Core-shell dye, near-infrared absorption composition, film, filter, and complementary metal oxide semiconductor image sensor using the same

Abstract

The present disclosure relates to a core-shell dye, a near-infrared absorbing resin composition containing the same, a near-infrared absorbing film using the same, a filter, and a complementary metal oxide semiconductor image sensor. Specifically, an embodiment provides a core-shell dye including: a core represented by Chemical Formula 1; and a shell surrounding the core and represented by Chemical Formula 2. In Chemical Formula 1 and Chemical Formula 2, each substituent is as defined in the specification. The core-shell dye according to the embodiment has excellent durability while showing an improved match with the near-infrared absorption wavelength band. [Chemical Formula 1][Chemical Formula 2]

Description

[0001] Cross-reference to Related Applications

[0002] This application claims priority and the benefit of Korean Patent Application No. 10-2022-0024688, filed on February 24, 2022, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a core-shell dye, a near-infrared absorbing resin composition containing the same, a near-infrared absorbing film using the same, a filter, and a complementary metal oxide semiconductor image sensor. Background Art

[0004] An image sensor is a semiconductor that converts photons into electrons and displays them on a display device or stores them in a storage device.

[0005] According to manufacturing processes and application methods, image sensors are classified into charge coupled device (CCD) image sensors and complementary metal-oxide semiconductor (CMOS) image sensors.

[0006] In addition, a CMOS image sensor includes a color filter including filtering segments of additive and mixed primary colors of red, green, and blue. On the other hand, a silicon-based photodiode (Si-photodiode) of a CMOS image sensor has sensitivity in a near-infrared wavelength region (specifically, from about 750 nanometers to about 1,000 nanometers), and a filter including a near-infrared absorbing film is also required.

[0007] The near-infrared absorbing film is used to reduce or prevent optical distortion caused by light other than light in the visible region (e.g., near-infrared rays), and is generally formed by coating and drying a composition containing a specific compound.

[0008] Compounds for the near-infrared absorbing film are known as inorganic dyes. However, inorganic dyes are materials having low near-infrared absorption intensity and need to be used in excess when manufacturing the near-infrared absorbing film. Therefore, as the amount of the inorganic dye increases, the viscosity of the composition increases, thereby deteriorating processability and making the film thicker.

[0009] Therefore, as a compound for the near-infrared absorbing film, it is necessary to replace the inorganic dye with an organic dye, but compared with inorganic dyes, organic pigments, etc., the organic dyes known so far have poor durability (e.g., chemical resistance, light resistance, etc.). Summary of the Invention

[0010] One embodiment provides a core-shell dye that exhibits high near-infrared absorption intensity while ensuring durability.

[0011] Another embodiment provides a near-infrared absorption composition containing the core-shell dye.

[0012] Another embodiment provides a near-infrared absorption film prepared by using the near-infrared absorption composition.

[0013] One embodiment provides a core-shell dye comprising: a core represented by Chemical Formula 1; and a shell surrounding the core and represented by Chemical Formula 2:

[0014] [Chemical Formula 1]

[0015]

[0016] Wherein, in Chemical Formula 1, Y 1 and Y 3 are each independently =CH- or a nitrogen atom; Y 2 and Y 4 are each independently -CH 2 -, a sulfur atom, -NH-, or an oxygen atom;

[0017] [Chemical Formula 2]

[0018]

[0019] Wherein, in Chemical Formula 2, A1 and A2 are each independently a divalent substituted or unsubstituted C6 to C30 aromatic ring; L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C30 alkylene group; and a is an integer from 2 to 10.

[0020] Y 2 and Y 4 can both be a sulfur atom.

[0021] Y 1 and Y 3 can both be =CH-.

[0022] R 1 to R 4 can each independently be a C6 to C30 aryl group; and R 1 to R 4 can each independently be unsubstituted or substituted at the end with at least one of the following: a C1 to C10 alkyl group, a C1 to C10 alkoxy group, an epoxy group, a (meth)acrylate group, or a cyano group.

[0023] R 1 to R 4 can each independently be represented by Chemical Formula 3:

[0024] [Chemical Formula 3]

[0025]

[0026] Among them, in Chemical Formula 3, R 5 is a substituent represented by Chemical Formula 3-1; and b is an integer from 0 to 5;

[0027] [Chemical Formula 3-1]

[0028] *-(L 3 ) c -R 6

[0029] Among them, in Chemical Formula 3-1, L 3 is a single bond, an oxygen atom or a substituted or unsubstituted C1 to C10 alkylene group; R 6 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, an epoxy group, a (meth)acrylate group or a cyano group; and c is an integer from 1 to 5.

[0030] R 1 to R 4 can all be the same.

[0031] The nucleus can be represented by any one selected from the following: [Chemical Formula 1-1]

[0032]

[0033] [Chemical Formula 1-2]

[0034]

[0035] [Chemical Formula 1-3]

[0036]

[0037] [Chemical Formula 1-4]

[0038]

[0039] [Chemical Formula 1-5]

[0040]

[0041] [Chemical Formula 1-6]

[0042]

[0043] A1 and A2 can each independently be a divalent substituted or unsubstituted benzene ring, a divalent substituted or unsubstituted pyridine ring, or a divalent substituted or unsubstituted anthracene ring.

[0044] A1 and A2 can each independently be represented by Chemical Formula 4-1 or Chemical Formula 4-2:

[0045] [Chemical Formula 4-1]

[0046]

[0047] [Chemical Formula 4-2]

[0048]

[0049] Wherein, in Chemical Formula 4-1 and Chemical Formula 4-2, Z 1 is *-CH-* or a nitrogen atom; X 1 to X 3 are each independently a halogen group or a substituted or unsubstituted C1 to C20 alkyl group; and d, e, and f are each independently an integer from 0 to 4.

[0050] Chemical Formula 2 can be Chemical Formula 2-1 or Chemical Formula 2-2:

[0051] [Chemical Formula 2-1]

[0052]

[0053] Wherein, in Chemical Formula 2-1, L 11 and L 21 are each independently a substituted or unsubstituted C1 to C10 alkylene group; Z 11 and Z 12 are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group; X 11 and X 12 are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group; d1 and d2 are each independently an integer from 0 to 4; and a1 is an integer from 2 to 10;

[0054] [Chemical Formula 2-2]

[0055]

[0056] Wherein, in Chemical Formula 2-2, L 12 and L 22 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group; Z 13 is *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group; X13 , X 21 and X 31 are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group; a2 is an integer from 2 to 10; and d3, e1, and f1 are each independently an integer from 0 to 4.

[0057] Z 11 and Z 12 Any one of

[0058] X 11 and X 12 can each independently be a halogen group, and d1 + d2 can be an integer from 1 to 8.

[0059] L 11 and L 21 can each independently be a C1 to C10 alkylene group.

[0060] a1 can be 2.

[0061] X 13 , X 21 and X 31 can each independently be a halogen group, and d3 + e1 + f1 can be an integer from 1 to 12.

[0062] L 12 and L 22 can each independently be a C1 to C10 alkylene group.

[0063] a2 can be 2.

[0064] The shell can be represented by any one selected from the following:

[0065] [Chemical formula 2-1-1]

[0066]

[0067] [Chemical formula 2-1-2]

[0068]

[0069] [Chemical formula 2-1-3]

[0070]

[0071] [Chemical formula 2-1-4]

[0072]

[0073] [Chemical formula 2-2-1]

[0074]

[0075] [Chemical formula 2-2-2]

[0076]

[0077] [Chemical formula 2-2-3]

[0078]

[0079] [Chemical formula 2-2-4]

[0080]

[0081] The core-shell dye may include a core and a shell with a molar ratio of about 1:1. The core-shell dye may be represented by any one selected from the following: [Chemical formula 5-1]

[0082]

[0083] [Chemical formula 5-2]

[0084]

[0085] [Chemical formula 5-3]

[0086]

[0087] [Chemical formula 5-4]

[0088]

[0089] [Chemical formula 5-5]

[0090]

[0091] [Chemical formula 5-6]

[0092]

[0093] [Chemical formula 5-7]

[0094]

[0095] [Chemical formula 5-8]

[0096]

[0097] [Chemical formula 5-9]

[0098]

[0099] [Chemical formula 5-10]

[0100]

[0101] [Chemical Formula 5-11]

[0102]

[0103] [Chemical Formula 5-12]

[0104]

[0105] [Chemical Formula 5-13]

[0106]

[0107] [Chemical Formula 5-14]

[0108]

[0109] [Chemical Formula 5-15]

[0110]

[0111] [Chemical Formula 5-16]

[0112]

[0113] [Chemical Formula 5-17]

[0114]

[0115] [Chemical Formula 5-18]

[0116]

[0117] [Chemical Formula 5-19]

[0118]

[0119] [Chemical Formula 5-20]

[0120]

[0121] [Chemical Formula 5-21]

[0122]

[0123] [Chemical Formula 5-22]

[0124]

[0125] [Chemical Formula 5-23]

[0126]

[0127] [Chemical Formula 5-24]

[0128]

[0129] [Chemical Formula 5-25]

[0130]

[0131] [Chemical Formula 5-26]

[0132]

[0133] [Chemical Formula 5-27]

[0134]

[0135] [Chemical Formula 5-28]

[0136]

[0137] [Chemical Formula 5-29]

[0138]

[0139] [Chemical Formula 5-30]

[0140]

[0141] [Chemical Formula 5-31]

[0142]

[0143] [Chemical Formula 5-32]

[0144]

[0145] [Chemical Formula 5-33]

[0146]

[0147] [Chemical Formula 5-34]

[0148]

[0149] [Chemical Formula 5-35]

[0150]

[0151] [Chemical Formula 5-36]

[0152]

[0153] [Chemical Formula 5-37]

[0154]

[0155] [Chemical formula 5-38]

[0156]

[0157] [Chemical formula 5-39]

[0158]

[0159] [Chemical formula 5-40]

[0160]

[0161] [Chemical formula 5-41]

[0162]

[0163] [Chemical formula 5-42]

[0164]

[0165] [Chemical formula 5-43]

[0166]

[0167] [Chemical formula 5-44]

[0168]

[0169] [Chemical formula 5-45]

[0170]

[0171] [Chemical formula 5-46]

[0172]

[0173] [Chemical formula 5-47]

[0174]

[0175] [Chemical formula 5-48]

[0176]

[0177] Approved to have a maximum absorption peak at a wavelength of about 750 nm to about 850 nm. The core-shell dye may have a maximum absorption peak of about 800 nm to about 1,000 nm.

[0178] The core-shell dye can be a near-infrared absorbing dye.

[0179] Another embodiment provides a near-infrared absorbing resin composition containing a core-shell dye.

[0180] The near-infrared absorbing resin composition may further contain a binder resin and a solvent.

[0181] The near-infrared absorbing resin composition can be used for a CMOS image sensor.

[0182] Another embodiment provides a near-infrared absorbing film prepared by using the near-infrared absorbing resin composition.

[0183] Another embodiment provides a filter including the near-infrared absorbing film.

[0184] Another embodiment provides a CMOS image sensor including the filter.

[0185] Other embodiments of the present invention are included in the following detailed description.

[0186] The core-shell dye according to the embodiment has excellent durability while showing an improved match with the near-infrared absorption wavelength band.

[0187] Therefore, the near-infrared absorbing resin composition containing the core-shell dye can form a fine pattern while reducing the dye content, thereby contributing to economically providing a near-infrared absorbing film for a CMOS image sensor. BRIEF DESCRIPTION OF THE DRAWINGS

[0188] Figure 1 A view showing the cage width of the shell represented by Chemical Formula 2. DETAILED DESCRIPTION

[0189] Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and the present invention is defined by the scope of the claims.

[0190] As used herein, when no specific definition is otherwise provided, "substituted" means that at least one hydrogen of a compound is replaced by the following: a halogen atom (F, Cl, Br, or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, a formamidyl group, a hydrazino group, a hydrazo group, a carbonyl group, a carbamoyl group, a mercapto 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.

[0191] As used herein, when no specific definition is otherwise provided, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl", and "heterocycloalkylidene" mean that at least one of N, O, S, or P is present in the cyclic compounds of cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylidene.

[0192] As used herein, when no specific definition is otherwise provided, "(meth)acrylate" means both "acrylate" and "methacrylate".

[0193] As used herein, when no specific definition is otherwise provided, the term "combination" means mixing or copolymerizing.

[0194] In the chemical formulas of this specification, unless a specific definition is otherwise provided, when a chemical bond is not shown at the position where it should be given, hydrogen is bonded at that position.

[0195] As used herein, when no specific definition is otherwise provided, when there are multiple substituents having the same number, these substituents are the same or different. For example, when there are four "X 1 " in Chemical Formula 2 to be described later, the four "X 1 " can all be the same as "F"; one "X 1 " can be "F", two "X 1 " can be "Cl", and one "X 1 " can be "Br".

[0196] However, these are examples.

[0197] In addition, as used herein, when no specific definition is otherwise provided, a dashed line or "*" means a moiety connected to the same or different atoms or chemical formulas.

[0198] (Core-shell dye)

[0199] The present invention relates to a compound for manufacturing a near-infrared absorption film, and provides an organic compound-based colorant that exhibits high near-infrared absorption intensity while ensuring durability.

[0200] Specifically, the examples provide a core-shell dye, comprising: a core represented by Chemical Formula 1; and a shell surrounding the core and represented by Chemical Formula 2:

[0201] [Chemical Formula 1]

[0202]

[0203] Wherein, in Chemical Formula 1, Y 1 and Y 3 are each independently =CH- or a nitrogen atom; Y 2 and Y 4 are each independently -CH 2 -, a sulfur atom, -NH-, or an oxygen atom; and R 1 to R 4 are each independently a C6 to C30 aryl group;

[0204] [Chemical Formula 2]

[0205]

[0206] Wherein, in Chemical Formula 2, A1 and A2 are each independently a divalent substituted or unsubstituted C6 to C30 aromatic ring; L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C30 alkylene group; and a is an integer from 2 to 10.

[0207] The core represented by Chemical Formula 1 is a croconium-based organic dye, and has a maximum absorption peak at a wavelength of about 750 nm to about 850 nm, and the intensity at the maximum absorption peak is higher than that of an inorganic dye. In addition, since the core represented by Chemical Formula 1 is an organic dye that does not form particles, it is more desirable than an organic pigment.

[0208] Therefore, when manufacturing a near-infrared absorbing film, compared with an inorganic dye, an organic pigment, etc., the core-shell dye containing the core represented by Chemical Formula 1 is desirable in terms of reducing the usage amount, increasing processability, thinning the film, etc.

[0209] On the other hand, compared with an inorganic dye, an organic pigment, etc., the core represented by Chemical Formula 1 has a problem of poor durability. The shell represented by Chemical Formula 2 is of a type of macrocyclic compound having a sufficient size to surround the core represented by Chemical Formula 1, and can compensate for the insufficient durability of the core represented by Chemical Formula 1.

[0210] In addition, without introducing a halogen group into the shell represented by Chemical Formula 2, the core-shell dye can have a maximum absorption peak at about 800 nm to about 900 nm, but when a halogen group is introduced into the shell represented by Chemical Formula 2, the core-shell dye can exhibit a maximum absorption peak between about 850 nm and about 1,000 nm. Shifting the maximum absorption peak of the core-shell dye to the long wavelength region by introducing a halogen group into the shell represented by Chemical Formula 2 means further improving the matching with the near-infrared absorption wavelength band.

[0211] Generally speaking, the core-shell dye of the embodiment can exhibit an improved matching with the near-infrared absorption wavelength band, as an effect of only the core represented by Chemical Formula 1; or alternatively, as a synergistic effect of the core represented by Chemical Formula 1 and the shell represented by Chemical Formula 2. In addition, the core-shell dye of the embodiment has excellent durability because the shell represented by Chemical Formula 2 surrounds the core represented by Chemical Formula 1.

[0212] Hereinafter, a core-shell dye of an embodiment will be described in more detail.

[0213] The nucleus represented by Chemical Formula 1

[0214] The nucleus represented by Chemical Formula 1 is a xanthenium-based organic dye, where Y 2 and Y 4 can both be sulfur atoms, and Y 1 and Y 3 can both be =CH-.

[0215] Specifically, compared with the case where the substituents at the same position are each independently a substituted or unsubstituted C1-C30 alkyl group or a C3-C30 cycloalkyl group, the four substituents (R 1 to R 4 ) contained in the nucleus represented by Chemical Formula 1 are each independently a substituted or unsubstituted C6-C30 aryl group, and the maximum absorption peak can be shifted to a longer wavelength region and the durability can be improved.

[0216] Specifically, R 1 to R 4 can each independently be a C6-C30 aryl group; and R 1 to R 4 can each independently be unsubstituted or substituted at the end with at least one of the following: a C1-C10 alkyl group, a C1-C10 alkoxy group, an epoxy group, a (meth)acrylate group, or a cyano group.

[0217] More specifically, R 1 to R 4 can each independently be a substituted or unsubstituted phenyl group and can be represented by Chemical Formula 3:

[0218] [Chemical Formula 3]

[0219]

[0220] wherein, in Chemical Formula 3, R 5 is a substituent represented by Chemical Formula 3-1; and b is an integer from 0 to 5;

[0221] [Chemical Formula 3-1]

[0222] *-(L 3 ) c -R 6

[0223] wherein, in Chemical Formula 3-1, L 3 is a single bond, an oxygen atom, or a substituted or unsubstituted C1-C10 alkylene group; R 6 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, an epoxy group, a (meth)acrylate group, or a cyano group; and c is an integer from 1 to 5.

[0224] More specifically, R 1 to R 4 can all be the same, and when R 1 to R 4 are all different, the maximum absorption peak can be shifted to the long wavelength region, and the durability can be improved.

[0225] The nucleus represented by Chemical Formula 1 can be represented by any one selected from the following:

[0226] [Chemical Formula 1-1]

[0227]

[0228] [Chemical Formula 1-2]

[0229]

[0230] [Chemical Formula 1-3]

[0231]

[0232] [Chemical Formula 1-4]

[0233]

[0234] [Chemical Formula 1-5]

[0235]

[0236] [Chemical Formula 1-6]

[0237]

[0238] The length of the nucleus represented by Chemical Formula 1 can be about 1 nanometer to about 3 nanometers, for example, about 1.5 nanometers to about 2 nanometers. When the nucleus represented by Chemical Formula 1 has a length within the above range, a core-shell dye can be easily formed.

[0239] In other words, when the nucleus represented by Chemical Formula 1 has a length within the above range, a shell as a macrocyclic compound can be obtained in the structure surrounding the compound represented by Chemical Formula 1. When using other compounds not within the above range, it is difficult to expect an improvement in durability because it is difficult for the shell to form a structure surrounding the nucleus.

[0240] The nucleus represented by Chemical Formula 1 itself can have a maximum absorption peak at a wavelength of about 750 nanometers to about 850 nanometers. A core-shell dye containing a nucleus having spectral characteristics can be applied to a composition for a near-infrared absorption film for a CMOS image sensor. A filter containing a near-infrared absorption film can smoothly transmit wavelengths of about 350 nanometers to about 650 nanometers while effectively implementing a near-infrared absorption function.

[0241] However, the maximum absorption peak of the core-shell dye can vary depending on whether a halogen group is introduced into the shell represented by Chemical Formula 2, which will be described later.

[0242] For reference purposes, the core represented by Chemical Formula 1 contains four resonance structures as shown in the following scheme, but in this specification, for convenience, only one structure of the compound represented by Chemical Formula 1 is shown:

[0243] [Scheme]

[0244]

[0245] That is, the core represented by Chemical Formula 1 can be represented by any one of the four resonance structures.

[0246] The shell represented by Chemical Formula 2

[0247] The shell represented by Chemical Formula 2 is a rotaxane-based macrocyclic compound and contains an amide bond (-CONH-). Therefore, the hydrogen atom contained in the amide bond of the shell represented by Chemical Formula 2 can form a non-covalent bond with the oxygen atom of the compound represented by Chemical Formula 1. Specifically, the two atoms form a hydrogen bond, thereby enhancing the durability of the core-shell dye.

[0248] In Chemical Formula 2, A1 and A2 can each independently be a divalent substituted or unsubstituted benzene ring, a divalent substituted or unsubstituted pyridine ring, or a divalent substituted or unsubstituted anthracene ring.

[0249] Specifically, A1 and A2 can each independently be represented by Chemical Formula 4-1 or Chemical Formula 4-2:

[0250] [Chemical Formula 4-1]

[0251]

[0252] [Chemical Formula 4-2]

[0253]

[0254] Wherein, in Chemical Formula 4-1 and Chemical Formula 4-2, Z 1 is *-CH-* or a nitrogen atom; X 1 to X 3 are each independently a halogen group or a substituted or unsubstituted C1 to C20 alkyl group; and d, e, and f are each independently an integer from 0 to 4.

[0255] More specifically, Chemical Formula 2 can be Chemical Formula 2-1 or Chemical Formula 2-2:

[0256] [Chemical Formula 2-1]

[0257]

[0258] Among them, in Chemical Formula 2-1, L 11 and L 21 are each independently a substituted or unsubstituted C1 to C10 alkylene group; Z 11 and Z 12 are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group; X 11 and X 12 are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group; d1 and d2 are each independently an integer from 0 to 4; and a1 is an integer from 2 to 10;

[0259] [Chemical Formula 2-2]

[0260]

[0261] Among them, in Chemical Formula 2-2, L 12 and L 22 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group; Z 13 is *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group; X 13 、X 21 and X 31 are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group; a2 is an integer from 2 to 10; and d3, e1, and f1 are each independently an integer from 0 to 4.

[0262] The description of the case where Chemical Formula 2 is Chemical Formula 2-1 is as follows.

[0263] Z 11 and Z 12 Any one of them can be *-CH-* or a nitrogen atom, and the other can be *-CH-*. When a nitrogen atom is introduced as any one of Z 11 and Z 12 , compared with the case where no nitrogen atom is introduced at all, the non-covalent bonds between the shell and the core or the non-covalent bonds inside the shell increase to further enhance the durability of the core-shell dye.

[0264] X 11 and X 12 can each independently be a halogen group, and d1 + d2 can be an integer from 1 to 8. When a fluorine atom is introduced as X 11 and X 12When at least one of them is present, compared with the case where no fluorine atom is introduced, the maximum absorption peak of the core-shell dye shifts to the long-wavelength region, making it possible to achieve an excellent match with the near-infrared absorption wavelength band. For example, X 11 and X 12 are both fluorine atoms (i.e., F), and d1 + d2 can be 8.

[0265] L 11 and L 21 can each independently be a C1 to C10 alkylene group. In this case, the solubility is improved, and it is easy to form a structure where the shell surrounds the core. For example, L 11 and L 21 can both be methylene groups (i.e., *-CH 2 -*).

[0266] a1 can be 2.

[0267] The description of the case where Chemical Formula 2 is Chemical Formula 2-2 is as follows.

[0268] Z 13 can be a nitrogen atom. When a nitrogen atom is introduced into Z 13 , compared with the case where no nitrogen atom is introduced at all, the non-covalent bonds between the shell and the core or the non-covalent bonds inside the shell increase to further enhance the durability of the core-shell dye.

[0269] X 13 , X 21 and X 31 can each independently be a halogen group, and d3 + e1 + f1 can be an integer from 1 to 12. When a fluorine atom is introduced as X 13 , X 21 and X 31 in at least one of them, compared with the case where no fluorine atom is introduced at all, the maximum absorption peak of the core-shell dye shifts to the long-wavelength region, and thus it is possible to achieve an excellent match with the near-infrared absorption wavelength band. For example, X 13 , X 21 and X 31 can all be fluorine atoms (i.e., F), and d3 + e1 + f1 can be 12.

[0270] L 12 and L 22 can each independently be a C1 to C10 alkylene group. In this case, the solubility is excellent, and it is easy to form a structure where the shell surrounds the core. For example, L 12 and L 22 can both be methylene groups (i.e., *-CH 2 -*).

[0271] a2 can be 2.

[0272] The shell can be represented by any one selected from the following: [Chemical formula 2-1-1]

[0273]

[0274] [Chemical formula 2-1-2]

[0275]

[0276] [Chemical formula 2-1-3]

[0277]

[0278] [Chemical formula 2-1-4]

[0279]

[0280] [Chemical formula 2-2-1]

[0281]

[0282] [Chemical formula 2-2-2]

[0283]

[0284] [Chemical formula 2-2-3]

[0285]

[0286] [Chemical formula 2-2-4]

[0287]

[0288] Compared with the shell represented by Chemical formula 2-1-1 to Chemical formula 2-1-4, the durability of the core-shell dye using the shell represented by Chemical formula 2-2-1 to Chemical formula 2-2-4 can be stronger. On the other hand, when the structure of the mother nucleus is the same, there is an effect of shifting the maximum absorption peak of the core-shell dye using the fluorine atom-substituted shell to the longer wavelength region.

[0289] The cage width of the shell can be about to about 7.5 Å, and the volume of the shell can be about to about 16 cubic Å. The cage width in the present disclosure refers to the internal distance of the shell. For example, in the shell represented by Chemical formula 2, it is the distance between two different phenylene groups connecting two methylene groups (see Figure 1 ). When the shell has a cage width within the above range, a core-shell dye having a structure surrounding the core represented by Chemical formula 1 can be obtained. Therefore, when the core-shell dye is added to the near-infrared absorbing resin composition, a near-infrared absorbing film having excellent durability and high brightness can be achieved.

[0290] Core-shell dye

[0291] Meanwhile, the core-shell dye may include a core and a shell with a molar ratio of about 1:1, and the core includes a compound represented by Chemical Formula 1. When the core and the shell are present in a molar ratio, a coating (shell) surrounding the core containing the compound represented by Chemical Formula 1 can be sufficiently formed.

[0292] Representative examples of the core-shell dye are as follows:

[0293] [Chemical Formula 5-1]

[0294]

[0295] [Chemical Formula 5-2]

[0296]

[0297] [Chemical Formula 5-3]

[0298]

[0299] [Chemical Formula 5-4]

[0300]

[0301] [Chemical Formula 5-5]

[0302]

[0303] [Chemical Formula 5-6]

[0304]

[0305] [Chemical Formula 5-7]

[0306]

[0307] [Chemical Formula 5-8]

[0308]

[0309] [Chemical Formula 5-9]

[0310]

[0311] [Chemical Formula 5-10]

[0312]

[0313] [Chemical Formula 5-11]

[0314]

[0315] [Chemical Formula 5-12]

[0316]

[0317] [Chemical Formula 5-13]

[0318]

[0319] [Chemical Formula 5-14]

[0320]

[0321] [Chemical Formula 5-15]

[0322]

[0323] [Chemical Formula 5-16]

[0324]

[0325] [Chemical Formula 5-17]

[0326]

[0327] [Chemical Formula 5-18]

[0328]

[0329] [Chemical Formula 5-19]

[0330]

[0331] [Chemical Formula 5-20]

[0332]

[0333] [Chemical Formula 5-21]

[0334]

[0335] [Chemical Formula 5-22]

[0336]

[0337] [Chemical Formula 5-23]

[0338]

[0339] [Chemical Formula 5-24]

[0340]

[0341] [Chemical Formula 5-25]

[0342]

[0343] [Chemical Formula 5-26]

[0344]

[0345] [Chemical Formula 5-27]

[0346]

[0347] [Chemical Formula 5-28]

[0348]

[0349] [Chemical Formula 5-29]

[0350]

[0351] [Chemical Formula 5-30]

[0352]

[0353] [Chemical Formula 5-31]

[0354]

[0355] [Chemical Formula 5-32]

[0356]

[0357] [Chemical Formula 5-33]

[0358]

[0359] [Chemical Formula 5-34]

[0360]

[0361] [Chemical Formula 5-35]

[0362]

[0363] [Chemical Formula 5-36]

[0364]

[0365] [Chemical Formula 5-37]

[0366]

[0367] [Chemical Formula 5-38]

[0368]

[0369] [Chemical Formula 5-39]

[0370]

[0371] [Chemical formula 5-40]

[0372]

[0373] [Chemical formula 5-41]

[0374]

[0375] [Chemical formula 5-42]

[0376]

[0377] [Chemical formula 5-43]

[0378]

[0379] [Chemical formula 5-44]

[0380]

[0381] [Chemical formula 5-45]

[0382]

[0383] [Chemical formula 5-46]

[0384]

[0385] [Chemical formula 5-47]

[0386]

[0387] [Chemical formula 5-48]

[0388]

[0389] The core-shell dye can have a maximum absorption peak at a wavelength of about 800 nanometers to about 1,000 nanometers.

[0390] Specifically, when no halogen group is introduced into the shell represented by Chemical formula 2, the core-shell dye containing the shell can have a maximum absorption peak at a wavelength of about 800 nanometers to about 900 nanometers. On the other hand, when a halogen group is introduced into the shell represented by Chemical formula 2, the core-shell dye can have a maximum absorption peak at a wavelength of about 850 nanometers to about 1,000 nanometers.

[0391] That is, when a halogen group is introduced into the shell represented by Chemical Formula 2, the maximum absorption peak of the core-shell compound shifts to the long-wavelength region compared to the case where no halogen group is introduced, and the matching with the near-infrared absorption wavelength band is improved.

[0392] The core-shell dye can be used alone as a near-infrared absorbing dye or can be used in combination with a conditioning dye.

[0393] Examples of the conditioning dye may include triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azaporphyrin dyes, indigo dyes, xanthene dyes, pyridone azo dyes, and the like.

[0394] (Near-infrared absorbing resin composition)

[0395] According to another embodiment, there is provided a near-infrared absorbing resin composition comprising a compound represented by Chemical Formula 1 or a core-shell dye.

[0396] The near-infrared absorbing resin composition may comprise (A) a colorant (core-shell dye), (B) a binder resin, and (C) a solvent.

[0397] Hereinafter, each component will be described in detail.

[0398] (A) Colorant

[0399] The colorant may comprise a core-shell dye, and the core-shell dye has been described above.

[0400] In addition to the core-shell dye, the colorant may further comprise a pigment.

[0401] The pigment may include a green pigment, a blue pigment, a red pigment, a purple pigment, a yellow pigment, a black pigment, and the like.

[0402] The red pigment may 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, etc. within the color index, and these pigments may be used alone or in combination of two or more, but the present disclosure is not necessarily limited thereto.

[0403] The purple pigment may include C.I. Pigment Violet 23:23, C.I. Pigment Violet 29, dioxazine violet, First Violet B, methyl violet lake, indanthrene bright violet, etc. in the color index, and these pigments may be used alone or in combination of two or more than two, but the present disclosure is not necessarily limited thereto.

[0404] The green pigment may include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, etc. in the color index, and these pigments may be used alone or in combination of two or more than two, but the present disclosure is not necessarily limited thereto.

[0405] The blue pigment may include copper phthalocyanine pigments in the color index, such as C.I. Pigment Blue 15:6, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6 or C.I. Pigment Blue 16, and these pigments may be used alone or in combination of two or more than two, but the present disclosure is not necessarily limited thereto.

[0406] The yellow pigment may include isoindoline pigments in the color index, such as C.I. Pigment Yellow 185, C.I. Pigment Yellow 139, etc.; quinoline yellow pigments, such as C.I. Pigment Yellow 138; nickel complex pigments, such as C.I. Pigment Yellow 150; etc., and these pigments may be used alone or in combination of two or more than two, but the present disclosure is not necessarily limited thereto.

[0407] The black pigment may include aniline black, perylene black, titanium black, carbon black, etc. in the color index, and these pigments may be used alone or in combination of two or more than two, but the present disclosure is not necessarily limited thereto.

[0408] The pigment may be included in the near-infrared absorbing resin composition in the form of a dispersion liquid. This pigment dispersion liquid may be composed of a pigment, a solvent, a dispersant, a dispersion resin, etc.

[0409] The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., and among these, propylene glycol methyl ether acetate may be preferably used.

[0410] Dispersants help pigments disperse evenly in the dispersion liquid, and all nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycol or its esters, polyoxyalkylene, polyol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines, etc. can be used, and these can be used alone or in combinations of two or more.

[0411] As the dispersing resin, an acrylic resin containing a carboxyl group can be used, which can improve the stability of the pigment dispersion liquid and the patterning ability of the pixel.

[0412] When mixing and using core-shell dyes and pigments, they can be used in a weight ratio of about 1:9 to about 9:1, and specifically, a weight ratio of about 3:7 to about 7:3. When mixed within the above weight ratio range, chemical resistance, durability, and the maximum absorption wavelength can be controlled within an appropriate range, and high brightness and contrast ratio can be exhibited in the desired color coordinates.

[0413] Based on the total amount of the near-infrared absorbing resin composition, the core-shell dye can be included in an amount of about 0.5 wt% to about 10 wt%. When the core-shell dye is used within the above range, chemical resistance, durability, and the maximum absorption wavelength can be controlled within an appropriate range, and high brightness and contrast ratio can be exhibited in the desired color coordinates. For example, the core-shell dye can be included in an amount of about 0.5 wt% to about 5 wt%, and even when the amount of the dye is reduced in this way, chemical resistance, durability, and the maximum absorption wavelength can be controlled within an appropriate range.

[0414] (B) Binder resin

[0415] The binder resin can be an organic binder, specifically, an acrylic binder. For example, the acrylic binder can be a curable binder and can include, for example, a thermosetting binder, a photo-curable binder, or a combination thereof.

[0416] The organic binder can include, for example, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose (HPMC), hydroxypropyl cellulose (HPC), xanthan gum, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), carboxymethyl cellulose, hydroxyethyl cellulose, or a combination thereof, but is not limited thereto.

[0417] A methyl methacrylate / benzyl methacrylate copolymer can be used, as in the examples to be described later, and its copolymerization ratio can be about 1:99 to about 99:1, and particularly about 10:90 to about 20:80, as the weight ratio of methyl methacrylate:benzyl methacrylate.

[0418] (C) Solvent

[0419] The solvent is not particularly limited, but specifically, for example, it is: alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisopentyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; cellulose acetates such as methyl cellulose acetate, ethyl cellulose acetate, diethyl cellulose acetate, etc.; 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, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; 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, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters such as methyl lactate, ethyl lactate, etc.; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, etc.; acetic acid alkoxyalkyl esters such as methoxyethyl acetate, ethoxyethyl acetate, methoxybutyl acetate, ethoxyethyl acetate, etc.; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, etc.; or keto acid esters such as ethyl pyruvate, etc., and may additionally be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellulose acetate, etc., and these may be used alone or as a mixture of two or more than two kinds.

[0420] In view of miscibility and reactivity, the solvent may be a glycol ether such as ethylene glycol monoethyl ether; an ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; an ester such as 2-hydroxyethyl propionate; a diethylene glycol such as diethylene glycol monomethyl ether; a propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0421] Based on the total amount of the near-infrared absorbing resin composition, the solvent may be included in a remaining amount of, for example, about 20% by weight to about 90% by weight. When the solvent is within the above range, the near-infrared absorbing resin composition has excellent applicability and can maintain excellent flatness in a film with a thickness of 3 microns or more than 3 microns.

[0422] (D) Other additives

[0423] The near-infrared absorbing resin composition may further include other additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing vinyl or (meth)acryloyloxy; a leveling agent; a fluorosurfactant; a radical polymerization initiator to prevent stains or spots during coating to adjust leveling, or to prevent pattern residues caused by non-development.

[0424] The near-infrared absorbing resin composition may further include an epoxy compound to improve the close contact characteristics with the substrate.

[0425] Examples of the epoxy compound may include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A epoxy compound, an alicyclic epoxy compound, or a combination thereof.

[0426] The usage amount of the additive can be controlled according to the desired characteristics.

[0427] Another embodiment provides a near-infrared absorbing film manufactured using the aforementioned near-infrared absorbing resin composition. The method for manufacturing the near-infrared absorbing film is as follows.

[0428] The aforementioned near-infrared absorbing resin composition can be coated on a polymer film by using an appropriate method (such as bar coating, spin coating, or slot coating). Thereafter, drying, thermal curing, or photocuring can be performed to finally obtain the near-infrared absorbing film.

[0429] Since the near-infrared absorbing film can effectively absorb light in the near-infrared region regardless of the incident direction, it effectively absorbs and blocks the light incident from the side direction in the near-infrared region, making it possible to reduce or prevent signal distortion caused by light in the visible region by the light incident from the side in the near-infrared region.

[0430] Another embodiment provides a filter including the aforementioned near-infrared absorbing film. Additionally, another embodiment provides a CMOS image sensor including the aforementioned filter.

[0431] When a filter including a near-infrared absorption film is applied to a CMOS image sensor, the occurrence of optical distortion caused by near-infrared rays can be reduced or prevented.

[0432] Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the present invention in any sense.

[0433] (Synthesis Example)

[0434] Synthesis Example 1: Synthesis of a core-shell dye represented by Chemical Formula 5-1

[0435] [Reaction Scheme 1]

[0436]

[0437] In a round-bottom flask, 2-iodothiophene (4.7 mmol), diphenylamine (9.5 mmol), Pd(OAc) 2 (0.33 mmol), t-BuONa (5.9 mmol), and 10 mL of toluene were sequentially placed and then stirred. Under a nitrogen atmosphere, P(t-Bu) 3 (0.75 mmol) was added thereto, and then the mixture was stirred at 110 °C for 24 hours. Subsequently, the organic layer was separated therefrom using ethyl acetate and distilled water, purified by column chromatography, and dried. (Yield: 45%)

[0438] [Reaction Scheme 2]

[0439]

[0440] In a round-bottom flask, the product represented by Reaction Scheme 1 (14.3 mmol), croconic acid (7 mmol), 20 mL of n-BuOH, and 20 mL of toluene were placed and then stirred at 110 °C for 4 hours. The resulting product was cooled to room temperature, solidified, washed with hexane, filtered, and dried. (Yield: 66%)

[0441] [Reaction Scheme 3]

[0442]

[0443] The product of Reaction Scheme 2 (5 mmol) was dissolved in 600 mL of a chloroform solvent, and then, while stirring at room temperature, m-phthaloyl chloride (20 mmol) and p-xylenediamine (20 mmol) dissolved in 60 mL of chloroform were added dropwise thereto over 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the core-shell dye represented by Chemical Formula 5-1. (Yield: 23%)

[0444] [Chemical Formula 5-1]

[0445]

[0446] Maldi-tof MS: 1141.33 m / z

[0447] Synthesis Example 2: Synthesis of the core-shell dye represented by Chemical Formulas 5-7

[0448] The core-shell dye represented by Chemical Formulas 5-7 was synthesized in the same manner as in Synthesis Example 1, except that tetrafluoroterephthalamide was used instead of terephthalamide.

[0449] [Chemical Formulas 5-7]

[0450]

[0451] Maldi-tof MS: 1285.2 m / z

[0452] Synthesis Example 3: Synthesis of the core-shell dye represented by Chemical Formulas 5-13

[0453] The core-shell dye represented by Chemical Formulas 5-13 was synthesized in the same manner as in Synthesis Example 1, except that pyridine dicarbonyl chloride was used instead of isophthaloyl chloride.

[0454] [Chemical Formulas 5-13]

[0455]

[0456] Maldi-tof MS: 1143.3 m / z

[0457] Synthesis Example 4: Synthesis of the core-shell dye represented by Chemical Formulas 5-19

[0458] The core-shell dye represented by Chemical Formulas 5-19 was synthesized in the same manner as in Synthesis Example 1, except that pyridine dicarbonyl chloride was used instead of isophthaloyl chloride and tetrafluoroterephthalamide was used instead of terephthalamide.

[0459] [Chemical Formulas 5-19]

[0460]

[0461] Maldi-tof MS: 1287.2 m / z

[0462] Synthesis Example 5: Synthesis of the core-shell dye represented by Chemical Formulas 5-25

[0463] The core-shell dye represented by Chemical Formulas 5-25 was synthesized in the same manner as in Synthesis Example 1, except that 9,10-bis(methylamino)-anthracene was used instead of terephthalamide.

[0464] [Chemical Formula 5-25]

[0465]

[0466] Maldi-tof MS: 1341.5 m / z

[0467] Synthesis Example 6: Synthesis of a core-shell dye represented by Chemical Formula 5-31

[0468] The core-shell dye represented by Chemical Formula 5-31 was synthesized in the same manner as in Synthesis Example 1, except that octafluoro-9,10-bis(methylamine)-anthracene was used instead of p-xylenediamine.

[0469] [Chemical Formula 5-31]

[0470]

[0471] Maldi-tof MS: 1629.4 m / z

[0472] Synthesis Example 7: Synthesis of a core-shell dye represented by Chemical Formula 5-37

[0473] The core-shell dye represented by Chemical Formula 5-37 was synthesized in the same manner as in Synthesis Example 1, except that pyridine dicarbonyl chloride was used instead of isophthaloyl chloride and 9,10-bis(methylamine)-anthracene was used instead of p-xylenediamine.

[0474] [Chemical Formula 5-37]

[0475]

[0476] Maldi-tof MS: 1343.5 m / z

[0477] Synthesis Example 8: Synthesis of a core-shell dye represented by Chemical Formula 5-43

[0478] The core-shell dye represented by Chemical Formula 5-43 was synthesized in the same manner as in Synthesis Example 1, except that pyridine dicarbonyl chloride was used instead of isophthaloyl chloride and tetrafluoro-9,10-bis(methylamine)-anthracene was used instead of p-xylenediamine.

[0479] [Chemical Formula 5-43]

[0480]

[0481] Maldi-tof MS: 1631.3 m / z

[0482] Synthesis Example 9: Synthesis of a core-shell dye represented by Chemical Formula 5-44

[0483] The core-shell dye represented by Chemical Formula 5-44 was synthesized in the same manner as in Synthesis Example 1, except that bis(2,4-dimethylphenyl)amine was used instead of diphenylamine, pyridine dicarbonyl chloride was used instead of isophthaloyl chloride, and tetrafluoro-9,10-bis(methylamino)anthracene was used instead of p-xylenediamine.

[0484] [Chemical Formula 5-44]

[0485]

[0486] Maldi-tof MS: 1743.6 m / z

[0487] Synthesis Example 10: Synthesis of the core-shell dye represented by Chemical Formula 5-45

[0488] [Reaction Scheme 4]

[0489]

[0490] Compound A as an intermediate was obtained by the same synthesis method as in Reaction Scheme 1, except that 4,4'-dihydroxydiphenyl was used instead of diphenylamine.

[0491] [Reaction Scheme 5]

[0492]

[0493] In a round-bottom flask, intermediate A (3 mmol), KOH (7.5 mmol), epichlorohydrin (9 mmol), and 10 mL of DMSO were sequentially placed, and then stirred at 50 °C for 4 hours. Subsequently, the organic layer was separated using ethyl acetate and distilled water, purified by column chromatography, and dried to obtain Compound B. (Yield: 30%)

[0494] The core-shell dye represented by Chemical Formula 5-45 was synthesized in the same manner as in Synthesis Example 1, except that Compound B was used, pyridine dicarbonyl chloride was used instead of isophthaloyl chloride, and tetrafluoro-9,10-bis(methylamino)anthracene was used instead of p-xylenediamine.

[0495] [Chemical Formula 5-45]

[0496]

[0497] Maldi-tof MS: 1919.5 m / z

[0498] Synthesis Example 11: Synthesis of the core-shell dye represented by Chemical Formula 5-46

[0499] [Reaction Scheme 6]

[0500]

[0501] In a round-bottom flask, intermediate A (3 mmol), triethylamine (7.5 mmol), methacryloyl chloride (9 mmol), and 10 mL of chloromethane were placed in sequence, and then stirred at room temperature for 30 minutes. Subsequently, the organic layer was separated therefrom using ethyl acetate and distilled water, purified by column chromatography, and dried to obtain compound C as an intermediate. (Yield: 50%)

[0502] Except for using compound C and using pyridine dicarbonyl chloride instead of isophthaloyl chloride and tetrafluoro-9,10-bis(methylamino)anthracene instead of p-xylenediamine, the core-shell dye represented by Chemical Formula 5-46 was synthesized by the same synthesis method as in Synthesis Example 1.

[0503] [Chemical Formula 5-46]

[0504]

[0505] Maldi-tof MS: 1967.6 m / z

[0506] Synthesis Example 12: Synthesis of the core-shell dye represented by Chemical Formula 5-47

[0507] Except for using 4,4'-dihydroxydiphenyl instead of diphenylamine, pyridine dicarbonyl chloride instead of isophthaloyl chloride, and tetrafluoro-9,10-bis(methylamino)anthracene instead of p-xylenediamine, the core-shell dye represented by Chemical Formula 5-47 was synthesized by the same synthesis method as in Synthesis Example 1.

[0508] [Chemical Formula 5-47]

[0509]

[0510] Maldi-tof MS: 1731.4 m / z

[0511] Synthesis Example 13: Synthesis of the core-shell dye represented by Chemical Formula 5-48

[0512] [Reaction Scheme 7]

[0513]

[0514] In a round-bottom flask, intermediate A (3 mmol), K 2 CO 3 (7.5 mmol), 1-bromo-2-ethylhexane (7.5 mmol), and 10 mL of DMF were placed in sequence, and then stirred at 120 °C for 24 hours. Subsequently, the organic layer was separated using ethyl acetate and distilled water, purified by column chromatography, and dried to obtain compound D as an intermediate. (Yield: 75%)

[0515] The core-shell dye represented by Chemical Formula 5-48 was synthesized by the same synthesis method as in Synthesis Example 1, except that Compound D was used, pyridine dicarbonyl chloride was used instead of isophthaloyl chloride, and tetrafluoro-9,10-bis(methylamino)anthracene was used instead of p-xylenediamine.

[0516] [Chemical Formula 5-48]

[0517]

[0518] Maldi-tof MS: 2144.2 m / z

[0519] Comparative Synthesis Example 1: Synthesis of a dye containing only a core represented by Chemical Formula E

[0520] The core-only compound represented by Chemical Formula E was synthesized by the same synthesis method as in Reaction Schemes 1 and 2, except that bis(2-ethylhexyl)amine was used instead of diphenylamine.

[0521] [Chemical Formula E]

[0522]

[0523] Maldi-tof MS: 640.9 m / z

[0524] Comparative Synthesis Example 2: Synthesis of a core-shell dye represented by Chemical Formula F

[0525] The core-shell dye represented by Chemical Formula F was synthesized by the same synthesis method as in Synthesis Example 1, except that bis(2-ethylhexyl)amine was used instead of diphenylamine.

[0526] [Chemical Formula F]

[0527]

[0528] Maldi-tof MS: 1173.5 m / z

[0529] Comparative Synthesis Example 3: Synthesis of a core-shell dye represented by Chemical Formula G

[0530] The compound represented by Chemical Formula G was synthesized by the same synthesis method as in Synthesis Example 1, except that dicyclohexylamine was used instead of diphenylamine.

[0531] [Chemical Formula G]

[0532]

[0533] Maldi-tof MS: 1165.5 m / z

[0534] Comparative Synthesis Example 4: Inorganic Colorant Represented by Chemical Formula H

[0535] [Reaction Scheme 8]

[0536]

[0537] In a round-bottom flask, place in sequence the intermediate of 4-tert-butylphthalonitrile (10 mmol), ammonium molybdate (2 mmol), and guanidine hydrochloride (12 mmol), and then stir at 300 °C for 2 hours. Purify the reaction mixture by column chromatography and dry it to obtain the compound represented by Chemical Formula H. (Yield: 15%)

[0538] [Chemical Formula H]

[0539]

[0540] Maldi-tof MS: 1105.1 m / z

[0541] (Preparation of Near-Infrared Absorbing Resin Composition)

[0542] Use the following components to prepare the near-infrared absorbing resin composition.

[0543] (A) Colorant

[0544] (A-1) Core-Shell Dye Prepared in Synthesis Example 1 (Chemical Formula 5-1)

[0545] (A-2) Core-Shell Dye Prepared in Synthesis Example 2 (Chemical Formula 5-7)

[0546] (A-3) Core-Shell Dye Prepared in Synthesis Example 3 (Chemical Formula 5-13)

[0547] (A-4) Core-Shell Dye Prepared in Synthesis Example 4 (Chemical Formula 5-19)

[0548] (A-5) Core-Shell Dye Prepared in Synthesis Example 5 (Chemical Formula 5-25)

[0549] (A-6) Core-Shell Dye Prepared in Synthesis Example 6 (Chemical Formula 5-31)

[0550] (A-7) Core-Shell Dye Prepared in Synthesis Example 7 (Chemical Formula 5-37)

[0551] (A-8) Core-Shell Dye Prepared in Synthesis Example 8 (Chemical Formula 5-43)

[0552] (A-9) Core-Shell Dye Prepared in Synthesis Example 9 (Chemical Formula 5-44)

[0553] (A-10) Core-shell dye prepared in Synthesis Example 10 (Chemical Formula 5-45)

[0554] (A-11) Core-shell dye prepared in Synthesis Example 11 (Chemical Formula 5-46)

[0555] (A-12) Core-shell dye prepared in Synthesis Example 12 (Chemical Formula 5-47)

[0556] (A-13) Core-shell dye prepared in Synthesis Example 13 (Chemical Formula 5-48)

[0557] (A-14) Core-shell dye prepared in Comparative Synthesis Example 1 (Chemical Formula E)

[0558] (A-15) Core-shell dye prepared in Comparative Synthesis Example 2 (Chemical Formula F)

[0559] (A-16) Core-shell dye prepared in Comparative Synthesis Example 3 (Chemical Formula G)

[0560] (A-17) Inorganic dye prepared in Comparative Synthesis Example 4 (Chemical Formula H)

[0561] (B) Binder resin

[0562] Methacrylic acid / phenyl methacrylate copolymer with a weight average molecular weight of 22,000 g / mol (mixing weight ratio 15 wt% / 85 wt%)

[0563] (C) Solvent

[0564] (C-1) Cyclohexanone

[0565] (C-2) Propylene glycol monomethyl ether acetate

[0566] Examples 1 to 13 and Comparative Examples 1 to 4

[0567] Each photosensitive resin composition was prepared by mixing the components in the compositions shown in Tables 1 to 3. Specifically, the colorant was added to the solvent, and then stirred for 30 minutes, and the binder resin was added thereto and then stirred at room temperature for 2 hours. This solution was filtered three times to remove impurities, thereby obtaining a near-infrared absorbing resin composition.

[0568] (Table 1)

[0569] (Unit: wt%)

[0570]

[0571] (Table 2)

[0572] (Unit: wt%)

[0573]

[0574] (Table 3)

[0575] (Unit: wt%)

[0576]

[0577] (Evaluation)

[0578] Evaluation 1: Wavelength matching evaluation

[0579] Use each of the near-infrared absorbing resin compositions according to Examples 1 to 13 and Comparative Examples 1 to 4 to prepare filter samples.

[0580] Specifically, coat each near-infrared absorbing resin composition on a degreased and washed 1-mm-thick glass substrate to a thickness of 1 to 3 µm, and dry it on a hot plate at 90 °C for 2 minutes to form a near-infrared absorbing film, thereby obtaining a filter sample containing the near-infrared absorbing film.

[0581] Detect the wavelength matching of the filter samples by the maximum absorption wavelength (λmax). Specifically, use a UV-Vis-NIR spectrometer (UV-3600 + UV-Vis-NIR spectrometer, Shimadzu Corp.) to measure the maximum absorption wavelength (λmax) of each filter sample, and simultaneously measure the absorption intensity at that wavelength. Herein, the measured maximum absorption wavelengths are shown in Table 4.

[0582] (Table 4)

[0583]

[0584] Referring to Table 4, the core-shell dyes according to Examples 1 to 13 are suitable for near-infrared absorption.

[0585] Specifically, the core-shell dyes of Examples 1 to 13 contain a xanthene-based organic dye as the core and exhibit a maximum absorption peak at a wavelength of 750 nm or greater than 750 nm. In particular, the core contained in the core-shell dyes of Examples 1 to 3 is represented by Chemical Formula 1, and when a substituted or unsubstituted C1 to C30 alkyl or C3 to C30 cycloalkyl is independently introduced into R 1 to R 4 compared with when a substituted or unsubstituted C6 to C30 aryl is independently introduced into the same position (Comparative Examples 1 to 3), the maximum absorption peak can be shifted to the long-wavelength region.

[0586] On the other hand, in Examples 1 to 13, the effect of the core structure was almost the same, but its maximum absorption wavelength varied depending on whether a halogen group (specifically, F) was introduced into the shell.

[0587] Specifically, when the core had the same structure, when a halogen group was introduced into the shell, the maximum absorption wavelength shifted to the long-wavelength region by about 20 nm, thus achieving an excellent match with the near-infrared absorption wavelength band at a level comparable to that of inorganic dyes (Comparative Example 4).

[0588] However, introducing a halogen group into the shell was optional.

[0589] Briefly, the core-shell dye of one embodiment exhibited an excellent match with the near-infrared absorption wavelength band due to the single effect of the core represented by Chemical Formula 1; or the synergistic effect of the core represented by Chemical Formula 1 and the shell represented by Chemical Formula 2.

[0590] Evaluation 2: Evaluation of light resistance and chemical resistance

[0591] (1) Light resistance evaluation: The filter sample obtained under the same conditions as in Evaluation 1 was exposed to light using a high-pressure mercury lamp with a main wavelength of 365 nm, and then dried in an oven at 230 °C for 20 minutes.

[0592] The absorption intensity of the substrate after the exposure described above at the maximum absorption wavelength (λmax) was measured by the foregoing method. This measured value and the measured value of Evaluation 1 were substituted into Equation 1 to calculate the light resistance, and the results are shown in Table 5.

[0593] [Equation 1]

[0594] Light resistance = 100% x {1 - (absorption intensity after exposure treatment) / (absorption intensity before exposure treatment)}

[0595] (2) Chemical resistance evaluation: The filter sample obtained under the same conditions as in Evaluation 1 was immersed in an NMP (N-methylpyrrolidone) solution at room temperature for 10 minutes.

[0596] The absorption intensity of the substrate after the chemical treatment described above at the maximum absorption wavelength (λmax) was measured by the foregoing method. This measured value and the measured value of Evaluation 1 were substituted into Equation 2 to calculate the chemical resistance, and the results are shown in Table 5.

[0597] [Equation 2]

[0598] Chemical resistance = 100% x {1 - (absorption intensity after chemical treatment) / (absorption intensity before chemical treatment)}

[0599] (Table 5)

[0600] Light resistance Chemical resistance Example 1 20％ 30％ Example 2 21％ 28％ Example 3 19％ 28％ Example 4 18％ 27％ Example 5 27％ 36％ Example 6 25％ 33％ Example 7 24％ 33％ Example 8 24％ 31％ Example 9 23％ 30％ Example 10 23％ 18％ Example 11 22％ 19％ Example 12 17％ 25％ Example 13 24％ 32％ Comparative Example 1 53％ 67％ Comparative Example 2 42％ 51％ Comparative Example 3 45％ 49％ Comparative Example 4 17％ 20％

[0601] Referring to Table 5, compared with Comparative Example 1, the core-shell dyes of Examples 1 to 13 exhibit significantly improved durability (light resistance and chemical resistance).

[0602] Specifically, compared with the dyes composed of only the core according to Comparative Example 1, the core-shell dyes according to Examples 1 to 13 further include a shell represented by Chemical Formula 2, and thus compensate for the insufficient durability of the core represented by Chemical Formula 1.

[0603] On the other hand, compared with the dyes composed of only the core according to Comparative Example 1, the dyes of Comparative Example 2 have a core-shell structure and exhibit improved durability (light resistance and chemical resistance).

[0604] However, the core included in the core-shell dyes of Examples 1 to 13 improves durability (light resistance and chemical resistance), the core is represented by Chemical Formula 1 and in which a substituted or unsubstituted C6 to C30 aryl group is independently introduced into R 1 to R 4 (compared with when a substituted or unsubstituted C1 to C30 alkyl group or C3 to C30 cycloalkyl group is independently introduced into the same position (Comparative Examples 2 and 3)).

[0605] In Examples 1 to 13, the effects of the shell structure are almost the same, but the durability is changed depending on whether an epoxy group and / or a (meth)acrylate group is introduced into the core.

[0606] Specifically, the (meth)acrylate group is a functional group that helps to improve heat resistance, and the *-O-* (epoxy) group is a functional group that helps to improve chemical resistance. Therefore, compared with when R 1 is unsubstituted, when substituted with at least one (meth)acrylate group, *-O-* (epoxy) group or a combination thereof, the chemical resistance, heat resistance, etc. of the core are appropriately improved.

[0607] Although the present invention has been described in connection with presently considered practical example embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, the present invention is intended to cover various modifications and equivalent configurations included within the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood as exemplary but not limiting the present invention in any way.

Claims

1. A core-shell dye, comprising a core represented by Chemical Formula 1; and a shell surrounding the core and represented by Chemical Formula 2-1 or 2-2: [Chemical Formula 1] wherein, in Chemical Formula 1, Y 1 and Y 3 each independently represents =CH- or a nitrogen atom; Y 2 and Y 4 each independently represents -CH 2 -, a sulfur atom, -NH-, or an oxygen atom; and R 1 to R 4 each is independently unsubstituted or substituted at the end with at least one of the following: C1 to C10 alkyl, C1 to C10 alkoxy, epoxy group, (meth)acrylate group or cyano group; [Chemical Formula 2-1] wherein, in Chemical Formula 2-1, L 11 and L 21 each independently represents a methylene group; Z 11 and Z 12 each independently represents *-CR-* or a nitrogen atom, where R is a hydrogen atom; X 11 and X 12 is a fluorine atom; d1 and d2 are each independently an integer from 0 to 4; and a1 is an integer from 2 to 10; [Chemical Formula 2-2] wherein, in Chemical Formula 2-2, L 12 and L 22 each independently represents a single bond or a methylene group; Z 13 is *-CR-* or a nitrogen atom, where R is a hydrogen atom; X 13 、X 21 and X 31 are fluorine atoms; a2 is an integer from 2 to 10; and d3, e1, and f1 are each independently an integer from 0 to 4.

2. The core-shell dye according to claim 1, wherein Y 2 and Y 4 are both sulfur atoms.

3. The core-shell dye according to claim 2, wherein Y 1 and Y 3 are both =CH-.

4. The core-shell dye according to claim 1, wherein R 1 to R 4 each independently represented by Chemical Formula 3: [Chemical Formula 3] wherein, in Chemical Formula 3, R 5 a substituent represented by Chemical Formula 3-1; and b is an integer from 0 to 5; [Chemical Formula 3-1] *-(L 3 ) c -R 6 wherein, in Chemical Formula 3-1, L 3 is a single bond, an oxygen atom or a methylene group; R 6 is an unsubstituted C1-C8 alkyl group, glycidyl group, (meth)acrylate group or cyano group; and c is an integer from 1 to 5.

5. The core-shell dye according to claim 4, wherein R 1 to R 4 All the same.

6. The core-shell dye according to claim 1, wherein the core is represented by any one selected from the following: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] 7. The core-shell dye according to claim 1, wherein d1 + d2 is an integer from 1 to 8.

8. The core-shell dye according to claim 1, wherein a1 is 2.

9. The core-shell dye according to claim 1, wherein d3 + e1 + f1 is an integer from 1 to 12.

10. The core-shell dye according to claim 1, wherein L 12 and L 22 are each independently a methylene group.

11. The core-shell dye according to claim 1, wherein a2 is 2.

12. The core-shell dye according to claim 1, wherein the shell is represented by any one selected from the following: [Chemical Formula 2-1-1] [Chemical Formula 2-1-2] [Chemical Formula 2-1-3] [Chemical Formula 2-1-4] [Chemical Formula 2-2-1] [Chemical Formula 2-2-2] [Chemical Formula 2-2-3] [Chemical Formula 2-2-4] 13. The core-shell dye according to claim 1, wherein the core-shell dye contains the core and the shell in a molar ratio of 1:

1.

14. The core-shell dye according to claim 1, wherein the core-shell dye is represented by any one selected from the following: [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] [Chemical Formula 5-4] [Chemical Formula 5-5] [Chemical Formula 5-6] [Chemical Formula 5-7] [Chemical Formula 5-8] [Chemical Formula 5-9] [Chemical Formula 5-10] [Chemical Formula 5-11] [Chemical Formula 5-12] [Chemical Formula 5-13] [Chemical Formula 5-14] [Chemical Formula 5-15] [Chemical Formula 5-16] [Chemical Formula 5-17] [Chemical Formula 5-18] [Chemical Formula 5-19] [Chemical Formula 5-20] [Chemical Formula 5-21] [Chemical Formula 5-22] [Chemical Formula 5-23] [Chemical Formula 5-24] [Chemical Formula 5-25] [Chemical Formula 5-26] [Chemical Formula 5-27] [Chemical Formula 5-28] [Chemical Formula 5-29] [Chemical Formula 5-30] [Chemical Formula 5-31] [Chemical Formula 5-32] [Chemical Formula 5-33] [Chemical Formula 5-34] [Chemical Formula 5-35] [Chemical Formula 5-36] [Chemical Formula 5-37] [Chemical Formula 5-38] [Chemical Formula 5-39] [Chemical Formula 5-40] [Chemical Formula 5-41] [Chemical Formula 5-42] [Chemical Formula 5-43] [Chemical Formula 5-44] [Chemical Formula 5-45] [Chemical Formula 5-46] [Chemical Formula 5-47] [Chemical Formula 5-48] 15. The core-shell dye according to claim 1, wherein the core has a maximum absorption peak at a wavelength of 750 nm to 850 nm.

16. The core-shell dye according to claim 15, wherein the core-shell dye has a maximum absorption peak at a wavelength of 800 nm to 1,000 nm.

17. The core-shell dye according to claim 1, wherein the core-shell dye is a near-infrared absorbing dye.

18. A near-infrared absorbing resin composition comprising the core-shell dye according to claim 1.

19. The near-infrared absorbing resin composition according to claim 18, wherein the near-infrared absorbing resin composition further comprises a binder resin and a solvent.

20. The near-infrared absorbing resin composition according to claim 18, wherein the near-infrared absorbing resin composition is for a complementary metal oxide semiconductor image sensor.

21. A near-infrared absorbing film manufactured by using the near-infrared absorbing resin composition according to claim 18.

22. A filter comprising the near-infrared absorbing film according to claim 21.

23. A complementary metal oxide semiconductor image sensor comprising the filter according to claim 22.

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