Compound, antireflection film comprising the same, and display device

Abstract

Provided are a compound represented by a specific chemical formula, an antireflection film, and a display device including the antireflection film.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a compound, an anti-reflection film including the same, and a display device including the anti-reflection film. BACKGROUND

[0002] In a typical liquid crystal display (LCD), light emitted from a white light source passes through RGB color filters of each pixel to form a sub-pixel of each color, and colors within the RGB range can be produced by combining these.

[0003] In recent years, new displays using emitters that emit the color of each sub-pixel such as quantum dots and organic-inorganic phosphors are being developed, and a method using a UV light source and a method using a blue light source have been proposed as a method of exciting these blue, green, and red light sources.

[0004] When a UV light source is used, each color is produced and realized by blue, green, and red emitters, but when a blue light source is used, green and red are each color produced by emitters, and a blue pixel transmits the light source as it is.

[0005] In the case of display materials including quantum dots that have recently been commercialized or are being developed, light emission by green quantum dots and red quantum dots through a blue light source or a white light source is used. Quantum dot-containing display devices aim to improve color gamut and luminance by using quantum dot materials, and development of quantum dot-emitting panels using various light sources has been continuously conducted. In addition, viewing angle can be improved depending on the position of the quantum dot material in the panel configuration. Next-generation quantum dot display devices are being developed to increase the intensity of the light source or to develop a light source having an expanded blue area to improve the light emission efficiency of quantum dots.

[0006] In quantum dot display devices, the spectrum of light reaching the quantum dot material has a very close influence on the efficiency of the quantum dots. Since the characteristics of each light source differ depending on the type of light source, each field is continuously striving to introduce a new method to improve the efficiency of each light source.

[0007] On the other hand, in the case of new displays using emitters, there is a need to reduce reflectance caused by external light or adjust the panel color caused by scattering reflection. To solve this problem, attempts have been made to use dyes in optical members constituting the panel. When quantum dots are used as emitters, it is difficult to reduce the reflectance of external light or adjust the panel color.

[0008] Accordingly, in the case of the new display, an antireflection film having an improved luminance loss or color correction is being introduced, and recently an attempt is made to additionally apply a cyanine-based dye or an azo-based dye as a dye capable of absorbing light of a specific wavelength to maximize the low reflection property of the antireflection film.

[0009] However, the cyanine-based dye or the azo-based dye is capable of absorbing light in a short wavelength region, but has a problem in that light resistance reliability is reduced, and thus it is difficult to apply the same to the antireflection film. SUMMARY

[0010] TECHNICAL PROBLEM

[0011] An object of the present application is to provide a compound capable of absorbing light in a red wavelength region of a light source.

[0012] Another embodiment provides an antireflection film including the compound.

[0013] Another embodiment provides a display device including the antireflection film.

[0014] Another object of the present application is to provide an optical member having a high color correction effect and a significantly reduced reflectance to improve reflected color and having a high total light transmittance.

[0015] TECHNICAL SOLUTION

[0016] One embodiment provides a compound represented by Chemical Formula 1.

[0017] [Chemical Formula 1]

[0018]

[0019] In Chemical Formula 1,

[0020] M is two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a metal hydroxide atom, or a metal oxide atom,

[0021] R 1 to R 16Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, a sulfonamide group represented by formula 2, or a combination thereof, and

[0022] R 1 To R 8 At least one of them and R 9 To R 16 At least one of them is a sulfonamide group represented by chemical formula 2.

[0023] [Chemical Formula 2]

[0024]

[0025] In chemical formula 2,

[0026] R 17 and R 18 Each of the following is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C20 heteroaryl.

[0027] R 17 and R 18 At least one of them is a C3 to C20 cycloalkyl group, and

[0028] *Indicates the moiety that is bonded to the benzene ring of chemical formula 1.

[0029] R 17 and R 18 Each can be independently hydrogenated or substituted or unsubstituted C3 to C20 cycloalkyl, and R 17 and R 18 At least one of them can be a C3 to C20 cycloalkyl group.

[0030] M can be Cu, Co, Zn, V (=O) or Ag.

[0031] R 1 To R 4 At least one of them can be a sulfonamide group represented by chemical formula 2, R 5 To R 8 At least one of them can be a sulfonamide group represented by chemical formula 2, R 9 To R 12 At least one of them can be a sulfonamide group represented by chemical formula 2, and R 13 To R 16 At least one of them can be a sulfonamide group represented by chemical formula 2.

[0032] R 1 at least one of R 4 to R 5 may be a sulfonamide group represented by Chemical Formula 2, and the rest can be hydrogen atoms; R 8 to R 9 may be a sulfonamide group represented by Chemical Formula 2, and the rest can be hydrogen atoms; R 12 to R 13 may be a sulfonamide group represented by Chemical Formula 2, and the rest can be hydrogen atoms. 16

[0033] The compound can be a compound represented by Chemical Formula 3.

[0034] [Chemical Formula 3]

[0035]

[0036] In Chemical Formula 3,

[0037] M is Cu, Co, Zn, V(=O), or Ag,

[0038] n1 to n4 are each independently an integer of 0 or 1, and

[0039] n5 is an integer of 1 to 4,

[0040] with the proviso that n1+n2+n3+n4≠0.

[0041] The compound can include a compound represented by any one of Chemical Formula 4 to Chemical Formula 14.

[0042] [Chemical Formula 4]

[0043]

[0044] [Chemical Formula 5]

[0045]

[0046] [Chemical Formula 6]

[0047]

[0048] [Chemical Formula 7]

[0049]

[0050] [Chemical Formula 8]

[0051]

[0052] ​[Chemical Formula 9]

[0053]

[0054] [Chemical Formula 10]

[0055]

[0056] [Chemical Formula 11]

[0057]

[0058] [Chemical Formula 12]

[0059]

[0060] [Chemical Formula 13]

[0061]

[0062] [Chemical Formula 14]

[0063]

[0064] The compound can be a red absorbing dye.

[0065] The dye can have a maximum absorption peak at a wavelength of 650 nm to 750 nm.

[0066] Another embodiment provides an antireflection film including the compound.

[0067] The antireflection film can include an adhesive layer and an antireflection layer on the adhesive layer, and the compound can be included in the adhesive layer.

[0068] The antireflection film can include an adhesive layer, a dye-containing layer, and an antireflection layer on the dye-containing layer, and the compound can be included in the dye-containing layer.

[0069] Another embodiment provides a display device including the antireflection film.

[0070] The display device can further include a quantum dot-containing layer.

[0071] The display device can further include a quantum dot-containing layer, a light source, a color filter, and a substrate.

[0072] In the display device, the quantum dot-containing layer can be disposed on the light source, the color filter can be disposed on the quantum dot-containing layer, the substrate can be disposed on the color filter, and the anti-reflection film can be disposed on the substrate.

[0073] The substrate can include a glass substrate.

[0074] Other embodiments of the present application include in the following detailed description.

[0075] Advantages

[0076] The compound according to one embodiment is contained in the anti-reflection film to absorb light sources in a near-infrared (650 nm to 750 nm) region, so that even a very small amount can block the near-infrared region to reduce reflectance of the display device due to external light and improve light resistance reliability and improve luminance loss and color saturation. BRIEF DESCRIPTION OF DRAWINGS

[0077] Figure 1 and Figure 2 are each independently a schematic diagram illustrating an anti-reflection film according to an embodiment.

[0078] Figure 3 and Figure 4 are each independently a schematic diagram illustrating a display device according to an embodiment.

[0079] Figure 5 is a graph showing light transmittance of a dye according to Synthesis Example 1 and Comparative Example 2 as a function of wavelength. DETAILED DESCRIPTION

[0080] Hereinafter, embodiments of the present application will be described in detail. However, these embodiments are exemplary, the present application is not limited thereto, and the present application is defined by the scope of claims.

[0081] In the present specification, when a specific definition is not otherwise provided, "substituted" means that at least one hydrogen of a compound is replaced with a substituent selected from a halogen atom (F, Cl, Br, or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imine group, an azido group, an amidine group, a hydrazine group, a hydrazo group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

[0082] In the present specification, when no specific definition is provided otherwise, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl", and "heterocycloalkylene" mean cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene, respectively, which contain at least one heteroatom of N, O, S, or P in a ring compound.

[0083] In the present specification, when no specific definition is provided otherwise, the term "combination" means mixing or copolymerization.

[0084] In the present specification, when no definition is provided otherwise, a chemical bond in a chemical formula is not drawn at a position where it should be drawn.

[0085] In the present specification, when no specific definition is provided otherwise, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid".

[0086] In the present specification, when no specific definition is provided otherwise, "alkyl" means C1 to C20 alkyl, specifically C1 to C15 alkyl, "cycloalkyl" means C3 to C20 cycloalkyl, specifically C3 to C18 cycloalkyl, "alkoxy" means C1 to C20 alkoxy, specifically C1 to C18 alkoxy, "aryl" means C6 to C20 aryl, specifically C6 to C18 aryl, "alkenyl" means C2 to C20 alkenyl, specifically C2 to C18 alkenyl, "alkylene" means C1 to C20 alkylene, specifically C1 to C18 alkylene, and "arylene" means C6 to C20 arylene, specifically C6 to C16 arylene.

[0087] In the present specification, when no definition is provided otherwise, "*" means a connecting moiety between the same or different atoms or chemical formulas.

[0088] In the present specification, "the maximum absorption wavelength (λmax)" of a compound (dye) means a wavelength at which the maximum absorbance appears when the absorbance of a solution of the compound (dye) having a concentration of 10 ppm in cyclohexanone is measured. The maximum absorbance can be measured according to a method known to those skilled in the art.

[0089] In the present specification, "light resistance reliability" is evaluated by the change in light transmittance. The light transmittance of a display device is measured at the maximum absorption wavelength of a dye before and after irradiation under the conditions of a xenon test chamber (Q-SUN) [light source lamp: xenon lamp, irradiation intensity: 0.35 W / cm 2 , irradiation temperature: 63°C, irradiation time: 500 hours, irradiation direction: irradiation from the side of an antireflection film].

[0090] One embodiment provides a compound represented by Chemical Formula 1.

[0091] [Chemical Formula 1]

[0092]

[0093] In Chemical Formula 1,

[0094] M is Zn, Co, or Cu,

[0095] R 1 to R 16 each independently is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heteroaryl, a sulfonamide group represented by Chemical Formula 2, or a combination thereof, and

[0096] R 1 to R 8 at least one of R 9 to R 16 is a sulfonamide group represented by Chemical Formula 2,

[0097] [Chemical Formula 2]

[0098]

[0099] wherein, in Chemical Formula 2,

[0100] R 17 and R 18 each independently is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C20 heteroaryl, wherein at least one of R 17 and R 18 is C3 to C20 cycloalkyl, and * indicates a portion bonded to the benzene ring of Chemical Formula 1.

[0101] When a near-infrared blocking dye (generally, Zn-PC dye) commonly used in a plasma display is applied to an anti-reflection film, the amount of the dye is increased to achieve a color correction function, but the anti-reflection film using the same has a problem in that the transmittance of the film is increased due to discoloration of the dye in an evaluation of light resistance reliability.

[0102] The present invention is to apply a Cu-PC (phthalocyanine) having a specific substituent structure to an anti-reflection film to strongly absorb light in a near-infrared region, while reducing the amount of the dye due to improved wavelength matching, and thus, to achieve a predetermined level of reflectance and excellent light resistance reliability due to the structural characteristics of the dye.

[0103] When the compound represented by Chemical Formula 1 is used as a dye, the compound can strongly absorb near-infrared light, i.e., light in the wavelength range of 650 nm to 750 nm, thereby increasing color reproducibility in the red region and improving luminance loss of a panel compared to a method using a near-infrared blocking dye (general Zn-PC dye). When the compound represented by Chemical Formula 1 according to the embodiment is applied to an anti-reflection film, light resistance reliability can be ensured.

[0104] Specifically, when the compound represented by Chemical Formula 1 is used as a dye, luminance in the blue region (450 nm to 485 nm) and the red region (625 nm to 740 nm) can be improved.

[0105] Since the compound according to the embodiment includes a substituent represented by Chemical Formula 2, even if a small amount is used, a more clear color can be exhibited, the luminance of a display is improved, and a display device having excellent color characteristics is obtained.

[0106] In order to achieve a similar purpose, attempts have been made to use a conventional dye to absorb light in the wavelength region of 750 nm to 850 nm, in which, since the amount of use of the conventional dye is large, there is a problem in that it is not possible to ensure the process margin of the entire composition.

[0107] However, when the compound according to the embodiment is used as a dye, a sufficiently high color reproducibility can be achieved with only a small amount of the compound, which solves the problem.

[0108] R 17 and R 18 may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C14 aryl, or substituted or unsubstituted C2 to C14 heteroaryl, wherein R 17 and R 18 at least one of which can be C3 to C10 cycloalkyl.

[0109] R 17 and R 18 may each independently be hydrogen, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C10 aryl, or substituted or unsubstituted C2 to C10 heteroaryl, wherein R 17 and R 18 at least one of which can be C3 to C6 cycloalkyl.

[0110] R 17 and R 18Each can be independently hydrogen or substituted or unsubstituted C3 to C20 cycloalkyl, wherein R 17 and R 18 At least one of them can be a C3 to C20 cycloalkyl group.

[0111] R 17 and R 18 Each can be independently hydrogen or substituted or unsubstituted C3 to C10 cycloalkyl, wherein R 17 and R 18 At least one of them can be a C3 to C10 cycloalkyl group.

[0112] R 17 and R 18 Each can be independently hydrogen or substituted or unsubstituted C3 to C6 cycloalkyl, wherein R 17 and R 18 At least one of them can be a C3 to C6 cycloalkyl group.

[0113] R 1 To R 4 At least one of them can be a sulfonamide group represented by chemical formula 2, R 5 To R 8 At least one of them can be a sulfonamide group represented by chemical formula 2, R 9 To R 12 At least one of them can be a sulfonamide group represented by chemical formula 2, and R 13 To R 16 At least one of them can be a sulfonamide group represented by chemical formula 2.

[0114] R 1 To R 4 At least one of them can be a sulfonamide group represented by chemical formula 2, and the rest can be hydrogen atoms; R 5 To R 8 At least one of them can be a sulfonamide group represented by chemical formula 2, and the rest can be hydrogen atoms; R 9 To R 12 At least one of them can be a sulfonamide group represented by chemical formula 2, and the rest can be hydrogen atoms; and R 13 To R 16 At least one of them can be a sulfonamide group represented by chemical formula 2, and the rest can be hydrogen atoms.

[0115] The compound can be a compound represented by chemical formula 3.

[0116] [Chemical Formula 3]

[0117]

[0118] In chemical formula 3,

[0119] M is Cu, Co, Zn, V(=O) or Ag,

[0120] n1 to n4 are each independently an integer of 0 or 1, and

[0121] n5 is an integer of 1 to 4,

[0122] with the proviso that n1+n2+n3+n4≠0.

[0123] Like the structure of the compound represented by Chemical Formula 3, the sulfonamide group substituted to the benzene ring can be substituted at the positions of the two α (adjacent) and β (second) carbons, wherein one compound can be substituted with 1 to 4 sulfonamide groups, most preferably 3 or 4 sulfonamide groups, which obtain the most excellent light absorption in the red wavelength region.

[0124] For example, when the compound represented by Chemical Formula 3 can be substituted with four sulfonamide groups, since the sulfonamide group can be substituted at the α (adjacent) or β (second) carbon of the benzene ring, a mixture of more than five structural isomers can be produced, and the present application can include the mixture of structural isomers.

[0125] For example, the compound represented by Chemical Formula 1 can be a compound represented by any one of Chemical Formula 4 to Chemical Formula 14, but is not necessarily limited thereto.

[0126] [Chemical Formula 4]

[0127]

[0128] [Chemical Formula 5]

[0129]

[0130] [Chemical Formula 6]

[0131]

[0132] [Chemical Formula 7]

[0133]

[0134] [Chemical Formula 8]

[0135]

[0136] [Chemical Formula 9]

[0137]

[0138] [Chemical Formula 10]

[0139]

[0140] [Chemical Formula 11]

[0141]

[0142] [Chemical Formula 12]

[0143]

[0144] [Chemical Formula 13]

[0145]

[0146] [Chemical Formula 14]

[0147]

[0148] In the present application, two or more compounds represented by Chemical Formula 4 to Chemical Formula 14 can be included simultaneously as a mixture.

[0149] The compound can be a red absorption dye.

[0150] The dye can have a maximum absorption peak at a wavelength of 650 nm to 750 nm, specifically, at a wavelength of 650 nm to 700 nm. That is, when the compound is used as a dye contained in an anti-reflection film, light in the near-infrared region can be maximally absorbed to block the spectrum of the region.

[0151] According to another embodiment, there is provided an adhesive composition including the compound according to the embodiment.

[0152] The adhesive composition can include the compound represented by Chemical Formula 1 in an amount of 0.0001 wt% to 1 wt% based on the total amount of the adhesive composition, for example, 0.001 wt% to 1 wt%, for example, 0.01 wt% to 1 wt%, for example, 0.1 wt% to 1 wt%, for example, 0.0001 wt% to 0.5 wt%, for example, 0.001 wt% to 0.5 wt%, for example, 0.01 wt% to 0.5 wt%, for example, 0.1 wt% to 0.5 wt%. When the compound represented by Chemical Formula 1 is contained in the above content range, it is effective to improve light resistance reliability by adjusting the panel color of a display device to which the anti-reflection film is applied.

[0153] Another embodiment provides an anti-reflection film including the compound.

[0154] The anti-reflection film includes an adhesive layer and an anti-reflection layer formed on the adhesive layer, and the compound represented by Chemical Formula 1 can be contained in the adhesive layer.

[0155] Further, the antireflection film includes an adhesive layer, a dye-containing layer, and an antireflection layer formed on the dye-containing layer, and the compound represented by Chemical Formula 1 can be contained in the dye-containing layer.

[0156] That is, in the stacked structure of the antireflection film according to the embodiment, the compound represented by Chemical Formula 1 can be contained in the adhesive layer or can be contained in a separate dye-containing layer (see Figure 1 and Figure 2 ).

[0157] The antireflection layer can consist only of the low-refractive layer or can include the low-refractive layer.

[0158] The low-refractive layer reduces the reflectance of the antireflection film due to the difference in refractive index between the substrate and / or the high-refractive layer described later.

[0159] The low-refractive layer can include a curable adhesive resin, a fluorine atom-containing monomer, and fine particles (e.g., hollow silica) having an average particle diameter of 5 nm to 300 nm, and the thickness of the low-refractive layer can be 0.01 μm to 0.15 μm. The refractive index of the low-refractive layer can be 1.20 to 1.40.

[0160] By further forming a functional coating layer on one surface of the low-refractive layer, i.e., on the upper surface of the low-refractive layer, the antireflection film can be given additional functions. The functional coating layer can include an anti-fingerprint layer, an anti-static layer, a hard coating layer, an anti-glare layer, a barrier layer, etc., but is not limited thereto.

[0161] The antireflection layer can further include a high-refractive layer.

[0162] The high-refractive layer is formed between the substrate described later and the low-refractive layer, has a refractive index between the substrate and the low-refractive layer, and thus reduces the reflectance of the antireflection layer. The high-refractive layer is directly formed with the substrate and the low-refractive layer, respectively. "Directly formed" means that there is no other layer between the layers.

[0163] The thickness of the high-refractive layer is 0.05 μm to 20 μm, the refractive index is 1.45 to 2, the haze value according to JIS-K7361 is not different from or is different from the haze value of the substrate by 10% or less, and it is excellent in transparency and excellent in antireflection properties.

[0164] The hard coating layer increases the hardness of the antireflection layer, so that scratches do not occur even if the antireflection layer is used on the outermost surface of a display device. It is not necessarily required to provide the hard coating layer. If the target hardness is ensured in the high- or low-refractive layer, the hard coating layer can be omitted.

[0165] The hard coating layer can be formed between the substrate and the high-refractive layer or between the substrate and the low-refractive layer.

[0166] The hard coat layer can be a cured layer formed by uniformly mixing, in a cured adhesive, ultra-fine metal oxide particles having an average particle diameter of 1 nm to 30 nm and a particle size distribution range of less than or equal to ± 5 nm. The hard coat layer can have a thickness of 1 μm to 15 μm, and the refractive index of the hard coat layer can be greater than or equal to 1.54.

[0167] The anti-reflection layer can have a thickness of 50 μm to 500 μm, for example, 50 μm to 300 μm, for example, 50 μm to 150 μm. When the anti-reflection layer has a thickness within the above range, it can be easily applied to a display device.

[0168] The adhesive layer can be formed on a lower surface of the anti-reflection layer to adhere an optical element, for example, a display, to a panel or the like. As described above, the adhesive layer can include the compound (dye) represented by Chemical Formula 1.

[0169] The adhesive layer can have a glass transition temperature of -70℃ to 0℃, for example, -65℃ to -20℃. When the glass transition temperature of the adhesive layer is within the above range, the adhesion to a panel can be improved.

[0170] The adhesive layer can be a thermosetting adhesive layer or a light-curable adhesive layer. Desirably, since the adhesive layer becomes a thermosetting adhesive layer, the influence of ultraviolet rays caused by the absorption wavelength of the compound (dye) represented by Chemical Formula 1 does not need to be considered, thereby facilitating the manufacture of the adhesive layer. The "thermosetting adhesive layer" can include not only an adhesive layer cured by a predetermined heat treatment at 40℃ to 100℃, but also an adhesive layer cured at room temperature (for example, 20℃ to 30℃).

[0171] The adhesive layer can be formed of a composition for an adhesive layer including an adhesive resin and a curing agent.

[0172] The type of the adhesive resin is not limited as long as it can secure the glass transition temperature of the adhesive layer. For example, the adhesive resin can be a silicone-based, urethane-based, (meth)acryl-based resin, or the like, but desirably, a (meth)acryl-based adhesive resin can be used.

[0173] The glass transition temperature of the adhesive resin can be -70℃ to 0℃, desirably -65℃ to -20℃. When the glass transition temperature of the adhesive resin has the above range, the adhesion to a panel can be improved.

[0174] The adhesive resin can have a weight average molecular weight of 500,000 g / mol to 2,000,000 g / mol, for example, 800,000 g / mol to 1,500,000 g / mol. When the weight average molecular weight of the adhesive resin has the above range, the adhesion to a panel can be improved.

[0175] The adhesive resin can include a random copolymer of at least one of a (meth)acryl-based monomer having an alkyl group, a (meth)acryl-based monomer having a hydroxyl group, and a (meth)acryl-based monomer having an aromatic group, a (meth)acryl-based monomer having an alicyclic group, and a (meth)acryl-based monomer having a heteroalicyclic group, desirably having an alkyl group.

[0176] The (meth)acryl-based monomer having an alkyl group can include a (meth)acrylic acid ester having an unsubstituted C1 to C10 alkyl group. Specifically, the (meth)acryl-based monomer having an alkyl group can include one or more of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate, but is not limited thereto. These can be included individually or in combination of two or more. The (meth)acryl-based monomer having an alkyl group can be included in an amount of 60 wt% to 99.99 wt%, for example, 60 wt% to 90 wt%, for example, 80 wt% to 99.9 wt% of the monomer mixture.

[0177] The (meth)acryl-based monomer having a hydroxyl group can include one or more of a (meth)acryl-based monomer having a C1 to C20 alkyl group having at least one hydroxyl group, a (meth)acryl-based monomer having a C3 to C20 cycloalkyl group having at least one hydroxyl group, and a (meth)acryl-based monomer having a C6 to C20 aromatic group having at least one hydroxyl group. Specifically, the (meth)acryl-based monomer having a hydroxyl group can desirably include one or more of a (meth)acryl-based monomer having a C1 to C20 alkyl group having at least one hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1-chloro-2-hydroxypropyl (meth)acrylate. These can be included individually or in combination of two or more. The content of the (meth)acryl-based monomer having a hydroxyl group can be 0.01 wt% to 20 wt%, for example, 0.1 wt% to 10 wt% of the monomer mixture.

[0178] The (meth)acryl-based monomer having an aromatic group can include a (meth)acrylate having a C6 to C20 aryl group or a C7 to C20 aralkyl group. Specifically, the (meth)acryl-based monomer having an aromatic group can include, but is not limited to, phenyl (meth)acrylate, benzyl (meth)acrylate, and the like. The content of the (meth)acryl-based monomer having an aromatic group can be 0 wt% to 50 wt%, for example, 0 wt% to 20 wt% of the monomer mixture.

[0179] In the present specification, when an alkyl group is mixed in a monomer along with a cycloaliphatic group, it is classified as a (meth)acryl-based monomer having a cycloaliphatic group.

[0180] The (meth)acryl-based monomer having a cycloaliphatic group can be a (meth)acrylate having a C5 to C20 monocyclic or heterocyclic cycloaliphatic group, and can include at least one of cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. The content of the (meth)acryl-based monomer having a cycloaliphatic group can be 0 wt% to 50 wt%, for example, 1 wt% to 30 wt% or 1 wt% to 20 wt% of the monomer mixture.

[0181] The (meth)acryl-based monomer having a heterocycloaliphatic group can include a (meth)acrylate having a C4 to C9 heterocycloaliphatic group including at least one of nitrogen, oxygen, or sulfur. Specifically, the (meth)acryl-based monomer having a heterocycloaliphatic group can include (meth)acryloyl morpholine, but is not limited thereto. The content of the (meth)acryl-based monomer having a heterocycloaliphatic group can be 0 wt% to 50 wt%, for example, 0 wt% to 10 wt% of the monomer mixture.

[0182] The adhesive resin can include a (meth)acryl-based copolymer of a monomer mixture including 70 wt% to 99.99 wt%, for example, 90 wt% to 99.5 wt% of a (meth)acryl-based monomer having an alkyl group, 0.01 wt% to 30 wt%, for example, 0.5 wt% to 10 wt% of a (meth)acryl-based monomer having a hydroxyl group. When each monomer constituting the adhesive resin has the above range, the adhesive strength can be easily secured.

[0183] The curing agent can include an isocyanate-based curing agent. The content of the curing agent can be 0.01 parts by weight to 20 parts by weight, for example, 0.01 parts by weight to 10 parts by weight, for example, 0.1 parts by weight to 4 parts by weight, based on 100 parts by weight of the adhesive resin. When the curing agent has the above range, the composition can be crosslinked to form an adhesive layer and prevent a decrease in transparency and poor reliability due to excessive use thereof.

[0184] The composition can further include conventional additives such as a silane coupling agent, an antioxidant, a tackifying resin, a plasticizer, an antistatic agent, a rework agent, and a curing catalyst. The content of the silane coupling agent can be 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, for example, 0.1 to 4 parts by weight, based on 100 parts by weight of the adhesive resin. When the silane coupling agent has the above range, adhesion can be controlled and reliability defects can be prevented.

[0185] The composition for the adhesive layer can be a solvent-free type or can further include a conventional organic solvent to improve coating properties.

[0186] The adhesive layer can have a thickness of 1 to 50 μm, for example, 5 to 25 μm. When the adhesive layer has a thickness within the above range, it can be easily used in a display device.

[0187] According to another embodiment, a display device including an anti-reflection film is provided. For example, a display device including an anti-reflection film and a quantum dot-containing layer can be provided.

[0188] For example, the display device can further include a light source, a color filter, and a substrate.

[0189] For example, the display device can have a stacked structure in which the quantum dot-containing layer can be disposed on the light source, the color filter can be disposed on the quantum dot-containing layer, the substrate can be disposed on the color filter, and the anti-reflection film can be disposed on the substrate (see Figure 3 and Figure 4 ).

[0190] For example, the light source can be a blue light source.

[0191] For example, the substrate can be a glass substrate.

[0192] In addition to the quantum dots, the components constituting the quantum dot-containing layer can further include an adhesive resin, a reactive unsaturated compound, a photopolymerization initiator, a diffusing agent, and other additives, which will be described later.

[0193] The quantum dots can have a maximum fluorescence emission wavelength (fluorescence λmax) in the wavelength range of 350 to 550 nm of 400 to 500 nm.

[0194] The quantum dots can have a full width at half maximum (FWHM) in the range of 20 to 100 nm, for example, 20 to 50 nm. When the quantum dots have a full width at half maximum (FWHM) within the range, the quantum dots have high color purity, and thus have an effect of improving color reproducibility when used as a color material in a color filter.

[0195] The quantum dot can be an organic material, an inorganic material, or a mixture (hybrid) of an organic material and an inorganic material.

[0196] The quantum dot can each independently include a core and a shell surrounding the core, and herein, the core and the shell can have, for example, a structure including a core of Group II-IV, Group III-V, etc., a core / shell, a core / first shell / second shell, an alloy, an alloy / shell, etc., each independently, but are not limited thereto.

[0197] For example, the core can 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 can include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

[0198] In one embodiment, since the interest in the environment has greatly increased worldwide recently, and the regulation on toxic materials has also been strengthened, a cadmium-free light emitting material (InP / ZnS) having little low quantum efficiency (quantum yield) but being environmentally friendly is used instead of a light emitting material having a core based on cadmium, but is not necessarily limited thereto.

[0199] The quantum dot having a core / shell structure can have an overall size (average particle diameter) including the shell of 1 nm to 15 nm, for example, 5 nm to 15 nm, but its structure is not particularly limited.

[0200] For example, the quantum dot can be a red quantum dot, a green quantum dot, or a combination thereof. For example, the quantum dot can include green quantum dots and red quantum dots. In this case, the content of the green quantum dots can be greater than the content of the red quantum dots. The red quantum dots can have an average particle diameter of 10 nm to 15 nm. The green quantum dots can have an average particle diameter of 5 nm to 8 nm.

[0201] Simultaneously, dispersants can be used to ensure the dispersion stability of quantum dots. Dispersants help to uniformly disperse light-conversion materials such as quantum dots in a curable composition and include nonionic, anionic, or cationic dispersants. Specifically, dispersants may include polyalkylene glycols or their esters, polyoxyethylene, polyhydric alcohol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonates, sulfonates, carboxylates, carboxylates, alkyl amide alkylene oxide addition products, and alkylamines, and may be used alone or as a mixture of two or more. Based on the solids content of the light-conversion material, such as quantum dots, the dispersant may be used in amounts from 0.1 wt% to 100 wt%, for example, from 10 wt% to 20 wt%.

[0202] Based on 100 parts by weight of the components constituting the quantum dot layer, the quantum dot content can be from 1 to 40 parts by weight, for example, from 1 to 10 parts by weight. When the quantum dots are contained within the above range, the light conversion efficiency is improved while the patterning and development properties are not compromised, thereby achieving excellent processability.

[0203] Adhesive resins may include acryloyl-based resins, epoxy resins, or combinations thereof.

[0204] Acryloyl-based resins are copolymers of a first olefinically unsaturated monomer and a second olefinically unsaturated monomer that can be copolymerized therewith, and are resins containing at least one repeating unit based on an acrylate group.

[0205] First-order olefinic unsaturated monomers are olefinic unsaturated monomers containing at least one carboxyl group. Examples of monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0206] The content of the first olefin unsaturated monomer can be from 5 wt% to 50 wt%, for example, from 10 wt% to 40 wt%, depending on the total amount of acryloyl-based adhesive resin.

[0207] The second ethylenically unsaturated monomer can be an aromatic vinyl compound such as styrene, a-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, and the like; an unsaturated carboxylic ester compound such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and the like; an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, and the like; a carboxylic acid vinyl ester compound such as vinyl acetate, vinyl benzoate, and the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth)acrylate, and the like; a vinyl cyanide compound such as (meth)acrylonitrile, and the like; an unsaturated amide compound such as (meth)acrylamide, and the like; and the like, and can be used alone or in a mixture of two or more kinds.

[0208] Specific examples of the acryl-based resin can be polymethylbenzyl acrylate, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and can be used alone or as a mixture of two or more kinds.

[0209] The acryl-based resin can have a weight average molecular weight of 1,000 g / mol to 15,000 g / mol. When the acryl-based resin has a weight average molecular weight within this range, close contact properties with a substrate and physical and chemical properties are improved and the viscosity is suitable.

[0210] The epoxy resin can be a thermally polymerizable monomer or oligomer, and can include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0211] The epoxy resin can further include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether, but is not necessarily limited thereto.

[0212] The commercially available product of the compound can be YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co., Ltd.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 or EOCN-1027 of Nippon Kayaku Co. Ltd. and EPIKOTE 180S75 of Yuka Shell Epoxy Co., Ltd.; bisphenol A epoxy resins such as EPIKOTE 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 of Yuka Shell Epoxy Co., Ltd.; bisphenol F epoxy resins such as EPIKOTE 807 and 834 of Yuka Shell Epoxy Co., Ltd.; phenol novolac epoxy resins such as EPIKOTE 152, 154 or 157H65 of Yuka Shell Epoxy Co., Ltd. and EPPN 201, 202 of Nippon Kayaku Co., Ltd.; cyclic aliphatic epoxy resins such as CY175, CY177 and CY179 of CIBA-GEIGY A.G Corp., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 of U.C.C., Showdyne 509 of Showa Denko K.K., Araldite CY-182 of CIBA-GEIGY A.G Corp., CY-192 and CY-184 of Dainippon Ink & Chemicals Inc., EPICLON 200 and 400, EPIKOTE 871, 872 of Yuka Shell Epoxy Co. and EP1032H60, ED-5661 and ED-5662 of Celanese Coating Corp.; aliphatic polyglycidyl ether can be EPIKOTE 190P and 191P of Yuka Shell Epoxy Co., EPOLITE 100MF of Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EPIOL TMP of Nihon Yushi K.K. and the like.

[0213] The content of the adhesive resin can be 1 to 40 parts by weight, for example, 5 to 20 parts by weight, based on 100 parts by weight of the components constituting the quantum dot-containing layer. When the adhesive resin is contained within the above range, excellent pattern sensitivity, developability, resolution and linearity can be obtained.

[0214] The reactive unsaturated compound can be used by mixing monomers or oligomers generally used for conventional photocurable compositions and thermosetting compositions.

[0215] The reactive unsaturated compound can be an acrylate compound. For example, at least one of ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, phenol novolac acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a mixture thereof can be used.

[0216] The reactive unsaturated compound can be treated with an acid anhydride to improve developability.

[0217] The content of the reactive unsaturated compound can be 1 to 10 parts by weight, for example, 1 to 5 parts by weight, based on 100 parts by weight of the components constituting the quantum dot-containing layer. When the reactive unsaturated compound is contained within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability, heat resistance, light resistance, chemical resistance, resolution, and close contact performance of the pattern.

[0218] The photopolymerization initiator can be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, an oxime compound, or the like.

[0219] Examples of the acetophenone compound can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, or the like.

[0220] Examples of the benzophenone compound can be benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, or the like.

[0221] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0222] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0223] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)- s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0224] Examples of oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one, etc. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylthioalkylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthioalkylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthioalkylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylthioalkylphenyl)-but-1-one oxime-O-acetate.

[0225] In addition to the compounds mentioned above, photopolymerization initiators may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc.

[0226] Photopolymerization initiators can be used with photosensitizers that can induce a chemical reaction by absorbing light, being excited, and then transferring their energy.

[0227] Examples of the photosensitizer can be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, or the like.

[0228] The content of the photopolymerization initiator can be 0.1 parts by weight to 10 parts by weight, for example, 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of components constituting the quantum dot-containing layer. When the photopolymerization initiator is contained within the above range, the balance between sensitivity and developability during exposure is improved, so that a pattern having excellent resolution without a residual film can be obtained.

[0229] The quantum dot-containing layer can further include a diffusing agent.

[0230] For example, the diffusing agent can include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or a combination thereof.

[0231] The diffusing agent reflects light that is not absorbed by the aforementioned quantum dot, so that the reflected light can be absorbed by the quantum dot again. In other words, the diffusing agent increases the amount of light absorbed in the quantum dot, thereby increasing the light conversion efficiency of the curable composition.

[0232] The average particle diameter (D 50 ) of the diffusing agent can be in the range of 150 nm to 250 nm, specifically, 180 nm to 230 nm. When the average particle diameter of the diffusing agent is in the range, a more excellent light scattering effect can be obtained, and the light conversion efficiency can be improved.

[0233] The content of the diffusing agent can be 0.1 wt% to 20 wt%, for example, 0.1 wt% to 5 wt%, based on the solid content of 100 parts by weight of components constituting the quantum dot-containing layer. When the content of the diffusing agent is less than 0.1 wt% based on 100 parts by weight of components constituting the quantum dot-containing layer, it is difficult to expect the effect of improving the light conversion efficiency by using the diffusing agent, and when the content of the diffusing agent is greater than 20 wt%, the pattern properties can be deteriorated.

[0234] In order to improve the stability and dispersibility of the quantum dot, the quantum dot-containing layer can further include a thiol-based additive.

[0235] The thiol-based additive can replace the shell surface of the quantum dot, and can improve the dispersion stability of the quantum dot in a solvent and can stabilize the quantum dot.

[0236] The thiol-based additive can have one or more, for example, 2 to 10, for example, 2 to 4, thiol groups (-SH) at the terminal, depending on its structure.

[0237] For example, the thiol-based additive can include at least two functional groups represented by Chemical Formula 15.

[0238] [Chemical Formula 15]

[0239]

[0240] In Chemical Formula 15,

[0241] L 7 and L 8 are each independently 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.

[0242] For example, the thiol-based additive can be represented by Chemical Formula 16.

[0243] [Chemical Formula 16]

[0244]

[0245] In Chemical Formula 16,

[0246] L 7 and L 8 are each independently 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

[0247] u1 and u2 are each independently an integer of 0 or 1.

[0248] For example, in Chemical Formula 15 and Chemical Formula 16, L 7 and L 8 may be each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene.

[0249] Specific examples of the thiol-based additive can be selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate) represented by Chemical Formula 16a, trimethylolpropane tri(3-mercaptopropionate) represented by Chemical Formula 16b, pentaerythritol tetra(mercaptoacetate) represented by Chemical Formula 16c, trimethylolpropane tri(2-mercaptoacetate) represented by Chemical Formula 16d, diol di-3-mercaptopropionate represented by Chemical Formula 16e, and combinations thereof.

[0250] [Chemical Formula 16a]

[0251]

[0252] [Chemical Formula 16b]

[0253]

[0254] [Chemical Formula 16c]

[0255]

[0256] [Chemical Formula 16d]

[0257]

[0258] [Chemical Formula 16e]

[0259]

[0260] The content of the thiol-based additive can be 0.1 parts by weight to 10 parts by weight, for example, 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of the components constituting the quantum dot-containing layer. When the thiol-based additive is included in this range, the stability of the light conversion material such as the quantum dot can be improved, for example, the thiol group in the component reacts with the acrylic group of the resin or the monomer to form a covalent bond, and thus the heat resistance of the light conversion material such as the quantum dot can be improved.

[0261] The quantum dot-containing layer can further include a polymerization inhibitor including a hydroquinone-based compound, a catechol-based compound, or a combination thereof. Since the quantum dot-containing layer further includes the hydroquinone-based compound, the catechol-based compound, or the combination thereof, crosslinking can be prevented from occurring at room temperature during exposure after printing (coating) the composition including the quantum dot.

[0262] For example, the hydroquinone-based compound, the catechol-based compound, or the combination thereof can include hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, tert-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium, or a combination thereof, but is not necessarily limited thereto.

[0263] The hydroquinone compound, the catechol compound, or the combination thereof can be used in the form of a dispersion, and the content of the polymerization inhibitor in the form of a dispersion can be 0.001 parts by weight to 1 part by weight, for example, 0.01 parts by weight to 0.1 parts by weight, based on 100 parts by weight of components constituting the layer including quantum dots and a fluorescent dye or the quantum dot-containing layer (excluding the fluorescent dye). When the stabilizer is contained within the above range, the problem of aging at room temperature can be solved and a decrease in sensitivity and surface peeling can be prevented.

[0264] The quantum dot-containing layer can further include malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, or a combination thereof (in addition to the thiol-based additive and the polymerization inhibitor).

[0265] In addition, the quantum dot-containing layer can further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, or the like, to improve the close contact property thereof with the substrate.

[0266] Examples of the silane-based coupling agent can include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, or the like, which can be used alone or as a mixture of two or more.

[0267] The content of the silane coupling agent can be 0.01 parts by weight to 10 parts by weight, based on 100 parts by weight of components constituting the quantum dot-containing layer. When the silane coupling agent is contained within the range, close contact property, storability, or the like can be improved.

[0268] In addition, if necessary, the quantum dot-containing layer can further include a surfactant, for example, a fluorine-based surfactant, to improve the coating and prevent defects.

[0269] Examples of the fluorine-based surfactant can be BM-1000 and BM-1100 of BM Chemie Inc. , F 172 , F 173 , and F 183 of Dainippon Ink Kagaku Kogyo Co., Ltd. , FULORAD FC-170C , FULORAD FC-430 and FULORAD FC-431 SURFLON S-112 by ASAHI Glass Co., Ltd. SURFLON S-113 SURFLON S-131 SURFLON S-141 SURFLON S-145 SH-28PA by Toray Silicone Co., Ltd. SH-190 SH-193 SZ-6032 SF-8428 F-482, F-484, F-478, F-554, etc. by DIC Co., Ltd.

[0270] The content of the fluorine-based surfactant can be 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the components constituting the quantum dot-containing layer. When the fluorine-based surfactant is included in this range, excellent wetting of the glass substrate and uniform coating can be ensured without causing stains.

[0271] Furthermore, other additives such as antioxidants, stabilizers can also be added to the quantum dot-containing layer within a range that does not impair the physical properties.

[0272] The method of manufacturing each quantum dot-containing layer can include forming a pattern by jet ink spraying (S1) a curable composition containing the above components, etc. on a substrate; and curing the pattern (S2).

[0273] (S1) Formation of Pattern

[0274] The curable composition is coated on the substrate in a thickness of 0.5 to 10 μm by the jet ink dispersion method. According to the jet ink dispersion liquid, the pattern can be formed by repeatedly dispersing the desired color one by one or simultaneously dispersing the desired colors to simplify the process.

[0275] (S2) Curing

[0276] The pattern obtained by curing can obtain a cured resin film. At this time, a thermal curing process is preferred as the curing method. The thermal curing process can be a process of first removing the solvent in the curable composition by heating at a temperature of greater than or equal to about 100°C for about 3 minutes, and then curing by heating at a temperature of 160°C to 300°C, more desirably at a temperature of 180°C to 250°C for about 30 minutes.

[0277] Further, each quantum dot layer can be manufactured without inkjet. The manufacturing method in this case includes coating a curable composition containing the above components on a substrate subjected to predetermined pretreatment, using a suitable method such as spin coating, roll coating, spray coating, and the like, at a thickness of, for example, 0.5 to 10 μm, and irradiating the resultant with light to form a pattern required for a color filter. As a light source for irradiation, UV, electron beam, or X-ray can be used, and, for example, UV in the region of 190 to 450 nm, specifically, 200 to 400 nm can be irradiated. In the irradiation process, a photoresist mask can also be used. After the irradiation treatment in this way, the composition layer irradiated with the light source is treated with a developer. At this time, the unexposed portion of the composition layer is dissolved to form a pattern required for a color filter. By repeating this process according to the number of colors required, a color filter having a desired pattern can be obtained. Further, when the image pattern obtained by development through the above process is heated again or cured by irradiation with actinic rays, the resistance to cracking and solvent resistance can be improved.

[0278] The curable composition can further include a solvent.

[0279] The solvent can include compounds such as alcohols such as methanol, ethanol, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, and the like; cellulose acetate solvents such as methyl cellulose acetate, ethyl cellulose acetate, diethyl cellulose 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-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactic acid alkyl esters such as methyl lactate, ethyl lactate, and the like; glycolic acid alkyl esters such as methyl glycolate, ethyl glycolate, butyl glycolate, and the like; acetic acid alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, and the like; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, and the like; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and the like; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, and the like; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and the like; 2-alkoxy-2-methylpropionic acid alkyl esters 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 keto acid esters such as ethyl pyruvate. In addition, N-methyl formamide, N,N-dimethyl formamide, N-methyl formanilide, N-methyl acetamide, N,N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, dimethyl adipate, and the like can also be used, but are not limited thereto.

[0280] For example, the solvent can desirably be a glycol ether such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, or the like; an ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate, or the like; an ester such as 2-hydroxyethyl propionate, or the like; a carbitol such as diethylene glycol monomethyl ether, or the like; a propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, or the like; an alcohol such as ethanol, or the like; or a combination thereof.

[0281] For example, the solvent can include propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, dimethylacetamide, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, gamma-butyrolactone, dimethyl adipate, or a combination thereof.

[0282] The solvent can be included in a balanced amount based on the total amount of the curable composition.

[0283] Hereinafter, embodiments of the present application are described. However, these embodiments should not be construed in any sense as limiting the scope of the present application.

[0284] (Synthesis of compound)

[0285] Synthesis Example 1: Synthesis of compound represented by Chemical Formula 10

[0286] (1) 35 g of chlorosulfonic acid was added to a 500 ml round bottom flask, and then stirred at less than 30°C. 5 g of CuPC (copper (II) phthalocyanine) was slowly added thereto at less than or equal to 50°C, and then stirred at 90°C for 3 hours. The reactant was again cooled to less than 30°C, and thionyl chloride (4 g) was slowly added dropwise thereto at less than 30°C. When the addition was completed, the reactant was stirred at 95°C for 1 hour. Subsequently, the reactant was cooled to room temperature and neutralized by using 300 mL of water at less than or equal to 10°C. Then, the solid therein was washed with water several times.

[0287] (2) The filtered solid was put into a flask, 100 mL of water was added thereto, and then stirred and cooled to 10°C. Subsequently, cyclohexylamine (3.4 g) was slowly added dropwise thereto, and then stirred for 1 hour. After the reaction temperature was increased to 65°C, the mixture was reacted for 6 hours. The reactant was filtered and washed, and the resulting solid therein was dried to obtain 53 g of a compound represented by Chemical Formula 10.

[0288] [Chemical Formula 10]

[0289]

[0290] [M+H] + (1222), λmax = (673) nm

[0291] Synthesis Example 2: Synthesis of a compound represented by chemical formula 17

[0292] Except that cyclopentylamine was used instead of cyclohexylamine, the compound represented by chemical formula 17 was synthesized in the same manner as in Synthesis Example 1.

[0293] [Chemical Formula 17]

[0294]

[0295] [M+H] + (1165), λmax=(673)nm

[0296] Comparative Synthesis Example 1: Synthesis of a compound represented by chemical formula 18

[0297] 4-(2-phenylphenoxy)phthalonitrile (4 g), diazabicycloundecane-7-ene (2.5 g), and 40 mL of 1-pentenol were placed in a 250 mL flask, and the solid was dissolved by heating. Copper acetate (1.8 g) was added, and the mixture was refluxed while heating. When the reaction was complete, the solvent was removed, and the residue was purified by column chromatography. The resulting solid was dissolved in an appropriate amount of dichloromethane and then crystallized in methanol. The resulting solid was filtered and dried under vacuum to synthesize the compound represented by chemical formula 18.

[0298] [Chemical Formula 18]

[0299]

[0300] [M+H] + (1249), λmax=(673)nm

[0301] Comparative Synthesis Example 2: Synthesis of the compound represented by chemical formula 19

[0302] Except that 2-ethylhexylamine was used instead of cyclohexylamine, the compound represented by chemical formula 19 was synthesized in the same manner as in Synthesis Example 1.

[0303] [Chemical Formula 19]

[0304]

[0305] [M+H] + (1342), λmax=(672)nm

[0306] Comparative Synthesis Example 3: Synthesis of the compound represented by chemical formula 20

[0307] Except that leucine methyl ester was used instead of cyclohexylamine, the compound represented by chemical formula 20 was synthesized in the same manner as in Synthesis Example 1.

[0308] [Chemical Formula 20]

[0309]

[0310] [M+H] + (1406), λmax = (671) nm

[0311] Preparation Example: Preparation of Copolymer of Composition for Adhesion Layer

[0312] A monomer mixture of 100 parts by weight including 99 parts by weight of n-butyl acrylate and 1 part by weight of 2-hydroxyethyl acrylate and 150 parts by weight of ethyl acetate was put into a 1L reactor equipped with a condenser to facilitate temperature control, in which nitrogen was refluxed, and while stirring the flask, nitrogen was introduced thereinto for 1 hour to replace oxygen in the reactor with nitrogen, and then the reactor was maintained at 70°C. 0.06 parts by weight of 2,2'-azobisisobutyronitrile was added thereto as an initiator, and then the reaction was carried out for 8 hours to prepare a solution containing a (meth)acryl-based copolymer. The Tg of the (meth)acryl-based copolymer was -46°C, and the weight average molecular weight was 1,100,000 g / mol. Ethyl acetate was added thereto to prepare a 19.4 wt% (meth)acryl-based copolymer solution.

[0313] Example 1

[0314] The composition for a thermosetting coating layer was directly coated on the lower surface of a PET film of a base film which was an anti-reflection film (an anti-reflection film in which a hard coating layer, a high-refractive layer, and a low-refractive layer were sequentially laminated on the upper surface of a PET film as a base film, reflectance: 0.2%, DNP, LLC.) using a bar coater, and then dried in a 90°C oven for 4 minutes to make a sheet for an optical member including a 20 μm-thick thermosetting coating layer.

[0315] Based on 100 parts by weight of the (meth)acryl-based copolymer prepared in the preparation example, 0.193 parts by weight of an XDI-based isocyanate-based crosslinking agent (solid: 75%, TD-75, Soken Chemical & Engineering Co., Ltd.) and 0.154 parts by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin Etsu Chemical Co., Ltd.) as a silane coupling agent were mixed. As a selective wavelength absorbing dye, 0.06 parts by weight of the compound of Synthesis Example 1 (represented by Chemical Formula 10) and 25 parts by weight of methyl ethyl ketone were added thereto, to prepare a composition for an adhesive layer. The composition for the adhesive layer was applied on a PET release film, dried in an oven at 90°C for 4 minutes, to make an adhesive sheet of 20 μm in thickness.

[0316] The obtained adhesive sheet was laminated on the lower surface of a PET film of a base film that was an anti-reflection film (anti-reflection film in which a hard coat layer, a high-refractive layer, and a low-refractive layer were sequentially laminated on the upper surface of a PET film as a base film, reflectance: 0.2%, DNP, LLC.), to manufacture the optical element of Example 1 in which the release film, the adhesive layer, and the anti-reflection film were sequentially laminated.

[0317] Example 2

[0318] An optical element was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 2 (represented by Chemical Formula 17) was used instead of the compound of Synthesis Example 1 (represented by Chemical Formula 10).

[0319] Comparative Example 1

[0320] An optical element was manufactured in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 1 (represented by Chemical Formula 18) was used instead of the compound of Synthesis Example 1 (represented by Chemical Formula 10).

[0321] Comparative Example 2

[0322] An optical element was manufactured in the same manner as in Example 1, except that a phthalocyanine dye (maximum absorption wavelength: 752 nm, IN-88, Ukseung Chemical Co., Ltd.) was used instead of the compound of Synthesis Example 1 (represented by Chemical Formula 10).

[0323] Comparative Example 3

[0324] An optical element was manufactured in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 2 (represented by Chemical Formula 19) was used instead of the compound of Synthesis Example 1 (represented by Chemical Formula 10).

[0325] Comparative Example 4

[0326] An optical element was produced in the same manner as in Example 1, except that the compound represented by Chemical Formula 20 of Comparative Synthesis Example 3 was used instead of the compound represented by Chemical Formula 10 of Synthesis Example 1.

[0327] Evaluation 1: Transmittance

[0328] The transmittance of the optical elements according to Example 1 and Comparative Example 2 at each wavelength was measured using a UV-visible spectrophotometer, and the results are shown in Table 1.

[0329] [Table 1]

[0330]

[0331] Referring to Table 1, the optical element of Example 1 and the optical element of Comparative Example 2 absorb light equally in the region of 673 nm, exhibit almost the same transmittance in the regions of 460 nm and 630 nm, but the optical element of Example 1 shows higher transmittance than the optical element of Comparative Example 2, thus improving the light emission characteristics in the corresponding regions.

[0332] Evaluation 2: Light Resistance Reliability

[0333] In order to confirm whether the light resistance reliability was evaluated, the light transmittance of each compound at the maximum absorption wavelength was measured in a xenon test chamber (Q-SUN) under the conditions [light source lamp: xenon lamp, irradiation intensity: 0.35 W / cm 2 , irradiation temperature: 63°C, irradiation time: 500 hours, irradiation direction: from the side of the antireflection film] according to the optical elements of Examples 1, 2, and Comparative Examples 1 to 4, and the light resistance reliability was evaluated using the change in light transmittance, and the results are shown in Table 2.

[0334] [Table 2]

[0335] Light resistance reliability (ΔT%) Example 1 0.1 Example 2 0.1 Comparative Example 1 12.1 Comparative Example 2 94.2 Comparative Example 3 1.3 Comparative Example 4 5.4

[0336] Referring to Table 2, as in Examples 1 and 2, the antireflection film containing a dye having a cyclic substituent exhibited excellent light resistance reliability compared to the antireflection films contained in Comparative Examples 1 to 4.

[0337] In particular, the antireflection film containing a dye having a zinc phthalocyanine structure according to Comparative Example 2 exhibited very weak light resistance reliability.

[0338] While the application has been described in connection with the exemplary embodiments currently considered to be the most practical and preferred, it is to be understood that the application is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements. Accordingly, the above-described embodiments are to be considered as illustrative only. The described embodiments are not intended to limit the scope of the application but rather are presented as examples from a number of alternative embodiments in which various modifications can be made and equivalents can be substituted for elements thereof. It will be appreciated that those skilled in the art will be able to devise modifications of the aforementioned embodiment or will be able to appreciate aspects of the application that are evident within the context of the various embodiments.

[0339] [Legend of Reference Numerals]

[0340] 10 blue light source

[0341] 20 quantum dot-containing layer

[0342] 30 color filter

[0343] 40 substrate

[0344] 50 adhesive layer

[0345] 60 dye-containing layer

[0346] 70 antireflection layer

[0347] 80 antireflection film

[0348] 100 display device

Claims

1. An antireflective film comprising a compound represented by chemical formula 1: [Chemical Formula 1] in, In chemical formula 1, M is Cu. R 1 To R 16 Each is independently hydrogen or a sulfonamide group represented by chemical formula 2, and R 1 To R 4 At least one of them is a sulfonamide group represented by chemical formula 2. R 5 To R 8 At least one of them is a sulfonamide group represented by chemical formula 2. R 9 To R 12 At least one of them is a sulfonamide group represented by chemical formula 2, and R 13 To R 16 At least one of them is a sulfonamide group represented by chemical formula 2; [Chemical Formula 2] In chemical formula 2, R 17 and R 18 Each is independently hydrogen or a C3 to C6 cycloalkyl group. R 17 and R 18 At least one of them is a C3 to C6 cycloalkyl group, and * indicates the portion bonded to the benzene ring of Formula 1.

2. The antireflective film according to claim 1, wherein... The compound is represented by chemical formula 3: [Chemical Formula 3] in, In chemical formula 3, M is Cu. n1 to n4 are all 1, and n5 is an integer from 1 to 2.

3. The antireflective film according to claim 1, wherein... The compounds include those represented by any one of chemical formulas 10 to 14: [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] 4. The antireflective film according to any one of claims 1 to 3, wherein The antireflective film includes an adhesive layer and an antireflective layer on the adhesive layer, and the compound is contained in the adhesive layer.

5. The antireflective film according to any one of claims 1 to 3, wherein The antireflective film includes an adhesive layer, a dye-containing layer, and an antireflective layer on the dye-containing layer, and The compound is contained in the dye-containing layer.

6. A display device comprising the antireflective film according to any one of claims 1 to 5.

7. The display device according to claim 6, wherein The display device also includes a quantum dot layer.

8. The display device according to claim 7, wherein The display device also includes a light source, a color filter, and a substrate.

9. The display device according to claim 8, wherein In the display device, The content sub-dot layer is disposed on the light source. The color filter is disposed on the content sub-dot layer. The substrate is disposed on the color filter, and The anti-reflective film is disposed on the substrate.

10. The display device according to claim 8, wherein The substrate includes a glass substrate.

11. The use of compounds represented by chemical formula 1 in the preparation of antireflective films. [Chemical Formula 1] in, In chemical formula 1, M is Cu. R 1 To R 16 Each is independently hydrogen or a sulfonamide group represented by chemical formula 2, and R 1 To R 4 At least one of them is a sulfonamide group represented by chemical formula 2, R 5 To R 8 At least one of them is a sulfonamide group represented by chemical formula 2, R 9 To R 12 At least one of them is a sulfonamide group represented by chemical formula 2, and R 13 To R 16 At least one of them is a sulfonamide group represented by chemical formula 2; [Chemical Formula 2] In chemical formula 2, R 17 and R 18 Each is independently hydrogen or a C3 to C6 cycloalkyl group. R 17 and R 18 At least one of them is a C3 to C6 cycloalkyl group, and *Indicates the portion bonded to the benzene ring of chemical formula 1. The compound in question is a red absorbing dye.

12. The use according to claim 11, wherein The dye has a maximum absorption peak at wavelengths between 650 nm and 750 nm.

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