5 wt%, based on the total amount of the curable composition. For example, the thiol-based additive may be included in an amount of about 0.1 wt% to about 10 wt%, such as about 0.5 wt% to about 8 wt%, based on total solids of the curable composition. When the thiol-based additive is included within the range, the stability of the light conversion material such as the quantum dot, in which the thiol group in this component reacts with the acrylic group of the resin or monomer to form a covalent bond, may be improved, and thus the heat resistance of the light conversion material such as the quantum dot, may be improved.
The curable composition according to the embodiment may further include a polymerization inhibitor including a hydroquinone-based compound (hydroquinone-based compound), a catechol-based compound (cathehol-based compound), or a combination thereof. The curable composition according to the embodiment may inhibit crosslinking at room temperature during exposure after coating the photosensitive composition by further comprising a hydroquinone-based compound, a catechol-based compound, or a combination thereof.
For example, the hydroquinone-based compound, the catechol-based compound, or the combination thereof may be hydroquinone, methyl hydroquinone, methoxy hydroquinone, t-butyl hydroquinone, 2, 5-di-t-butyl hydroquinone, 2, 5-bis (1, 1-dimethylbutyl) hydroquinone, 2, 5-bis (1,1,3, 3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyrogallol, 2, 6-di-t-butyl-4-methylphenol, 2-naphthol, tris (N-hydroxy-N-nitrosophenylamine-O, O') aluminum), or the combination thereof, but is not limited thereto.
The hydroquinone-based compound, the catechol-based compound, or combinations thereof may be used in dispersed form and the polymerization inhibitor may be included in dispersed form in an amount of from about 0.001 wt% to about 1 wt%, for example from about 0.01 wt% to about 0.1 wt%, based on the total amount of the curable composition. When the polymerization inhibitor is included within the range, the time lapse at room temperature may be solved, and at the same time, the sensitivity deterioration and the surface delamination phenomenon may be suppressed.
The curable composition according to the embodiment may further include, in addition to the thiol-based additive and the polymerization inhibitor: malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; leveling agent; a fluorine-based surfactant; or a combination thereof.
For example, the curable composition may further include a silane-based coupling agent having a reactive substituent (e.g., a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc.) to improve close contact properties with the substrate.
Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta-epoxycyclohexylethyltrimethoxysilane, or the like, and the silane-based coupling agent may be used alone or in a mixture of two or more.
The silane-based coupling agent may be used in an amount of about 0.01 parts by weight to about 10 parts by weight, based on 100 parts by weight of the curable composition. When the silane-based coupling agent is contained within the range, close contact properties, storage ability, and the like are improved.
In addition, the curable composition may further optionally contain a surfactant, for example, a fluorine-based surfactant, to improve coating properties and suppress the generation of spots.
Examples of fluorine-based surfactants may be BM-
The fluorine-based surfactant may be included in an amount of about 0.001 parts by weight to about 5 parts by weight, based on 100 parts by weight of the curable composition. When the fluorine-based surfactant is contained in the range, coating uniformity may be ensured, no stain is generated, and wetting properties of the glass substrate may be improved.
The curable composition may further contain predetermined amounts of other additives such as antioxidants, stabilizers, etc., as long as these additives do not diminish the properties.
Another embodiment provides a resin layer manufactured using the curable composition.
A method of manufacturing a resin layer includes: coating the curable composition on a substrate using a spray coating method to form a pattern (S1); and curing the pattern (S2).
(S1) Pattern formation
The curable composition can be coated on the substrate to about 0.5 μm to about 10 μm using a spray coating process. The spray coating method can form a pattern by spraying a single color and thus repeatedly spraying as many times as the desired number of colors, but can form a pattern by spraying the desired number of colors at the same time.
(S2) curing
The obtained pattern is cured to obtain a cured resin layer. Herein, the curing may be thermal curing. Thermal curing may be performed by: heating the pattern at greater than or equal to about 100 ℃ for 3 minutes to remove the solvent from the curable composition, and subsequently heating the pattern at a temperature of about 160 ℃ to about 300 ℃ for about 30 minutes.
Another embodiment provides a display device including the resin layer.
The display device may further include a color filter and a liquid crystal layer, and herein, the color filter may be disposed on one side of the liquid crystal layer, and the resin layer may be disposed on the other side of the liquid crystal layer.
Referring to fig. 1, in a display device, color resist layers 6, 7, 8 having color filters and an overcoat layer 4 are provided with a liquid crystal layer 3 in between to face a resin layer 2 formed of a curable composition according to an embodiment through columnar spacers. The glass 5 is provided on the color resist layers 6, 7, 8 having color filters and the overcoat layer 4, and the color resist layers 6, 7, 8 having color filters and the overcoat layer 4 are provided on the liquid crystal layer 3. In addition, a silica deposition layer is present on one surface of the resin layer 2, and the silica deposition layer absorbs blue light from the light source through the light guide 1. In the display device according to fig. 1, the layer containing quantum dots (resin layer 2) is formed separately from the color resist layers 6, 7, 8, and thus the quantum efficiency of the quantum dots 9, 10 can be prevented from deteriorating. In addition, the light guide may not be a polymethyl methacrylate (PMMA) light guide 1 but a glass light guide. A glass light guide is used instead of the PMMA light guide, and thus the glass light guide may help make the panel thin and improve brightness.
Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.
(preparation of curable composition)
Examples 1 and 2 and comparative examples 1 and 2
Each of the curable compositions according to examples 1 and 2 and comparative examples 1 and 2 was prepared by using the following components in the following compositions shown in table 1.
(A) Quantum dots
(A-1) InP/ZnSe/ZnS Quantum dots (fluorescence. lambda.)em532nm, FWHM 37nm, green QD, Hansol Chemical co., Ltd.))
(A-2) InP/ZnSe/ZnS Quantum dots (fluorescence. lamda.)em630nm, FWHM 39nm, Red QD, Korea chemical Co., Ltd.)
(B) Adhesive resin
(B-1) an adhesive resin (Takema corporation (TAKOMA), TSR-TB04) (weight average molecular weight: 4,500g/mol) comprising a structural unit represented by the formula E-1 and structural units represented by the formula E-2 at both ends
[ chemical formula E-1]
[ chemical formula E-2]
(B-2) an adhesive resin (Takema, TSR-TA01) (weight-average molecular weight: 4,000g/mol) comprising a structural unit represented by the formula E-1, a structural unit represented by the formula E-3, and a structural unit represented by the formula E-4, and structural units represented by the formula E-5 at both ends
[ chemical formula E-3]
[ chemical formula E-4]
[ chemical formula E-5]
In the chemical formula E-5, the compound represented by the formula,
Rxand RyIndependently is-O (C ═ O) CHCH2Or unsubstituted thiophenyl.
(B-3) an adhesive resin (Takema, TSR-TA01-2) comprising a structural unit represented by the formula E-1, a structural unit represented by the formula E-3, and a structural unit represented by the formula E-4, and structural units represented by the formula E-5 at both ends (weight average molecular weight: 8,000g/mol)
(B-4) acrylic Binder resin (SHOWA DENKO, SP-RY67-1)
(B-5) acrylic Binder resin (SMS Co., 400H)
(B-6) epoxy adhesive resin (ISA Co., Ltd., EHPE 3150)
(B-7) epoxy adhesive resin (ISA Co., Ltd., OXT-221)
(C) Solvent(s)
(C-1) Cyclohexylacetate (Sigma-Aldrich)
(C-2) propylene glycol monomethyl ether acetate (PGMEA, Sigma-Aldrich Co.)
(D) Reactive unsaturated compound
Acrylate monomer (V1000, Osaka Organic chemical industry Ltd.)
(E) Dispersing agent
Titanium dioxide Dispersion (TiO)2Solid content: 20 wt%, average particle diameter: 200nm, Ditto Technology, Inc.)
(F) Other additives
(F-1) fluorine surfactant (F-554, Di Aisheng Co., Ltd., (DIC Co., Ltd.))
(F-2) silane-based coupling agent (KBM803, Shin-Etsu Chemical Co., Ltd.)
(Table 1)
(unit: wt%)
Evaluation: curing shrinkage and Brightness of the composition
15ml of each of the curable compositions according to examples 1 and 2 and comparative examples 1 and 2 was taken and coated to a thickness of about 10 μm on a glass substrate using a spin coater (wobbe ott (optical) MS-a150, michassa Corp.)), prebaked at 100 ℃ for 3 minutes on a hot plate, and then postbaked (180 μm) in 2 steps (POB I, POB II)℃，N230 minutes) and then the shrinkage was measured. In addition, the color coordinates and brightness of the composition were measured on a 447nm Backlight Unit (BLU) after POB I using a CAS spectrometer. The measurement results are shown in table 2.
(Table 2)
Example 1
Example 2
Comparative example 1
Comparative example 2
Shrinkage (%) after POB I step
6.2
4.3
15
4.3
Shrinkage (%) after POB II step
0.6
0.3
3.2
0.2
Luminance (%)
102
103
85
64
As shown in table 2, examples 1 and 2 showed low curing shrinkage and excellent brightness, compared to comparative examples 1 and 2.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be 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. The above-described embodiments are therefore to be construed as illustrative and not limitative of the invention in any way whatsoever.
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