Core-shell dyes, photosensitive resin composition containing the same, photosensitive resin film, color filter, and CMOS image sensor

Abstract

The present invention provides a core-shell dye, a photosensitive resin composition containing the core-shell dye, a photosensitive resin film produced using the photosensitive resin composition, a color filter including the photosensitive resin film, and a complementary metal oxide semiconductor image sensor including the color filter, the core-shell dye including a core containing a compound represented by a specific chemical formula, and a shell surrounding the core.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a core-shell dye, a photosensitive resin composition including the same, a photosensitive resin film manufactured using the same, a color filter including the same, and a complementary metal-oxide semiconductor image sensor including the same. BACKGROUND

[0002] Among many types of displays, liquid crystal displays have advantages of lightness, thinness, low cost, low operating power consumption, and improved adherence to integrated circuits, and have been more widely used for laptop computers, monitors, and television (TV) screens. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an indium tin oxide (ITO) pixel electrode are formed, and an upper substrate on which an active circuit portion including a liquid crystal layer, a thin film transistor, and a capacitor layer, and an ITO pixel electrode are formed. Each pixel is formed by forming a color filter in a pixel area by sequentially stacking a plurality of pixel portions (typically formed of three primary colors such as red (R), green (G), and blue (B)) in a predetermined order, and a black matrix layer is disposed on a transparent substrate in a predetermined pattern to form a boundary between pixels.

[0003] A pigment dispersion method, which is one of methods of forming a color filter, provides a colored thin film by repeating a series of processes such as coating a photopolymerizable composition including a colorant on a transparent substrate including a black matrix, exposing the formed pattern, removing unexposed portions using a solvent, and performing thermal curing. A color photosensitive resin composition for manufacturing a color filter according to the pigment dispersion method generally includes an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, etc. The pigment dispersion method is actively applied to the manufacture of liquid crystal displays (LCDs) such as mobile phones, laptop computers, monitors, and televisions. However, photosensitive resin compositions for manufacturing color filters according to the pigment dispersion method recently require improved performance and excellent pattern characteristics. Specifically, there is an urgent need for high color reproducibility and high brightness and high contrast characteristics.

[0004] An image sensor is a component used to capture an image in a portable cellular phone camera or a digital still camera (DSC). The image sensor can be classified as a charge-coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor depending on a manufacturing process and an application method. A color imaging device for a charge-coupled device image sensor or a complementary metal oxide semiconductor image sensor includes a color filter each having a color filter segment that mixes red, green, and blue primary colors, and colors are separated. A latest color filter mounted in the color imaging device has a pattern size of 2 μm or less than 2 μm, which is 1 / 100 to 1 / 200 of a pattern size of a conventional color filter pattern for an LCD. Accordingly, increased resolution and reduced pattern residue are important factors that determine the performance of the device.

[0005] A color filter manufactured using a pigment-type photosensitive resin composition has limitations in brightness and contrast due to the size of the pigment particles. In addition, a color imaging device for an image sensor requires a smaller dispersed particle diameter to form a fine pattern. In order to correspond to these requirements, attempts have been made to realize a color filter having improved brightness and contrast by introducing a dye that does not form a particle instead of a pigment to prepare a photosensitive resin composition suitable for the dye. However, the dye has poorer durability (e.g., light resistance and heat resistance, etc.) than the pigment, and thus brightness can be deteriorated. SUMMARY

[0006] TECHNICAL CHALLENGES

[0007] An embodiment provides a core-shell dye having excellent coloring strength, chemical resistance, and contrast properties due to a low fluorescence quantum efficiency and a high light absorption efficiency.

[0008] Another embodiment provides a photosensitive resin composition including the core-shell dye.

[0009] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0010] Another embodiment provides a color filter including the photosensitive resin film.

[0011] Another embodiment provides a CMOS image sensor including the color filter.

[0012] TECHNICAL SOLUTION

[0013] Embodiments provide a core-shell dye including: a core including a compound represented by Chemical Formula 1 or Chemical Formula 2, and a shell surrounding the core.

[0014] [Chemical Formula 1]

[0015]

[0016] [Chemical Formula 2]

[0017]

[0018] In Chemical Formula 1 or Chemical Formula 2,

[0019] R 1 to R 7 each independently is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, a substituted or unsubstituted C2 to C20 heteroaryl, or a combination thereof.

[0020] R 1 to R 7 each independently can be a substituted or unsubstituted C1 to C20 alkyl, or a functional group represented by Chemical Formula 3.

[0021] [Chemical Formula 3]

[0022]

[0023] In Chemical Formula 3,

[0024] R a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C1 to C20 alkoxy, a nitro group (-NO2), a glycidyl group, a (meth)acrylate group, a carbamate group, or a combination thereof.

[0025] The core-shell dye can have a molar extinction coefficient greater than or equal to 3.1 x 10 5 M -1 ·cm -1 and a fluorescence quantum efficiency less than or equal to 5%.

[0026] The compound represented by Chemical Formula 1 can be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3, and the compound represented by Chemical Formula 2 can be represented by any one of Chemical Formula 2-1 to Chemical Formula 2-4.

[0027] [Chemical Formula 1-1]

[0028]

[0029] [Chemical Formula 1-2]

[0030]

[0031] [Chemical Formula 1-3]

[0032]

[0033] [Chemical Formula 2-1]

[0034]

[0035] [Chemical Formula 2-2]

[0036]

[0037] [Chemical Formula 2-3]

[0038]

[0039] [Chemical Formula 2-4]

[0040]

[0041] The shell can be represented by Chemical Formula 4 or Chemical Formula 5.

[0042] [Chemical Formula 4]

[0043]

[0044] [Chemical Formula 5]

[0045]

[0046] In Chemical Formula 4 or Chemical Formula 5,

[0047] R 8 and R 9 each independently is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C1 to C20 alkoxy, a nitro group (-NO2), a glycidyl group, a (meth)acrylate group, a carbamate group, or a combination thereof,

[0048] L a to L d each independently is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and

[0049] n is an integer of 1 to 4.

[0050] L a to L d each independently can be a substituted or unsubstituted C1 to C10 alkylene group.

[0051] The shell can be represented by Chemical Formula 4-1 or Chemical Formula 5-1.

[0052] [Chemical Formula 4-1]

[0053]

[0054] [Chemical Formula 5-1]

[0055]

[0056] In Chemical Formula 4-1 and Chemical Formula 5-1,

[0057] R 8 and R 9 each independently is hydrogen, a substituted or unsubstituted C1to C20alkyl, a substituted or unsubstituted C1to C20alkoxy, a nitro group (-NO2), a glycidyl group, a (meth)acrylate group, a carbamate group, or a combination thereof.

[0058] The shell can be represented by any one of Chemical Formula 4-a to Chemical Formula 4-d, and Chemical Formula 5-a to Chemical Formula 5-d.

[0059] [Chemical Formula 4-a]

[0060]

[0061] [Chemical Formula 4-b]

[0062]

[0063] [Chemical Formula 4-c]

[0064]

[0065] [Chemical Formula 4-d]

[0066]

[0067] [Chemical Formula 5-a]

[0068]

[0069] [Chemical Formula 5-b]

[0070]

[0071] [Chemical Formula 5-c]

[0072]

[0073] [Chemical Formula 5-d]

[0074]

[0075] The shell can have a cage width of 6.5 Angstroms to 7.5 Angstroms.

[0076] The core can have a length of 1 nm to 3 nm.

[0077] The core can have a maximum absorption peak at a wavelength of 590 nm to 670 nm.

[0078] The core-shell dye can be represented by any one of the compounds represented by Chemical Formula 6 to Chemical Formula 57.

[0079] [Chemical Formula 6]

[0080]

[0081] [Chemical Formula 7]

[0082]

[0083] [Chemical Formula 8]

[0084]

[0085] [Chemical Formula 9]

[0086]

[0087] [Chemical Formula 10]

[0088]

[0089] [Chemical Formula 11]

[0090]

[0091] [Chemical Formula 12]

[0092]

[0093] [Chemical Formula 13]

[0094]

[0095] [Chemical Formula 14]

[0096]

[0097] [Chemical Formula 15]

[0098]

[0099] [Chemical Formula 16]

[0100]

[0101] [Chemical Formula 17]

[0102]

[0103] [Chemical Formula 18]

[0104]

[0105] [Chemical Formula 19]

[0106]

[0107] [Chemical Formula 20]

[0108]

[0109] [Chemical Formula 21]

[0110]

[0111] [Chemical Formula 22]

[0112]

[0113] [Chemical Formula 23]

[0114]

[0115] [Chemical Formula 24]

[0116]

[0117] [Chemical Formula 25]

[0118]

[0119] [Chemical Formula 26]

[0120]

[0121] [Chemical Formula 27]

[0122]

[0123] [Chemical Formula 28]

[0124]

[0125] [Chemical Formula 29]

[0126]

[0127] [Chemical Formula 30]

[0128]

[0129] [Chemical Formula 31]

[0130]

[0131] [Chemical Formula 32]

[0132]

[0133] [Chemical Formula 33]

[0134]

[0135] [Chemical Formula 34]

[0136]

[0137] [Chemical Formula 35]

[0138]

[0139] [Chemical Formula 36]

[0140]

[0141] [Chemical Formula 37]

[0142]

[0143] [Chemical Formula 38]

[0144]

[0145] [Chemical Formula 39]

[0146]

[0147] [Chemical Formula 40]

[0148]

[0149] [Chemical Formula 41]

[0150]

[0151] [Chemical Formula 42]

[0152]

[0153] [Chemical Formula 43]

[0154]

[0155] [Chemical Formula 44]

[0156]

[0157] [Formula 45]

[0158]

[0159] [Formula 46]

[0160]

[0161] [Formula 47]

[0162]

[0163] [Formula 48]

[0164]

[0165] [Formula 49]

[0166]

[0167] [Formula 50]

[0168]

[0169] [Formula 51]

[0170]

[0171] [Formula 52]

[0172]

[0173] [Formula 53]

[0174]

[0175] [Formula 54]

[0176]

[0177] [Formula 55]

[0178]

[0179] [Formula 56]

[0180]

[0181] [Formula 57]

[0182]

[0183] The core-shell dye can comprise a core and a shell in a 1 : 1 molar ratio.

[0184] Another embodiment provides a photosensitive resin composition comprising the core-shell dye.

[0185] The photosensitive resin composition may also include an adhesive resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

[0186] The photosensitive resin composition may also contain malonic acid, 3-amino-1,2-propanediol, silane coupling agents including vinyl or (meth)acryloyloxy groups, leveling agents, surfactants, free radical polymerization initiators, or combinations thereof.

[0187] Another embodiment provides a photosensitive resin film manufactured using the aforementioned photosensitive resin composition.

[0188] Another embodiment provides a color filter including the photosensitive resin film.

[0189] Another embodiment provides a CMOS image sensor including the color filter.

[0190] Effects of the present invention

[0191] Color filters with improved brightness and contrast, as well as CMOS image sensors including said color filters, can be implemented using compounds or core-shell dyes according to the embodiments. Attached Figure Description

[0192] Figure 1 This is a diagram showing the cage width of the shell represented by chemical formula 5-1. Detailed Implementation

[0193] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto, nor is it limited by the scope of the claims.

[0194] In this specification, unless otherwise specifically defined, “substituted” means that at least one hydrogen atom of a compound is replaced by a substituent selected from the following: halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxy, nitro, glycidyloxy, (meth)acrylate, carbamate, cyano, amino, imino, azide, amidine, hydrazine, hydrazine, carbonyl, carbamoyl, thiol, ester, ether, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocyclic alkyl, C2 to C20 heterocyclic alkenyl, C2 to C20 heterocyclic alkynyl, and combinations thereof.

[0195] In the present specification, when a specific definition is not otherwise provided, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group", and "heterocycloalkylene group" mean cyclic alkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene cyclic compounds including at least one heteroatom of N, O, S, or P.

[0196] In the present specification, when a specific definition is not otherwise provided, "combination" means mixing or copolymerization.

[0197] In the present specification, when a definition is not otherwise provided, in a chemical formula, hydrogen is bound at the position where a chemical bond is not drawn when it should be given.

[0198] In the present specification, when a specific definition is not otherwise provided, "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid".

[0199] In the present specification, when a specific definition is not otherwise provided, "alkyl group" means C1 to C20 alkyl and specifically C1 to C15 alkyl, "cycloalkyl group" means C3 to C20 cycloalkyl and specifically C3 to C18 cycloalkyl, "alkoxy group" means C1 to C20 alkoxy and specifically C1 to C18 alkoxy, "aryl group" means C6 to C20 aryl and specifically C6 to C18 aryl, "alkenyl group" means C2 to C20 alkenyl and specifically C2 to C18 alkenyl, "alkylene group" means C1 to C20 alkylene and specifically C1 to C18 alkylene, and "arylene group" means C6 to C20 arylene and specifically C6 to C16 arylene.

[0200] In the present specification, when a specific definition is not otherwise provided, "*" indicates a point of connection of the same or different atoms or chemical formula.

[0201] Embodiments provide a core-shell dye including: a core including a compound represented by Chemical Formula 1 or Chemical Formula 2; and a shell surrounding the core.

[0202] [Chemical Formula 1]

[0203]

[0204] [Chemical Formula 2]

[0205]

[0206] In chemical formula 1 or chemical formula 2,

[0207] R 1 To R 7 Each of them independently comprises a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, a substituted or unsubstituted C2 to C20 heteroaryl, or a combination thereof.

[0208] R 1 To R 7 Each can be independently a substituted or unsubstituted C1 to C20 alkyl group, or can be represented by chemical formula 3.

[0209] [Chemical Formula 3]

[0210]

[0211] In chemical formula 3,

[0212] R a It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, nitro (-NO2), glycidoxy, (meth)acrylate, carbamate, or a combination thereof.

[0213] The nucleus dye according to the embodiments, comprising compounds represented by chemical formulas 1 and 2, may include both a nucleus with a symmetrical structure represented by chemical formula 1 and a nucleus with an asymmetrical structure represented by chemical formula 2. Since the nucleus dye according to the embodiments comprises compounds represented by chemical formulas 1 and 2, the photosensitive resin composition comprising the nucleus dye may exhibit excellent heat resistance and chemical resistance properties.

[0214] R 1 To R 7 It can be a functional group represented by chemical formula 3.

[0215] For example, in chemical formula 1, R 1 and R 3 At least one of them, and R 2 and R 4 At least one of them can be a functional group represented by chemical formula 3.

[0216] For example, in chemical formula 2, R 5 It can be a functional group represented by chemical formula 3, and R 6 and R 7 At least one of them can be a functional group represented by chemical formula 3.

[0217] The functional group represented by Chemical Formula 3 has R a A structure in which a para-carbon position is substituted, and hydrogen is entirely substituted at ortho-carbon positions and meta-carbon positions. Since the compound represented by Chemical Formula 3 has the above structure, a core-shell dye including a core represented by Chemical Formula 1 or 2 (including this compound as a substituent) exhibits an increased molar extinction coefficient, and thus improved light absorption efficiency characteristics, but reduced fluorescence quantum efficiency characteristics. Accordingly, a photosensitive resin composition including the core-shell dye can exhibit improved dye coloration intensity and chemical resistance characteristics, and excellent contrast and light emission characteristics.

[0218] Specifically, since both the ortho-carbon and the meta-carbon of the functional group represented by Chemical Formula 3 are substituted with hydrogen, the intermolecular steric effect of the compound represented by Chemical Formula 1 or 2 can be reduced, the intermolecular highest occupied molecular orbital (HOMO) / lowest unoccupied molecular orbital (LUMO) orbitals can be sufficiently overlapped, thereby increasing the molar extinction coefficient of the core-shell dye. In addition, since the intermolecular steric effect is reduced, the vibration / rotation of the nitrogen atom-substituted substituent of the compound represented by Chemical Formula 1 or 2 increases, which can facilitate non-radiative internal conversion, and thus reduce the fluorescence quantum efficiency.

[0219] In addition, when R 1 to R 7 is the functional group represented by Chemical Formula 3, the chemical resistance characteristics of the core-shell dye including the functional group can be improved.

[0220] The core-shell dye can have a molar extinction coefficient greater than or equal to 3.1 x 10 5 M -1 ·cm -1 and a fluorescence quantum efficiency less than or equal to 5%. Specifically, compared to a core-shell dye having a symmetric structure (maximum absorption wavelength: about 630 nm to about 670 nm), a core-shell dye having an asymmetric structure can have a molar extinction coefficient of 60% to 65% of the molar extinction coefficient of the core-shell dye having the symmetric structure, and in addition, have a maximum absorption wavelength of about 590 nm to about 630 nm, and thus have an excellent effect of blocking a short wavelength region.

[0221] The molar extinction coefficient of the core-shell dye is calculated by diluting the core-shell dye at a concentration of 0.001 wt% in a dilution solvent (e.g., cyclohexanone) and measuring the maximum absorption wavelength of the ultraviolet visible (UV-Vis) spectrum of each dye at room temperature using a UV-1800 (SHIMADZU Co., Ltd.).

[0222] The molar extinction coefficient of the core-shell dye may, for example, be greater than or equal to 3.1 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.2 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.3 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.4 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.5 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.6 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.7 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.8 x 10 5 M -1 ·cm -1 , for example, greater than or equal to 3.9 x 10 5 M -1 ·cm -1 , or, for example, greater than or equal to 4.0 x 10 5 M -1 ·cm -1 , but are not limited thereto. When the core-shell dye has a molar extinction coefficient within the range, the core-shell dye can have excellent color strength.

[0223] The fluorescence quantum efficiency of the core-shell dye is measured in the following manner. 4 mg to 7 mg of the core-shell dye is diluted in 3 mL to 6 mL of a cyclohexanone solution in terms of molecular weight to prepare a 2.5 x 10 -7A dye solution of mol / L was used to achieve a UV intensity (abs) of less than 0.1 au. Subsequently, the fluorescence quantum efficiency of the diluted solution was measured at room temperature using a Quantaurus-QY C11347 (HAMAMATSU Photonics KK) instrument, which used a 150W xenon lamp as the light source and set the maximum absorption wavelength of each sample to the excitation wavelength (full width at half maximum, FWHM) of 10 nm or less.

[0224] The fluorescence quantum efficiency of the core-shell dye measured under the aforementioned measurement conditions may be, for example, less than or equal to 5%, for example, less than or equal to 4.5%, for example, less than or equal to 4%, for example, less than or equal to 3.5%, for example, less than or equal to 3%, or for example, less than or equal to 2.5%, but is not limited thereto.

[0225] Since the core-shell dyes have molar extinction coefficients and fluorescence quantum efficiencies within the above range, the dye coloring strength, chemical resistance, contrast, and luminescence properties of the photosensitive resin composition containing the core-shell dyes can be improved.

[0226] For convenience, in this specification, compounds represented by chemical formula 1 or chemical formula 2 are shown as having one type of resonance structure, but compounds represented by chemical formula 1 or chemical formula 2 may also have all possible resonance structures other than those described above.

[0227] Compounds represented by chemical formula 1 may be represented by any of chemical formulas 1-1 to 1-3, and compounds represented by chemical formula 2 may be represented by any of chemical formulas 2-1 to 2-4.

[0228] [Chemical Formula 1-1]

[0229]

[0230] [Chemical Formula 1-2]

[0231]

[0232] [Chemical Formulas 1-3]

[0233]

[0234] [Chemical Formula 2-1]

[0235]

[0236] [Chemical Formula 2-2]

[0237]

[0238] [Chemical Formula 2-3]

[0239]

[0240] [Chemical Formula 2-4]

[0241]

[0242] The shell can be represented by Chemical Formula 4 or Chemical Formula 5.

[0243] [Chemical Formula 4]

[0244]

[0245] [Chemical Formula 5]

[0246]

[0247] In Chemical Formula 4 or Chemical Formula 5,

[0248] R 8 and R 9 each independently is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a nitro group (-NO2), a glycidyl group, a (meth)acrylate group, a urethane group, or a combination thereof, L a to L d each independently is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and n is an integer of 1 to 4. L a to L d each independently can be a substituted or unsubstituted C1 to C10 alkylene group.

[0249] In an embodiment, the shell corresponding to the macrocyclic compound forms a structure surrounding the compound represented by Chemical Formula 1 or Chemical Formula 2 (i.e., the structure of the compound represented by Chemical Formula 1 or Chemical Formula 2 inside the macrocycle), and thus the durability of the core-shell dye can be improved, thereby realizing a color filter having high brightness and high contrast.

[0250] On the other hand, the shell represented by Chemical Formula 4 or Chemical Formula 5 has R 8 or R 9 group as a substituent in the ring, wherein R 8 and R 9 each independently is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a nitro group (-NO2), a glycidyl group, a (meth)acrylate group, a urethane group, or a combination thereof. Since the shell has R8 Or R 9 As substituents, the durability properties of photosensitive resin compositions containing core-shell dyes can be improved.

[0251] The shell can be represented by chemical formula 4-1 or chemical formula 5-1.

[0252] [Chemical Formula 4-1]

[0253]

[0254] [Chemical Formula 5-1]

[0255]

[0256] In chemical formula 4-1 or chemical formula 5-1, R 8 and R 9 Defined as described above.

[0257] The shell can be represented by, for example, any of the chemical formulas 4-a to 4-d and 5-a to 5-d.

[0258] [Chemical formula 4-a]

[0259]

[0260] [Chemical Formula 4-b]

[0261]

[0262] [Chemical formula 4-c]

[0263]

[0264] [Chemical formula 4-d]

[0265]

[0266] [Chemical Formula 5-a]

[0267]

[0268] [Chemical Formula 5-b]

[0269]

[0270] [Chemical formula 5-c]

[0271]

[0272] [Chemical formula 5-d]

[0273]

[0274] The shell can have a cage width of 6.5 angstroms to 7.5 angstroms, a volume of 10 angstroms to 16 angstroms, and a length of 1 nm to 3 nm. In the present specification, the cage width refers to a distance inside the shell, for example, a distance between two different phenylene groups connected with methylene groups on both sides in the shell represented by Chemical Formula 4-1 or Chemical Formula 5-1 (see Figure 1 When the shell has a cage width within the range, a core-shell dye having a structure surrounding a core including a compound represented by Chemical Formula 1 or Chemical Formula 2 can be obtained, and thus, when the core-shell dye is added to a photosensitive resin composition, a color filter having excellent durability and high brightness can be implemented.

[0275] The compound represented by Chemical Formula 1 or Chemical Formula 2 included in or constituting the core can have a length of 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the length of the compound represented by Chemical Formula 1 is within the range, a core-shell dye having a core structure, and a shell surrounding the core structure can be easily formed. In other words, since the compound represented by Chemical Formula 1 has a length within the range, the shell of the macrocyclic compound can have a structure surrounding the compound represented by Chemical Formula 1. When another compound not having a length within the range is used, since the shell can hardly form a structure surrounding the compound of the core, the durability of the dye can not be improved.

[0276] The compound represented by Chemical Formula 1 or Chemical Formula 2 included in or constituting the core can have a maximum absorption peak at a wavelength of 590 nm to 670 nm. A core-shell dye using a compound represented by Chemical Formula 1 or Chemical Formula 2 having spectral properties as a core can be used, for example, as a green dye, thereby obtaining a photosensitive resin composition for a color filter having high brightness and excellent durability.

[0277] The core-shell dye can include a core including a compound represented by Chemical Formula 1 or Chemical Formula 2 and a shell at a molar ratio of 1:1. When the core and the shell are present at this molar ratio, a coating layer (shell) surrounding a core including a compound represented by Chemical Formula 1 or Chemical Formula 2 can be well formed.

[0278] For example, the core-shell dye can be represented as one compound represented by one of Chemical Formula 6 to Chemical Formula 57, but is not limited thereto.

[0279] [Chemical Formula 6]

[0280]

[0281] [Chemical Formula 7]

[0282]

[0283] [Chemical Formula 8]

[0284]

[0285] [Chem. 9]

[0286]

[0287] [Chem. 10]

[0288]

[0289] [Chem. 11]

[0290]

[0291] [Chem. 12]

[0292]

[0293] [Chem. 13]

[0294]

[0295] [Chem. 14]

[0296]

[0297] [Chem. 15]

[0298]

[0299] [Chem. 16]

[0300]

[0301] [Chem. 17]

[0302]

[0303] [Chem. 18]

[0304]

[0305] [Chem. 19]

[0306]

[0307] [Chem. 20]

[0308]

[0309] [Chem. 21]

[0310]

[0311] [Chemical Formula 22]

[0312]

[0313] [Chemical Formula 23]

[0314]

[0315] [Chemical Formula 24]

[0316]

[0317] [Chemical Formula 25]

[0318]

[0319] [Chemical Formula 26]

[0320]

[0321] [Chemical Formula 27]

[0322]

[0323] [Chemical Formula 28]

[0324]

[0325] [Chemical Formula 29]

[0326]

[0327] [Chemical Formula 30]

[0328]

[0329] [Chemical Formula 31]

[0330]

[0331] [Chemical Formula 32]

[0332]

[0333] [Chemical Formula 33]

[0334]

[0335] [Chemical Formula 34]

[0336]

[0337] [Chemical Formula 35]

[0338]

[0339] [Chemical Formula 36]

[0340]

[0341] [Chemical Formula 37]

[0342]

[0343] [Chemical Formula 38]

[0344]

[0345] [Chemical Formula 39]

[0346]

[0347] [Chemical Formula 40]

[0348]

[0349] [Chemical Formula 41]

[0350]

[0351] [Chemical Formula 42]

[0352]

[0353] [Chemical Formula 43]

[0354]

[0355] [Chemical Formula 44]

[0356]

[0357] [Chemical Formula 45]

[0358]

[0359] [Chemical Formula 46]

[0360]

[0361] [Chemical Formula 47]

[0362]

[0363] [Chemical Formula 48]

[0364]

[0365] [Chemical Formula 49]

[0366]

[0367] [Chemical Formula 50]

[0368]

[0369] [Chemical Formula 51]

[0370]

[0371] [Chemical Formula 52]

[0372]

[0373] [Chemical Formula 53]

[0374]

[0375] [Chemical Formula 54]

[0376]

[0377] [Chemical Formula 55]

[0378]

[0379] [Chemical Formula 56]

[0380]

[0381] [Chemical Formula 57]

[0382]

[0383] The core-shell dye can be used alone as a green dye, and can be mixed with an auxiliary dye.

[0384] The auxiliary dye can be a triarylmethane-based dye, an anthraquinone-based dye, a benzalmethylene-based dye, a cyanine-based dye, a phthalocyanine-based dye, an azaporphyrin-based dye, an indigo-based dye, a xanthene-based dye, a pyridone azo-based dye, or the like.

[0385] The core-shell dye can be mixed with a pigment.

[0386] The pigment can be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

[0387] Examples of the red pigment can be C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red Pigment 89, or the like. Examples of the green pigment can be C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green Pigment 59, or the like. Examples of the blue pigment can be copper phthalocyanine pigments, such as C.I. Blue Pigment 15:6, C.I. Blue Pigment 15, C.I. Blue Pigment 15:1, C.I. Blue Pigment 15:2, C.I. Blue Pigment 15:3, C.I. Blue Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 16, or the like. Examples of the yellow pigment can be: isoindoline-based pigments, such as C.I. Yellow Pigment 139, or the like; quinophthalone-based pigments, such as C.I. Yellow Pigment 138, or the like; nickel complex pigments, such as C.I. Yellow Pigment 150, or the like. Examples of the black pigment can be aniline black, perylene black, titanium black, carbon black, or the like. The pigments can be used alone or as a mixture of two or more, and are not limited thereto.

[0388] The pigment can be contained in the photosensitive resin composition for a color filter in a pigment dispersion liquid state. The pigment dispersion liquid can be composed of a pigment and a solvent, a dispersant, a dispersing resin, or the like.

[0389] The solvent can be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like, and can be preferably propylene glycol methyl ether acetate.

[0390] The dispersant contributes to uniform dispersion of the pigment, and can include a nonionic, anionic, or cationic dispersant. Specific examples can be polyalkylene glycol or esters thereof, polyoxyalkylene, polyol ester alkylene oxide adduct, alcohol alkylene oxide addition product, sulfonate ester, sulfonate salt, carboxylate ester, carboxylate salt, alkylamide alkylene oxide adduct, alkylamine, and can be used alone or as a mixture of two or more.

[0391] The dispersing resin can be an acrylic resin including a carboxyl group, and improves the stability of the pigment dispersion liquid and the pattern property of the pixel.

[0392] When the core-shell dye and the pigment are mixed, the core-shell dye and the pigment can be mixed in a weight ratio of 1:9 to 9:1, and specifically in a weight ratio of 3:7 to 7:3. When the core-shell dye and the pigment are mixed in the weight ratio range, high brightness and contrast can be obtained while maintaining color characteristics.

[0393] According to another embodiment, a photosensitive resin composition including a core-shell dye is provided.

[0394] The photosensitive resin composition can further include (A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent.

[0395] Hereinafter, each component is described in detail.

[0396] (A) Colorant

[0397] The colorant can include the core-shell dye already described above.

[0398] In addition to the core-shell dye, the colorant can include a pigment, and the pigment has been described above.

[0399] The core-shell dye can be included in an amount of 0.5 to 10 wt%, for example, 0.5 to 5 wt% based on the total amount of the photosensitive resin composition for a color filter. When the core-shell dye is used within the above range, high brightness and contrast can be exhibited in the desired color coordinates.

[0400] (B) Binder resin

[0401] The binder resin can be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a resin including at least one acrylic repeating unit.

[0402] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer including at least one carboxyl group. Examples of the monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0403] The first ethylenically unsaturated monomer can be included in an amount of 5 to 50 wt%, for example, 10 to 40 wt% based on the total amount of the alkali-soluble resin.

[0404] Examples of the second ethylenically unsaturated monomer can include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylbenzene, and the like; unsaturated carboxylate compounds 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; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, and the like; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl benzoate, and the like; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate, and the like; cyano ethylene compounds such as (meth)acrylonitrile, and the like; unsaturated amide compounds such as (meth)acrylamide, and the like, and the second ethylenically unsaturated monomer can be used alone or as a mixture of two or more.

[0405] Examples of the binder resin can include a methyl methacrylate / methyl benzyl acrylate copolymer, a methyl methacrylate / methyl benzyl acrylate / styrene copolymer, a methyl methacrylate / methyl benzyl acrylate / 2-hydroxyethyl methacrylate copolymer, a methyl methacrylate / methyl benzyl acrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and the binder resin can be used alone or as a mixture of two or more.

[0406] The binder resin can have a weight average molecular weight of 3,000 g / mol to 150,000 g / mol, for example, 5,000 g / mol to 50,000 g / mol, or 20,000 g / mol to 30,000 g / mol. When the binder resin has a weight average molecular weight within the range, the composition can have excellent close contact properties with a substrate, good physical and chemical properties, and an appropriate viscosity.

[0407] The binder resin can have an acid value of 15 mgKOH / g to 60 mgKOH / g, for example, 20 mgKOH / g to 50 mgKOH / g. When the binder resin has an acid value within the range, the binder resin can bring about excellent pixel resolution.

[0408] The binder resin can be included in an amount of 0.1 wt% to 30 wt%, for example, 5 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the range, the composition can have excellent developability and improved crosslinking, and thus has excellent surface flatness when manufactured into a color filter.

[0409] (C) Photopolymerizable monomer

[0410] The photopolymerizable monomer can be a monofunctional or a polyfunctional ester of (meth)acrylic acid including at least one ethylenically unsaturated double bond.

[0411] The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during exposure in a patterning process, and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0412] Specific examples of the photopolymerizable monomer can be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, phosphoric acid tri(meth)acryloyloxyethyl ester, phenol novolac epoxy(meth)acrylate, and the like.

[0413] Commercially available examples of the photopolymerizable monomer are as follows. The monofunctional (meth)acrylate can include Aronix (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); (KAYARAD) (Nippon Kayaku Co., Ltd.); These photo-polymerizable compounds can be used alone or as a mixture of two or more.

[0414] An acid anhydride can be used to treat the photo-polymerizable monomer to improve developability.

[0415] The photo-polymerizable monomer can be included in an amount of 0.1 to 30 wt%, for example, 5 to 20 wt% based on the total amount of the photosensitive resin composition. When the photo-polymerizable monomer is included within the range, the pattern characteristics and developability are excellent when manufacturing a color filter.

[0416] (D) Photopolymerization initiator

[0417] The photo-polymerization initiator can include an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, and the like.

[0418] Examples of the acetophenone-based compound can include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-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, and the like.

[0419] Examples of the benzophenone-based compound can include benzophenone, benzoylbenzoic acid, benzoyl methyl benzoate, 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, and the like.

[0420] Examples of the thioxanthone-based compound can include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0421] Examples of the benzoin-based compound can include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0422] Examples of the triazine-based compounds can 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, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthyl 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl(heliotryl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like.

[0423] Examples of the oxime-based compounds can include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and the like.

[0424] In addition to the compounds, the photopolymerization initiator can also include a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a bisimidazole-based compound, a fluorene-based compound, and the like.

[0425] The photopolymerization initiator can be included in an amount of 0.1 to 5 wt%, for example, 1 to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range, the composition can be sufficiently photopolymerized when exposed during the pattern forming process of preparing a color filter, thereby achieving excellent sensitivity and improving transmittance.

[0426] (E) Solvent

[0427] The solvent is not particularly limited, but examples of the solvent include: alcohols such as methanol, ethanol, and the like; ethers such as dichloroethane, n-butyl ether, diisopropyl ether, methyl phenyl ether, tetrahydrofuran, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, and the like; cellosolves such as methyl cellosolve, ethyl cellosolve, diethyl cellosolve, 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 methyl ether acetate, propylene glycol propyl ether acetate, and the like; aromatic hydrocarbons such as toluene, xylene, 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-pentyl 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; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, and the like; alkoxylated acetic acid alkyl 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-alkoxylated propionic 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-alkoxylated propionic 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-alkoxylated-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 ester compounds such as ethyl pyruvate. In addition, the solvent can be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 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, and the like. The solvent can be used alone or in the form of a mixture of two or more.

[0428] Considering miscibility, reactivity, etc., the solvent can include: glycol ethers such as ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, etc.; esters such as ethyl 2-hydroxypropionate, etc.; diethylene glycol such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0429] The solvent can be included in an amount of 20 wt% to 90 wt% based on the total amount of the photosensitive resin composition.

[0430] When the solvent is included in the range, the photosensitive resin composition can have excellent coating properties and maintain excellent flatness in a layer having a thickness of greater than or equal to 3 μm.

[0431] (F) Other additives

[0432] The photosensitive resin composition can further include other additives such as malonic acid; 3-amino-1,2-propanediol; silane-based coupling agents including a vinyl group or a (meth)acryloxy group; leveling agents; fluorine-based surfactants; radical polymerization initiators to prevent the generation of stains or spots during coating, adjust leveling, or prevent pattern residue from being generated due to non-development.

[0433] The photosensitive resin composition can further include an epoxy compound to improve close contact properties with a substrate.

[0434] Examples of the epoxy compound can include phenol novolac epoxy compounds, tetramethyl biphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0435] The amount of the additive can be controlled depending on the desired properties.

[0436] Another embodiment provides a photosensitive resin film manufactured using the aforementioned photosensitive resin composition.

[0437] Another embodiment provides a color filter including the photosensitive resin film. A method of manufacturing the color filter is as follows.

[0438] A protective layer SiN having a thickness of 500 angstroms to 1500 angstroms is coated on a bare glass substrate or on the bare glass substrate xA photosensitive resin composition for a color filter is coated on a glass substrate having a thickness of 3.1 to 3.4 μm using a suitable method such as spin coating, slit coating, and the like. After coating, the composition is irradiated with light to form a pattern required for a color filter. After irradiation with light, the coating is treated with an alkali developing solution, and the unirradiated region of the coating can be dissolved, thereby forming a pattern for a color filter. This process is repeated according to the necessary number of R, G, and B colors, thereby manufacturing a color filter having a desired pattern.

[0439] Further, the image pattern obtained by development is cured by heat treatment, irradiation of actinic rays, or the like, thereby improving the crack resistance, solvent resistance, and the like.

[0440] Another embodiment provides a CMOS image sensor including a color filter.

[0441] Detailed description of embodiments

[0442] Hereinafter, the present application is explained in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the present application in any manner.

[0443] (Preparation of compounds)

[0444] Synthesis Example 1: Synthesis of a nucleus dye represented by Chemical Formula 1-1

[0445]

[0446] To isopropyl alcohol were added 1,3-dimethylbutylamine (60 mmol), 4-bromotoluene (30 mmol), KOH (60 mmol), and CuCl (0.3 mmol), and then heated to 90°C and stirred for 12 hours. Subsequently, ethyl acetate was added to the solution, and then the organic layer was extracted by washing twice with a saturated aqueous NH4Cl solution and a 10% aqueous NaCl solution. The extracted organic layer was distilled under reduced pressure, and purified by column chromatography, thereby obtaining intermediate A-1.

[0447]

[0448] Intermediate A-1 (20 mmol), Pd(OAc)2(0.002 mmol), sodium tert-butoxide (30 mmol), and iodobenzene (20 mmol) were added to a toluene solvent, and then stirred at room temperature for 30 minutes, and P(t-Bu)3(0.004 mmol) was added thereto, and then stirred at 110°C for 15 hours. Subsequently, ethyl acetate was added to the solution, and then washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure, and purified by column chromatography, to obtain intermediate A-2.

[0449] Intermediate A-2 (60 mmol) and 3,4-dihydroxy-3-cyclobutyn-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL), and then refluxed, and water produced therefrom was removed through a Dean-Stark distillation apparatus. After stirring for 12 hours, the green reaction obtained therefrom was distilled under reduced pressure, and purified by column chromatography, to obtain a compound represented by Chemical Formula 1-1.

[0450] Synthesis Example 2: Synthesis of a core dye represented by Chemical Formula 1-2

[0451] A compound represented by Chemical Formula 1-2 was synthesized in the same manner as in Synthesis Example 1, except that N-(4-methylpentan-2-yl)-4-nitro-N-phenylaniline was used instead of intermediate A-2.

[0452] Synthesis Example 3: Synthesis of a core dye represented by Chemical Formula 1-3

[0453] A compound represented by Chemical Formula 1-3 was synthesized in the same manner as in Synthesis Example 1, except that 2-(((2-(4-((4-methylpentan-2-yl)(phenyl)amino)phenoxy)ethoxy)carbonyl)amino)ethyl methacrylate was used instead of intermediate A-2.

[0454] Synthesis Example 4: Synthesis of a core dye represented by Chemical Formula 2-1

[0455]

[0456] A mixture of 12 mmol (1 equivalent) of indole, 12 mmol (1 equivalent) of 4-iodotoluene, 2.4 mmol (0.2 equivalent) of copper (I) iodide, 24 mmol (2 equivalents) of cesium carbonate, and 20 mL of dimethyl formamide (DMF) was stirred at 120°C for 12 hours. Subsequently, ethyl acetate was added to the solution, and then the organic layer was extracted by washing twice with water. The extracted organic layer was distilled under reduced pressure, and purified by column chromatography, thereby obtaining intermediate B-1 in a yield of 30%.

[0457]

[0458] A mixture of 32 mmol (1 equivalent) of squaric acid, 80 mmol (2.5 equivalents) of thionyl chloride, and 10 drops of N,N-dimethylformamide was reacted at 75°C for 3 hours, and the yellow crystals thus obtained were filtered at room temperature, thereby obtaining intermediate B-2 in a yield of 50%.

[0459]

[0460] A 0.2 M toluene solution of intermediate A-2 was added dropwise to a 0.3 M toluene solution of intermediate B-2, and then stirred at room temperature for 1 hour, and in addition, at 80°C for 12 hours. After removing toluene under reduced pressure, the residue was purified by column chromatography, thereby obtaining intermediate B-3 in a yield of 50%.

[0461]

[0462] A mixture of 1 times of intermediate B-3, 8 times of acetic acid, 8 times of water, and 0.1 times of concentrated hydrochloric acid was stirred at 130°C for 12 hours. Subsequently, dichloromethane was added to the solution, and then the organic layer was extracted by washing twice with a 10% aqueous hydrochloric acid solution. The extracted organic layer was distilled under reduced pressure, thereby obtaining intermediate B-4 in a yield of 100%.

[0463]

[0464] 60 mmol of intermediate B-1 and 60 mmol of intermediate B-4 were added to toluene (200 mL) and butanol (200 mL), and then refluxed, and the water thus produced was removed by a Dean-Stark distillation apparatus. After stirring for 12 hours, the green reaction thus obtained was distilled under reduced pressure, and purified by column chromatography, thereby obtaining a compound represented by Chemical Formula 2-1.

[0465] (Synthesis of core-shell dye)

[0466] (Synthetic Example 5: Synthesis of Core-Shell Dye represented by Chemical Formula 17)

[0467] [Reaction Scheme]

[0468]

[0469] A compound represented by Chemical Formula 1-2 (5 mmol) was dissolved in 600 mL of a chloroform solvent, and triethylamine (50 mmol) was added thereto. 2,6-Pyridinedicarbonyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and then dropwise addition was simultaneously performed thereto at room temperature for 5 hours. After 12 hours, the reaction was distilled under reduced pressure, and separated by column chromatography, to obtain a compound represented by Chemical Formula 17.

[0470] (Synthetic Example 6: Synthesis of Core-Shell Dye represented by Chemical Formula 18)

[0471] A compound represented by Chemical Formula 18 was synthesized in the same manner as in Synthetic Example 5, except that a compound represented by Chemical Formula 1-3 was used as the compound represented by Chemical Formula 1-2.

[0472] [Chemical Formula 18]

[0473]

[0474] (Synthetic Example 7: Synthesis of Core-Shell Dye represented by Chemical Formula 22)

[0475]

[0476] A compound represented by Chemical Formula 1-1 (5 mmol) was dissolved in 600 mL of a chloroform solvent, and then triethylamine (50 mmol) was added thereto. Subsequently, 4-(oxiran-2-ylmethoxy)pyridine-2,6-dicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and then dropwise addition was simultaneously performed thereto for 5 hours. After 12 hours, the reaction was distilled under reduced pressure, and separated by column chromatography, to obtain a compound represented by Chemical Formula 22.

[0477] (Synthetic Example 8: Synthesis of Core-Shell Dye represented by Chemical Formula 23)

[0478] A compound represented by Chemical Formula 23 was synthesized in the same manner as in Synthesis Example 7, except that a compound represented by Chemical Formula 1-2 was used instead of a compound represented by Chemical Formula 1-1.

[0479] [Chemical Formula 23]

[0480]

[0481] (Synthesis Example 9: Synthesis of Core-Shell Dye represented by Chemical Formula 24)

[0482] A compound represented by Chemical Formula 24 was synthesized in the same manner as in Synthesis Example 7, except that a compound represented by Chemical Formula 1-3 was used instead of a compound represented by Chemical Formula 1-1.

[0483] [Chemical Formula 24]

[0484]

[0485] (Synthesis Example 10: Synthesis of Core-Shell Dye represented by Chemical Formula 25)

[0486] A compound represented by Chemical Formula 25 was synthesized in the same manner as in Synthesis Example 7, except that a compound of 2-(((2-((2,6-bis(chlorocarbonyl)pyridin-4-yl)oxy)ethoxy)carbonyl)amino)ethyl methacrylate was used instead of a compound of 4-(oxetan-2-ylmethoxy)pyridine-2,6-dicarbonyl dichloride.

[0487] [Chemical Formula 25]

[0488]

[0489] (Synthesis Example 11: Synthesis of Core-Shell Dye represented by Chemical Formula 26)

[0490] A compound represented by Chemical Formula 26 was synthesized in the same manner as in Synthesis Example 7, except that a compound of 2-(((2-((2,6-bis(chlorocarbonyl)pyridin-4-yl)oxy)ethoxy)carbonyl)amino)ethyl methacrylate was used instead of a compound of 4-(oxetan-2-ylmethoxy)pyridine-2,6-dicarbonyl dichloride, and a compound represented by Chemical Formula 1-2 was used instead of a compound represented by Chemical Formula 1-1.

[0491] [Chemical Formula 26]

[0492]

[0493] (Synthesis Example 12: Synthesis of Core-Shell Dye represented by Chemical Formula 27)

[0494] A compound represented by Chemical Formula 27 was synthesized in the same manner as in Synthesis Example 7, except that a compound of 2-(((2-((2,6-bis(chlorocarbonyl)pyridin-4-yl)oxy)ethoxy)carbonyl)amino)ethyl methacrylate was used instead of the compound of 4-(oxirane-2-ylmethoxy)pyridine-2,6-dicarbonyl dichloride, and a compound represented by Chemical Formula 1-3 was used instead of the compound represented by Chemical Formula 1-1.

[0495] [Chemical Formula 27]

[0496]

[0497] (Synthesis Example 13: Synthesis of Core-Shell Dye represented by Chemical Formula 50)

[0498] A compound represented by Chemical Formula 50 was synthesized in the same manner as in Synthesis Example 7, except that a compound represented by Chemical Formula 2-1 was used instead of the compound represented by Chemical Formula 1-1.

[0499] [Chemical Formula 50]

[0500]

[0501] (Synthesis Example 14: Synthesis of Core-Shell Dye represented by Chemical Formula 54)

[0502] A compound represented by Chemical Formula 54 was synthesized in the same manner as in Synthesis Example 7, except that a compound of 2-(((2-((2,6-bis(chlorocarbonyl)pyridin-4-yl)oxy)ethoxy)carbonyl)amino)ethyl methacrylate was used instead of the compound of 4-(oxirane-2-ylmethoxy)pyridine-2,6-dicarbonyl dichloride, and a compound represented by Chemical Formula 2-1 was used instead of the compound represented by Chemical Formula 1-1.

[0503] [Chemical Formula 54]

[0504]

[0505] (Comparative Synthesis Example 1: Synthesis of Core-Shell Dye of Symmetrical Structure)

[0506] [Chemical Formula A]

[0507]

[0508] A compound represented by Chemical Formula B was synthesized in the same manner as the last step of Synthesis Example 1, except that N-(heptan-2-yl)-2,4-dimethyl-N-phenylaniline was used instead of intermediate A-2. The core-shell dye of Comparative Synthesis Example 2 was synthesized in the same manner as in Synthesis Example 5, except that the compound represented by Chemical Formula B was used instead of the compound represented by Chemical Formula 1-2.

[0509] (Synthesis of core-shell dye having asymmetric structure)

[0510] [Chemical Formula C]

[0511]

[0512] A compound represented by Chemical Formula C was synthesized in the same manner as in Synthesis Example 4, except that N-(2-methoxycyclohexyl)-2,4-dimethyl-N-phenylaniline was used instead of intermediate A-2 and intermediate B-2. The core-shell dye of Comparative Synthesis Example 3 was synthesized in the same manner as in Synthesis Example 5, except that the compound represented by Chemical Formula C was used instead of the compound represented by Chemical Formula 1-2.

[0513] (Synthesis of core-shell dye having asymmetric structure)

[0514] [Chemical Formula D]

[0515]

[0516] A compound represented by Chemical Formula D was synthesized in the same manner as in Synthesis Example 4, except that N-(heptan-2-yl)-2,4-dimethyl-N-phenylaniline was used instead of intermediate A-2 and intermediate B-2. The core-shell dye of Comparative Synthesis Example 4 was synthesized in the same manner as in Synthesis Example 5, except that the compound represented by Chemical Formula D was used instead of the compound represented by Chemical Formula 1-2.

[0517] (Synthesis of core-shell dye having asymmetric structure)

[0518] [Chemical Formula D]

[0519]

[0520] A compound represented by Chemical Formula D was synthesized in the same manner as in Synthesis Example 4, except that N-(heptan-2-yl)-2,4-dimethyl-N-phenylaniline was used instead of intermediate A-2 and intermediate B-2. The core-shell dye of Comparative Synthesis Example 4 was synthesized in the same manner as in Synthesis Example 5, except that the compound represented by Chemical Formula D was used instead of the compound represented by Chemical Formula 1-2.

[0521] (Evaluation)

[0522] Evaluation 1 : Fluorescence quantum efficiency

[0523] Each of the core-shell dyes according to Synthesis Examples 5 to 14, and Comparative Synthesis Examples 1 to 4 was added to 3 mL to 6 mL of a cyclohexanone solution in an amount of 4 mg to 7 mg each of the molecular weight, and was diluted therein to prepare a 2.5 x 10 -7 mol / L dye solution, wherein the solution was diluted to have a UV intensity (abs) of less than 0.1 au. Subsequently, the fluorescence quantum efficiency of each of the diluted solutions was measured at room temperature by using a Quantaurus-QY C11347 (Hammamatsu Photonics K.K.), and the results are shown in Table 1. The Quantaurus-QY C11347 apparatus uses a 150 W xenon lamp as a light source, and the maximum absorption wavelength of each sample was set as the excitation wavelength (full width at half maximum (FWHM) of 10 nm or less).

[0524] (Table 1)

[0525] (Unit: %)

[0526] Fluorescence quantum efficiency Synthesis Example 5 5 Synthesis Example 6 4 Synthesis Example 7 5 Synthesis Example 8 5 Synthesis Example 9 4 Synthesis Example 10 2 Synthesis Example 11 3 Synthesis Example 12 4 Synthesis Example 13 37 Synthesis Example 14 32 Comparative Synthesis Example 1 71 Comparative Synthesis Example 2 58 Comparative Synthesis Example 3 95 Comparative Synthesis Example 4 90

[0527] Referring to Table 1, the symmetric core-shell dyes according to Synthesis Examples 5 to 12 exhibited a fluorescence quantum efficiency in the range of 5% or less measured under the foregoing conditions, but the core-shell dyes of Comparative Synthesis Examples 1 and 2 exhibited a much higher fluorescence quantum efficiency. The asymmetric core-shell dyes of Synthesis Examples 13 and 14 exhibited a fluorescence quantum efficiency greater than or equal to 30% higher than the symmetric core-shell dyes measured under the foregoing conditions, but the fluorescence quantum efficiency y was reduced by about 1 / 3 compared to the asymmetric core-shell dyes of Comparative Synthesis Examples 3 and 4. Accordingly, when included in a photosensitive resin composition, the symmetric core-shell dyes of Synthesis Examples 5 to 12 (asymmetric core-shell dyes of Synthesis Examples 13 and 14) exhibited superior contrast properties compared to the symmetric core-shell dyes of Comparative Synthesis Examples 1 and 2 (asymmetric core-shell dyes of Comparative Synthesis Examples 3 and 4).

[0528] Evaluation 2: Molar extinction coefficient

[0529] The core-shell dyes according to Synthesis Examples 5 to 14, and Comparative Synthesis Examples 1 to 4 were each diluted in a dilution solvent (cyclohexanone) at a concentration of 0.001 wt%, and then the maximum absorption wavelength of the UV-Vis spectrum was measured at room temperature using a UV-1800 (Shimadzu Corporation) apparatus, which was used to calculate the molar extinction coefficient, and the results are shown in Table 2.

[0530] (Table 2)

[0531] (unit: M -1 ·cm -1 )

[0532] Molar extinction coefficient Synthesis Example 5 3.10 x 10 5 ]]> Synthesis Example 6 3.12 x 10 5 ]]> Synthesis Example 7 3.11 x 10 5 ]] Synthesis Example 8 3.15 x 10 5 ]]> Synthesis Example 9 3.14 x 10 5 ]]> Synthesis Example 10 3.11 x 10 5 ]]> Synthesis Example 11 3.21 x 10 5 ]]> Synthesis Example 12 3.13 x 10 5 ]]> Synthesis Example 13 2.15 x 10 5 ]]> Synthesis Example 14 2.10 x 10 5 ]]> Comparative Synthesis Example 1 2.87 x 10 5 ]]> Comparative Synthesis Example 2 2.83 x 10 5 ]]> Comparative Synthesis Example 3 2.01 x 10 5 ]] Comparative Synthesis Example 4 2.00 x 10 5 ]]

[0533] Referring to Table 2, the symmetric core-shell dyes of Synthesis Examples 5 to 12 exhibited a molar extinction coefficient in the range of 3.10 x 10 5 M -1 ·cm -1 or greater than 3.10 x 10 5 M -1 ·cm -1 measured under the aforementioned conditions, and the core-shell dyes of Comparative Synthesis Examples 1 and 2 exhibited a 8% or greater increase in molar extinction coefficient. The asymmetric core-shell dyes of Synthesis Examples 13 and 14 exhibited a molar extinction coefficient in the range of 2.10 x 10 5 M -1 ·cm -1 or greater than 2.10 x 10 5 M -1 ·cm -1 measured under the aforementioned conditions, and the asymmetric core-shell dyes of Comparative Synthesis Examples 3 and 4 exhibited a 5% or greater increase in molar extinction coefficient.

[0534] (Preparation of photosensitive resin composition)

[0535] A photosensitive resin composition was prepared using the following components.

[0536] (A) Dye

[0537] (A-1) Core-shell dye prepared in Synthesis Example 9 (represented by Chemical Formula 24)

[0538] (A-2) Core-shell dye prepared in Synthesis Example 10 (represented by Chemical Formula 25)

[0539] (A-3) Core-shell dye prepared in Synthesis Example 11 (represented by Chemical Formula 26)

[0540] (A-4) Core-shell dye prepared in Synthesis Example 12 (represented by Chemical Formula 27)

[0541] (A-5) Core-shell dye prepared in Comparative Synthesis Example 1 (represented by Chemical Formula A)

[0542] (B) Binder resin

[0543] Methacrylic acid / methyl benzyl acrylate copolymer (mixed weight ratio: 15 wt% / 85 wt%) having a weight average molecular weight of 22,000 g / mol

[0544] (C) Photopolymerizable monomer

[0545] Dipentaerythritol hexaacrylate

[0546] (D) Photopolymerization initiator

[0547] (D-1) 1,2-octanedione

[0548] (D-2) 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

[0549] (E) Solvent

[0550] (E-1) Cyclohexanone

[0551] (E-2) Propylene glycol monomethyl ether acetate (PGMEA)

[0552] Examples 1 to 4 and Comparative Example 1

[0553] A photosensitive resin composition was prepared by mixing each component with the composition shown in Table 3. Specifically, a photopolymerization initiator was dissolved in a solvent, the solution was stirred at room temperature for 2 hours, a dye (or pigment dispersion) was added thereto, the mixture was stirred for 30 minutes, a binder resin and a photopolymerizable monomer were added thereto, and the obtained mixture was stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities and prepare a photosensitive resin composition.

[0554] (Table 3)

[0555] (Unit: wt%)

[0556]

[0557] Evaluation 3: Contrast of photosensitive colored resin composition

[0558] A photosensitive resin composition prepared using each core-shell dye according to Synthesis Examples 9 to 12 and Comparative Synthesis Example 1 was coated on a 1 mm-thick, degreased glass substrate to a thickness of 1 to 3 μm and dried on a hot plate at 90°C for 2 minutes to form a film. Subsequently, the film was exposed to light using a high-pressure mercury lamp with a main wavelength of 365 nm and dried in a forced convection drying oven of an oven at 200°C for 5 minutes. The contrast of the pixel layer was measured using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 4.

[0559] (Table 4)

[0560] (Unit: %)

[0561] Contrast Example 1 116 Example 2 129 Example 3 122 Example 4 121 Comparative Example 1 100

[0562] Referring to Table 4, the photosensitive resin compositions using the core-shell dyes of Synthesis Examples 9 to 12 (Examples 1 to 4) exhibited improved contrast of about 16 to 29% measured under the aforementioned conditions, compared to the photosensitive resin composition using the core-shell dye of Comparative Synthesis Example 1 (Comparative Example 1).

[0563] While the present application has been described in connection with the exemplary embodiments, as currently contemplated, it will be understood that the application is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the above-described embodiments are to be considered in all respects as illustrative only and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description.

Claims

1. A core-shell dye, comprising: a core including a compound represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3 or a compound represented by any one of Chemical Formula 2-1 to Chemical Formula 2-4, and a shell surrounding the core, the shell being represented by any one of Chemical Formula 4-b to Chemical Formula 4-d, and Chemical Formula 5-b to Chemical Formula 5-d: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 4-b] [Chemical Formula 4-c] [Chemical Formula 4-d] [Chemical Formula 5-b] [Chemical Formula 5-c] [Chemical Formula 5-d] 2.The core-shell dye of claim 1, wherein The core-shell dye has a molar extinction coefficient greater than or equal to 3.1 x 10 5 M -1 cm -1 and a fluorescence quantum efficiency less than or equal to 5%. 3.The core-shell dye of claim 1, wherein the shell has a cage width of 6.5 angstroms to 7.5 angstroms. 4.The core-shell dye of claim 1, wherein the core has a length of 1 nm to 3 nm. 5.The core-shell dye of claim 1, wherein the core has a maximum absorption peak at a wavelength of 590 nm to 670 nm. 6.The core-shell dye of claim 1, wherein the core-shell dye is represented by any one of compounds represented by Chemical Formula 8 to Chemical Formula 16, Chemical Formula 19 to Chemical Formula 27, Chemical Formula 31 to Chemical Formula 42, Chemical Formula 46 to Chemical Formula 57: [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] [Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] [Chemical Formula 46] [Chemical Formula 47] [Chemical Formula 48] [Chemical Formula 49] [Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53] [Chemical Formula 54] [Chemical Formula 55] [Chemical Formula 56] [Chemical Formula 57] 7.The core-shell dye of claim 1, wherein the core-shell dye includes the core and the shell in a molar ratio of 1:

1. 8.A photosensitive resin composition including the core-shell dye of any one of claims 1 to 7. 9.The photosensitive resin composition of claim 8, wherein the photosensitive resin composition further includes a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. 10.The photosensitive resin composition of claim 9, wherein the photosensitive resin composition further includes malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent including a vinyl group or a (methyl)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

11. A photosensitive resin film produced using the photosensitive resin composition according to claim 8.

12. A color filter comprising the photosensitive resin film according to claim 11.

13. A complementary metal-oxide semiconductor image sensor comprising the color filter according to claim 12.

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