Core-shell dye, near-infrared absorbing resin composition containing the same, and near-infrared absorbing film

Abstract

The present disclosure relates to a core-shell dye, a near infrared absorbing resin composition containing the same, and a near infrared absorbing film. Specifically, one embodiment provides a core-shell dye comprising a core represented by the following formula 1; and a shell surrounding the core and represented by the following formula 2: JPEG2024511242000091.jpg94151 (In the above chemical formulas 1 and 2, each substituent is as defined in the specification.)

Description

[Technical field]

[0001] This description relates to a core-shell dye, a near infrared absorbing resin composition containing the same, and a near infrared absorbing film. [Background technology]

[0002] An image sensor is a semiconductor that converts photons into electrons so that they can be displayed on a display or stored in a memory device.

[0003] The image sensors are classified into charge coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors according to their manufacturing process and application.

[0004] The CMOS image sensor also includes a color filter including filter segments of additive primary colors of red, green, and blue. Meanwhile, the silicon-based photodiode of the CMOS image sensor has sensitivity in the near-infrared wavelength range (specifically, 750 nm to 1,000 nm), so it is necessary to include an optical filter including a near-infrared absorbing film.

[0005] The near infrared absorbing film serves to reduce or prevent optical distortion caused by light other than the visible light region (e.g., near infrared), and is generally prepared by coating and drying a composition containing a specific compound.

[0006] Inorganic dyes are known as compounds for preparing the near infrared ray absorbing film. However, since the inorganic dyes are substances with low near infrared ray absorption intensity, they must be used in excess when preparing the near infrared ray absorbing film. As the amount of inorganic dye used increases, the viscosity of the composition increases, the processability decreases, and the thickness of the film produced increases.

[0007] Therefore, organic dyes are required to replace inorganic dyes as compounds for manufacturing the near infrared absorbing film. However, the organic dyes known to date have a problem in that their durability (e.g., chemical resistance, light resistance, etc.) is inferior to that of inorganic dyes and organic pigments. Summary of the Invention [Problem to be solved by the invention]

[0008] One embodiment is to provide a core-shell dye that exhibits high near infrared absorption intensity while ensuring durability.

[0009] Yet another embodiment is to provide a near infrared absorbing composition comprising the core-shell dye.

[0010] Another embodiment provides a near infrared ray absorbing film prepared using the near infrared ray absorbing composition. [Means for solving the problem]

[0011] One embodiment provides a core-shell dye comprising a core represented by the following formula 1; and a shell surrounding the core represented by the following formula 2:

[0012] [ka]

[0013] In the above chemical formula 1, R 1are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 1 to 30 carbon atoms; 2 can be bonded to form a substituted or unsubstituted cycloalkyl ring having 3 to 30 carbon atoms; R 3 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 4 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 1 to 30 carbon atoms; 4 can be bonded to form a substituted or unsubstituted cycloalkyl ring having 3 to 30 carbon atoms;

[0014] [ka]

[0015] In the above chemical formula 2, L 1 and L 2 each independently represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Z 1 and Z 2 are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; X 1 and X 2 each independently represents a halogen group or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a1 and a2 each independently represents an integer of 0 to 4; and n is an integer of 2 or greater.

[0016] R 1are the same or different and each is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; 1 The substituents may be one or more (meth)acrylate groups, *-O-* (epoxy) groups, or a combination thereof.

[0017] R 2 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted arylalkyl group having 1 to 10 carbon atoms; 2 are bonded to form a cycloalkyl ring having 1 to 10 carbon atoms, which may be substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms; 2 The substituent may be one or more alkyl groups having 1 to 5 carbon atoms.

[0018] R 3 are the same or different and each is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; 3 The substituents may be one or more (meth)acrylate groups, *-O-* (epoxy) groups, or a combination thereof.

[0019] R 4 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted arylalkyl group having 1 to 10 carbon atoms; 2 are bonded to form a cycloalkyl ring having 1 to 10 carbon atoms, which may be substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms; 4 The substituent may be one or more alkyl groups having 1 to 5 carbon atoms.

[0020] The core represented by Formula 1 may have a symmetric structure.

[0021] The core represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4 below:

[0022] [ka]

[0023] [ka]

[0024] In the above chemical formulas 1-1 to 1-4, R 11 , R 12 , R 13 , R 21 , R 31 , R 32 , R 33 , R 41 and R 42 are each independently the same or different and are an alkyl group having 1 to 10 carbon atoms; L 31 , L 32 , L 41 and L 42 are each independently the same or different and are an alkylene group having 1 to 10 carbon atoms; R 5 , R 6 , R 8 and R 10 are each independently the same or different and each represents an alkyl group having 1 to 10 carbon atoms; R 7 and R 9 are each independently the same or different and are a (meth)acrylate group or an *-O-*(epoxy) group; c, d, e, f and g are each independently an integer of 0 to 5.

[0025] The core represented by Formula 1 may be represented by any one of the following groups:

[0026] [ka]

[0027] [ka]

[0028] In the above chemical formula 1-1-1, o and p each independently represent an integer of 0 to 5.

[0029] Said Z 1 and Z 2 Any one of the groups may be *--CH-- or a nitrogen atom, and the other may be *--CH--.

[0030] X 1 and X 2 are each independently a halogen group, and a1+a2 may be an integer of 1 to 8.

[0031] Said L 1 and L 2 may each independently be an alkylene group having 1 to 10 carbon atoms.

[0032] The n may be 2.

[0033] The shell may be represented by any one of the following formulas 2-1 to 2-4:

[0034] [ka]

[0035] [ka]

[0036] The core-shell dye may comprise the core and the shell in a 1:1 molar ratio.

[0037] The core-shell dye may be represented by any one selected from the group consisting of:

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] In the above chemical formulas 3-1-1, 4-1-1, 5-1-1, and 6-1-1, o and p each independently represent an integer of 0 to 5.

[0047] The core may have a maximum absorption peak at a wavelength of 700 nm to 850 nm.

[0048] The core-shell dye may have a maximum absorption peak at a wavelength of 700 nm to 1,000 nm.

[0049] The core-shell dye may be a near infrared absorbing dye.

[0050] Another embodiment provides a near infrared absorbing resin composition comprising the core-shell dye.

[0051] The near infrared absorbing resin composition may further include a binder resin and a solvent.

[0052] The near infrared absorbing resin composition may be for a CMOS image sensor.

[0053] Yet another embodiment provides a near infrared absorbing film produced using the near infrared absorbing resin composition.

[0054] Yet another embodiment provides an optical filter including the near infrared absorbing film.

[0055] Yet another embodiment provides a CMOS image sensor including the optical filter.

[0056] Other specific details of embodiments of the invention are included in the following detailed description. Effect of the Invention

[0057] The core-shell dye according to an embodiment may exhibit excellent compatibility with the near-infrared absorption wavelength band while simultaneously ensuring light resistance, chemical resistance, heat resistance, and the like.

[0058] Therefore, the near infrared ray absorbing resin composition containing the core-shell dye can form a fine pattern while reducing the dye content, and contributes to economically providing a near infrared ray absorbing film for a CMOS image sensor. [Brief description of the drawings]

[0059] [Figure 1] FIG. 2 is a diagram showing the cage width of the shell represented by Chemical Formula 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0060] Hereinafter, embodiments of the present invention will be described in detail, but they are given by way of example only and are not intended to limit the present invention, which is defined only by the scope of the claims set forth below.

[0061] Unless otherwise specified in this specification, "substituted" means that at least one hydrogen atom in a compound is replaced with a halogen atom (F, Cl, Br, I), a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amine group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. It means being substituted by an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, a heterocycloalkenyl group having 2 to 20 carbon atoms, a heterocycloalkynyl group having 2 to 20 carbon atoms, or a substituent of a combination thereof.

[0062] Unless otherwise specified in this specification, the terms "heterocycloalkyl group," "heterocycloalkenyl group," "heterocycloalkynyl group," and "heterocycloalkylene group" mean that at least one N, O, S, or P heteroatom is present in the ring system of a cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene, respectively.

[0063] Unless otherwise specified in this specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0064] Unless otherwise specified herein, "combination" means blending or copolymerization.

[0065] Unless otherwise defined in the chemical formulas herein, when no chemical bond is drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded to said position.

[0066] Unless otherwise specified in this specification, when there are multiple substituents having the same number, these substituents may be the same or different. For example, in the following Chemical Formula 2, "X 1 When there are four "X 1 " are all "F" and identical; one "X 1 " is "F" and two "X 1 " is "Cl", and one "X 1 " may be "Br", however, this is merely an example.

[0067] In addition, unless otherwise specified in this specification, the dotted lines

[0068]

number

[0069] or "*" means a moiety linked to the same or different atom or chemical formula.

[0070] (Core-Shell Dyes) The present invention relates to a compound for producing a near-infrared absorbing film, and aims to provide an organic compound-based colorant that exhibits high near-infrared absorption intensity while simultaneously ensuring light resistance, chemical resistance, heat resistance, etc.

[0071] Specifically, one embodiment provides a core-shell dye comprising a core represented by the following formula 1; and a shell surrounding the core represented by the following formula 2:

[0072] [ka]

[0073] In the above chemical formula 1, R 1are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 1 to 30 carbon atoms; 2 can be bonded to form a substituted or unsubstituted cycloalkyl ring having 3 to 30 carbon atoms; R 3 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 4 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 1 to 30 carbon atoms; 4 can be bonded to form a substituted or unsubstituted cycloalkyl ring having 3 to 30 carbon atoms;

[0074] [ka]

[0075] In the above chemical formula 2, L 1 and L 2 each independently represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Z 1 and Z 2 are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; X 1 and X 2 each independently represents a halogen group or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a1 and a2 each independently represents an integer of 0 to 4; and n is an integer of 2 or greater.

[0076] The core represented by Formula 1 is a compound having a structure in which the aniline moiety in a squalene (SQ)-based compound is replaced with a diamine naphthalene moiety, and the maximum absorption peak can be shifted to a longer wavelength region compared to a squalene-based compound. The shift of the maximum absorption peak to a longer wavelength region means that the compatibility with the near-infrared absorption wavelength band is further improved.

[0077] Specifically, the core represented by Chemical Formula 1 has a maximum absorption peak at a wavelength of 700 nm to 850 nm, and the intensity at the maximum absorption peak is higher than that of inorganic dyes. In addition, the core represented by Chemical Formula 1 is an organic dye that does not form particles, and is therefore more advantageous than organic pigments.

[0078] Therefore, the core-shell dye having the core represented by Chemical Formula 1 has excellent wavelength matching compared to inorganic dyes, organic pigments, etc., and is also advantageous in terms of reducing the amount of dye used in manufacturing a near infrared absorbing film, improving processability, and thinning the film.

[0079] Meanwhile, the core represented by Chemical Formula 1 has a problem of inferior durability compared to inorganic dyes, organic pigments, etc. The shell represented by Chemical Formula 2 is a type of macrocyclic compound having a sufficient size to surround the core represented by Chemical Formula 1, and can complement the lack of durability of the core represented by Chemical Formula 1.

[0080] Furthermore, the core-shell dye without a halogen group introduced into the shell represented by Chemical Formula 2 has a maximum absorption peak at 700 nm to 850 nm, whereas the core-shell dye with a halogen group introduced into the shell represented by Chemical Formula 2 has a maximum absorption peak at 850 nm to 1,000 nm. The introduction of a halogen group into the shell represented by Chemical Formula 2 shifts the maximum absorption peak of the core-shell dye to a longer wavelength region, which means that the compatibility with the near-infrared absorption wavelength band is further improved.

[0081] Overall, the core-shell dye of one embodiment is shown to have excellent compatibility with the near-infrared absorption wavelength band, as an effect of the core represented by Chemical Formula 1 alone, or an enhanced effect of the core represented by Chemical Formula 1 and the shell represented by Chemical Formula 2. In addition, the core-shell dye of one embodiment has excellent durability as a result of the shell represented by Chemical Formula 2 surrounding the core represented by Chemical Formula 1.

[0082] The core-shell dye of one embodiment will be described in more detail below.

[0083] The core represented by formula 1 The core represented by the formula 1, 1 are the same or different and each is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; 1 When substituted, the substituents may be one or more (meth)acrylate groups, *-O-* (epoxy) groups, or a combination thereof.

[0084] Specifically, the R 1 may be identically a methyl group or a phenyl group; 1 may be unsubstituted or substituted; 1 When substituted, the substituent may be a (meth)acrylate group or a *-O-* (epoxy) group.

[0085] The (meth)acrylate group is a functional group that contributes to improving heat resistance, and the -O- (epoxy) group is a functional group that contributes to improving chemical resistance. 1 In contrast to when unsubstituted, when substituted with one or more (meth)acrylate groups, *-O-*(epoxy) groups, or a combination thereof, the chemical resistance, heat resistance, etc. of the core can be appropriately improved.

[0086] R 2are the same or different and are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted arylalkyl group having 1 to 10 carbon atoms; 2 are bonded to form a cycloalkyl ring having 1 to 10 carbon atoms, which may be substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms; 2 The substituent may be one or more alkyl groups having 1 to 5 carbon atoms.

[0087] Specifically, the R 2 are the same, an alkyl group having 1 to 10 carbon atoms or a benzyl group (*-CH 2 -C 6 H 5 ) may be; 2 may be unsubstituted.

[0088] Unlike this, the two adjacent R 2 can combine to form a cycloalkyl ring having six carbon atoms; in this case, the cycloalkyl ring having six carbon atoms can be unsubstituted or substituted; however, if the cycloalkyl ring having six carbon atoms is substituted, the substituents can be two methyl groups.

[0089] R 3 are the same or different and each is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; 3 When substituted, the substituents may be one or more (meth)acrylate groups, *-O-* (epoxy) groups, or a combination thereof.

[0090] Specifically, the R 3 may be identically a methyl group or a phenyl group; 1 may be unsubstituted or substituted; 3 When substituted, the substituent may be a (meth)acrylate group or a *-O-* (epoxy) group.

[0091] The (meth)acrylate group is a functional group that contributes to improving heat resistance, and the *-O-(epoxy) group is a functional group that contributes to improving chemical resistance. 3 In contrast to when unsubstituted, when substituted with one or more (meth)acrylate groups, *-O-*(epoxy) groups, or a combination thereof, the chemical resistance, heat resistance, etc. of the core can be appropriately improved.

[0092] R 4 are the same or different and are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted arylalkyl group having 1 to 10 carbon atoms; 2 are bonded to form a cycloalkyl ring having 1 to 10 carbon atoms, which may be substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms; 2 The substituent may be one or more alkyl groups having 1 to 5 carbon atoms.

[0093] Specifically, the R 4 are the same, an alkyl group having 1 to 10 carbon atoms or a benzyl group (*-CH 2 -C 6 H 5 ) may be; 4 may be unsubstituted.

[0094] Unlike this, the two adjacent R 4 can combine to form a cycloalkyl ring having six carbon atoms; in this case, the cycloalkyl ring having six carbon atoms can be unsubstituted or substituted; however, if the cycloalkyl ring having six carbon atoms is substituted, the substituents can be two methyl groups.

[0095] The core represented by Formula 1 may have a symmetric structure.

[0096] Specifically, the R 1 is the above R 3 and R 2 is the above R 4In this case, the synthesis mechanism is simpler than when the core represented by Formula 1 has an asymmetric structure, which is advantageous in terms of increasing yield, reducing synthesis difficulty, and reducing unit cost.

[0097] The core represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-4:

[0098] [ka]

[0099] [ka]

[0100] In the above chemical formulas 1-1 to 1-4, R 11 , R 12 , R 13 , R 21 , R 31 , R 32 , R 33 , R 41 and R 42 are each independently the same or different and are an alkyl group having 1 to 10 carbon atoms; L 31 , L 32 , L 41 and L 42 are each independently the same or different and are an alkylene group having 1 to 10 carbon atoms; R 5 , R 6 , R 8 and R 10 are each independently the same or different and each represents an alkyl group having 1 to 10 carbon atoms; R 7 and R 9 are each independently the same or different and are a (meth)acrylate group or an *-O-*(epoxy) group; c, d, e, f and g are each independently an integer of 0 to 5.

[0101] In particular, the core represented by Formula 1 may be represented by any one of the following groups:

[0102] [ka]

[0103] [ka]

[0104] In the above chemical formula 1-1-1, o and p each independently represent an integer of 0 to 5.

[0105] The length of the core represented by Chemical Formula 1 may be 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the core represented by Chemical Formula 1 has a length within the above range, a core-shell dye can be easily formed.

[0106] In other words, when the core represented by Chemical Formula 1 has a length within the above range, the shell, which is the macrocyclic compound, is obtained as a structure surrounding the compound represented by Chemical Formula 1. When other compounds not falling within the above range of length are used, it is difficult for the shell to form a structure surrounding the core, and improvement in durability is difficult to expect.

[0107] The core itself represented by Chemical Formula 1 may have a maximum absorption peak at a wavelength of 700 nm to 850 nm. A core-shell dye including a core having the above-mentioned spectral characteristics may be applied to a composition for a near-infrared absorbing film of a CMOS image sensor. An optical filter including the near-infrared absorbing film can smoothly transmit wavelengths of 350 nm to 650 nm while effectively achieving a near-infrared absorbing function.

[0108] However, the maximum absorption peak of the core-shell dye changes depending on whether or not a halogen group is introduced into the shell represented by Formula 2, which will be described later.

[0109] For reference, the core represented by Formula 1 includes three resonance structures as shown in the following diagram, but for convenience, only one structure is shown for the compound represented by Formula 1 in this specification:

[0110] [ka]

[0111] That is, the core represented by Formula 1 can be represented by any one of the three resonance structures.

[0112] Shell represented by chemical formula 2 The shell represented by Chemical Formula 2 is a rotaxane-based macrocyclic compound and includes an amide bond (-CONH-). Therefore, a hydrogen atom included in the amide bond of the shell represented by Chemical Formula 2 can form a non-covalent bond with an oxygen atom of the compound represented by Chemical Formula 1. Specifically, the two atoms form a hydrogen bond to enhance the durability of the core-shell dye.

[0113] Specifically, the Z 1 and Z 2 Any one of Z may be *-CH-* or a nitrogen atom, and the other may be *-CH-*. 1 and Z 2 When a nitrogen atom is introduced as any one of the above, the non-covalent bond between the shell and the core or the non-covalent bond within the shell increases compared to when no nitrogen atom is introduced at all, thereby further enhancing the durability of the core-shell dye.

[0114] X 1 and X 2 are each independently a halogen group, and d1+d2 may be an integer of 1 to 8. 1 and X 2When a fluorine atom is introduced as at least one of X, the maximum absorption peak of the core-shell dye is shifted to a long wavelength region, compared to when no fluorine atom is introduced, and it is possible to realize excellent compatibility with the near infrared absorption wavelength band. 1 and X 2 are all fluorine atoms (i.e., F), and a1+a2 may be 8.

[0115] Said L 1 and L 2 may each independently be an alkylene group having 1 to 10 carbon atoms. In this case, the solubility is excellent, and it is easy to form a structure in which the shell surrounds the core. For example, 1 and L 1 are all methylene groups (i.e., *-CH 2 -*) may also be used.

[0116] The n may be 2.

[0117] The shell may be represented by any one of the following formulas 2-1 to 2-4:

[0118] [ka]

[0119] [ka]

[0120] When the structure of the mother nucleus is the same among the above 2-1 to 2-4, there is an effect of shifting the maximum absorption peak of the core-shell dye using a shell substituted with a fluorine atom to a longer wavelength region.

[0121] The cage width of the shell may be 6.5 Å to 7.5 Å, and the volume of the shell may be 10 Å to 16 Å. In the present application, the cage width refers to the distance inside the shell, for example, the distance between two different phenylene groups with methylene groups connected to both sides in the shell represented by Chemical Formula 2 (see FIG. 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, and thus, when the core-shell dye is added to a near-infrared absorbing resin composition, a near-infrared absorbing film having excellent durability and high brightness can be realized.

[0122] Core-Shell Dyes Meanwhile, the core-shell dye may include a core containing the compound represented by Formula 1 and the shell in a molar ratio of 1:1. When the core and shell are present in this molar ratio, a coating layer (shell) surrounding the core containing the compound represented by Formula 1 is often formed.

[0123] Representative examples of said core-shell dyes are as follows:

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] In the above chemical formulas 3-1-1, 4-1-1, 5-1-1, and 6-1-1, o and p each independently represent an integer of 0 to 5.

[0133] The core-shell dye may have a maximum absorption peak at a wavelength of 700 nm to 1,000 nm.

[0134] Specifically, when no halogen group is introduced into the shell represented by Chemical Formula 2, the core-shell dye containing the same may have a maximum absorption peak at a wavelength of 700 nm to 850 nm. In contrast, when a halogen group is introduced into the shell represented by Chemical Formula 2, the core-shell dye may have a maximum absorption peak at a wavelength of 850 nm to 1,000 nm.

[0135] 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 is shifted to a longer wavelength region compared to the case where a halogen group is not introduced, and it is shown that the compatibility with the near-infrared absorption wavelength band is excellent.

[0136] The core-shell dye can be used alone as a near infrared absorbing dye, or can be used in combination with a toning dye.

[0137] Examples of the toning dye include triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azaporphyrin dyes, indigo dyes, xanthene dyes, and pyridone azo dyes.

[0138] (Near infrared absorbing resin composition) According to another embodiment, there is provided a near infrared absorbing resin composition comprising the compound represented by Chemical Formula 1 or the core-shell dye.

[0139] The near infrared absorbing resin composition can include (A) a colorant (the core-shell dye), (B) a binder resin, and (C) a solvent.

[0140] Each component will be specifically described below.

[0141] (A) Colorant The colorant can include the core-shell dyes described above.

[0142] The colorant may further include a pigment in addition to the core-shell dye.

[0143] As the pigment, a green pigment, a blue pigment, a red pigment, a purple pigment, a yellow pigment, a black pigment, etc. can be used.

[0144] The red pigment may be CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, etc., which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0145] The purple pigment may be CI Violet Pigment 23 (V.23), CI Violet Pigment 29, Dioxazine Violet, Fast Violet B, Methyl Violet Lake, Indanthrene Brilliant Violet, etc., in the Color Index, and may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0146] The green pigment may be, for example, CI Green Pigment 7, CI Green Pigment 36, CI Green Pigment 58, CI Green Pigment 59, etc., in the Color Index, which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0147] The blue pigment may be a copper phthalocyanine pigment such as CI Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3, CI Blue Pigment 15:4, CI Blue Pigment 15:5, CI Blue Pigment 15:6, CI Blue Pigment 16, etc., which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0148] The yellow pigment may be an isoindoline pigment such as CI Yellow Pigment 185, CI Yellow Pigment 139, etc., a quinophthalone pigment such as CI Yellow Pigment 138, etc., or a nickel complex pigment such as CI Yellow Pigment 150, etc., which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0149] The black pigment may be aniline black, perylene black, titanium black, carbon black, etc., which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0150] The pigments may be used alone or in combination of two or more thereof. For example, the pigment may be a blue pigment, a purple pigment, or a mixture thereof.

[0151] The pigment may be included in the near infrared absorbing resin composition in the form of a dispersion. The pigment dispersion may include the pigment, a solvent, a dispersant, a dispersion resin, and the like.

[0152] The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like. Among these, propylene glycol methyl ether acetate is preferred.

[0153] The dispersant helps the pigment to be uniformly dispersed in the dispersion liquid, and all nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc. can be used, and these can be used alone or in combination of two or more.

[0154] The dispersing resin may be an acrylic resin containing a carboxyl group, which can improve not only the stability of the pigment dispersion liquid but also the patternability of the pixels.

[0155] When the core-shell dye and the pigment are mixed and used, they can be mixed at a weight ratio of 1:9 to 9:1, specifically, 3:7 to 7:3. When mixed within this weight ratio range, chemical resistance, durability, and maximum absorption wavelength can be controlled within appropriate ranges, and high brightness and light-dark ratio can be achieved with desired color coordinates.

[0156] The core-shell dye may be included in an amount of 0.5% by weight to 10% by weight based on the total amount of the near infrared absorbing resin composition. When the core-shell dye is used within the above range, the chemical resistance, durability, and maximum absorption wavelength can be controlled within appropriate ranges, and high brightness and light-dark ratio can be expressed with desired color coordinates. For example, the core-shell dye may be included in an amount of 0.5% by weight to 5% by weight, and thus, even if the amount of dye used is reduced, the chemical resistance, durability, and maximum absorption wavelength can be controlled within appropriate ranges.

[0157] (B) Binder resin The binder resin may be an organic binder, specifically an acrylic binder. For example, the acrylic binder may be a curable binder, such as a thermosetting binder, a photocurable binder, or a combination thereof.

[0158] The organic binder may be, for example, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose (HPMC), hydroxylpropyl cellulose (HPC), xanthan gum, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), carboxy methyl cellulose, hydroxyl ethyl cellulose, or a combination thereof, but is not limited thereto.

[0159] A methacrylic acid / benzyl methacrylate copolymer as in the examples described later can be used, and the copolymerization ratio thereof may be 1:99 to 99:1, specifically 10:90 to 20:80, in terms of the weight ratio of methacrylic acid:benzyl methacrylate.

[0160] (C) Solvent The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; 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, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, Ketones such as cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, and 2-heptanone; alkyl esters of saturated aliphatic monocarboxylic acids such as ethyl acetate, n-butyl acetate, and isobutyl acetate; alkyl esters of lactate such as methyl lactate and ethyl lactate; alkyl esters of hydroxyacetate such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; methoxymethyl Alkoxyalkyl acetates, such as ethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; alkyl 3-hydroxypropionates, such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; alkyl 3-alkoxypropionates, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate;2-Hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate esters such as methyl butanoate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate; or ketone acid esters such as ethyl pyruvate; N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, 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 cellosolve acetate, etc., which may be used alone or in combination of two or more;

[0161] Among the above solvents, in consideration of miscibility and reactivity, it is preferable to use glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxyethyl propionate; diethylene glycols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.

[0162] The solvent may be contained as the remainder with respect to the total amount of the near infrared absorbing resin composition, specifically, may be contained in an amount of 20% by weight to 90% by weight. When the solvent is contained within the above range, the near infrared absorbing resin composition has excellent coatability and can maintain excellent flatness in a film having a thickness of 3 μm or more.

[0163] (D) Other additives The near infrared absorbing resin composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl group or a (meth)acryloxy group; a leveling agent; a fluorine-based surfactant; and a radical polymerization initiator in order to prevent stains or spots during application, improve leveling performance, and prevent the generation of residues due to undevelopment.

[0164] In addition, the near infrared absorbing resin composition may further include an additive such as an epoxy compound in order to improve adhesion to a substrate.

[0165] Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

[0166] The content of the additives can be easily adjusted depending on the desired physical properties.

[0167] In another embodiment, a near infrared absorbing film is produced using the near infrared absorbing resin composition. The near infrared absorbing film is produced by the following method.

[0168] The near-infrared absorbing resin composition can be applied onto a polymer film using a suitable method such as bar coating, spin coating, slit coating, etc., and then dried and cured by heat or light to finally obtain a near-infrared absorbing film.

[0169] The near-infrared absorbing film can effectively absorb light in the near-infrared region regardless of the incident direction, and can effectively absorb and block light in the near-infrared region incident from a lateral direction, thereby reducing or preventing distortion of a signal due to light in the visible light region caused by light in the near-infrared region incident from a lateral direction.

[0170] Another embodiment provides an optical filter including the near infrared absorbing film described above. Another embodiment provides a CMOS image sensor including the optical filter described above.

[0171] When an optical filter including the near-infrared absorbing film is applied to a CMOS image sensor, optical distortion caused by near-infrared rays can be reduced or prevented.

[0172] Hereinafter, preferred embodiments of the present invention will be described, however, the following embodiment is merely one preferred embodiment of the present invention and the present invention is not limited to the following embodiment. EXAMPLES

[0173] (Synthesis example) Synthesis Example 1: Synthesis of core-shell dye represented by chemical formula 3-1-1 (1) Synthesis of Compound A-1

[0174] [ka]

[0175] 1,8-diaminonaphthalene (6mmol), 2-octanone (6mmol), p-toluenesulfonic acid (0.6mmol), and toluene were placed in a round-bottom flask and refluxed. After about 15 hours, the mixture was washed several times with ethyl acetate (EA) and water. After vacuum distillation, the mixture was separated by column chromatography to obtain compound A-1 as an intermediate.

[0176] (2) Synthesis of Compound A-2

[0177] [ka]

[0178] Compound A-1 (5 mmol), sodium bicarbonate (25 mmol), iodo methane (12.5 mmol), and DMF were added to a round flask and stirred at 50° C. for 4 hours, then washed several times with ethyl acetate (EA) and water. After vacuum distillation, compound A-2 was obtained as an intermediate by separation using column chromatography.

[0179] (3) Synthesis of compound A-3

[0180] [ka]

[0181] Compound A-2 (10 mmol) and 3,4-Dihydroxy-cyclobut-3-ene-1,2-dione (5 mmol) were added to toluene and butanol and refluxed to remove the generated water using a Dean-Stark distillation apparatus. After stirring for 12 hours, the reactant was distilled under reduced pressure and purified by column chromatography to obtain compound A-3 as an intermediate.

[0182] (3) Synthesis of the core-shell dye represented by chemical formula 3-1-1 The compound A-3 (5 mmol) was dissolved in chloroform, and then isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 3-1-1.

[0183] [ka]

[0184] Synthesis Example 2: Synthesis of core-shell dye represented by chemical formula 4-1-1 The compound A-3 (5 mmol) was dissolved in chloroform, and then isophthaloyl chloride (20 mmol) and tetrafluoro-p-xylylenediamine (20 mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 4-1-1.

[0185] [ka]

[0186] Synthesis Example 3: Synthesis of core-shell dye represented by chemical formula 5-1-1 The compound A-3 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 5-1-1.

[0187] [ka]

[0188] Synthesis Example 4: Synthesis of core-shell dye represented by chemical formula 6-1-1 The compound A-3 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and tetrafluoro-p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 6-1-1.

[0189] [ka]

[0190] Synthesis Example 5: Synthesis of core-shell dye represented by chemical formula 6-2-1 (1) Synthesis of Compound B-1

[0191] [ka]

[0192] The compound was synthesized in the same manner as in the synthesis of the compound A-1, except that 2-octanone was changed to 3,4-dimethylcyclohexanone.

[0193] (2) Synthesis of compound B-2

[0194] [ka]

[0195] Compound A-1 was replaced with compound B-1 in the synthesis method for compound A-2, and the synthesis was otherwise the same as that for compound A-2.

[0196] (3) Synthesis of compound B-3

[0197] [ka]

[0198] Compound B-2 was used instead of Compound A-2 in the synthesis of Compound A-3, and the synthesis was otherwise the same as that of Compound A-3.

[0199] (4) Synthesis of the core-shell dye represented by formula 6-2-1 The compound B-3 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and tetrafluoro-p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 6-2-1.

[0200] [ka]

[0201] Synthesis Example 6: Synthesis of core-shell dye represented by chemical formula 6-3-1 (1) Synthesis of Compound C-1

[0202] [ka]

[0203] The compound was synthesized in the same manner as in the synthesis of compound A-2, except that iodo methane was changed to iodo benzene.

[0204] (2) Synthesis of compound C-2

[0205] [ka]

[0206] Compound A-2 was replaced with compound C-1 in the synthesis method for compound A-3, and the synthesis was otherwise the same as that for compound A-3.

[0207] (4) Synthesis of the core-shell dye represented by formula 6-3-1 The compound C-2 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and tetrafluoro-p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 6-3-1.

[0208] [ka]

[0209] Synthesis Example 7: Synthesis of core-shell dye represented by chemical formula 6-3-2 (1) Synthesis of compound D-1

[0210] [ka]

[0211] The compound was synthesized in the same manner as in the synthesis of compound A-2, except that iodo methane was changed to 4-iodophenol.

[0212] (2) Synthesis of compound D-2

[0213] [ka]

[0214] The compound D-1 (20 mmol) was dissolved in dichloromethane solvent, triethylamine (50 mmol) was added, and the inside was cooled with N2 charge and ice bath. After cooling, methacryloyl chloride (45 mmol) was added dropwise. The mixture was stirred for about 2 hours from 0°C to room temperature. After 2 hours, it was extracted with MC. The compound D-2 was obtained as an intermediate by vacuum distillation and separation by column chromatography.

[0215] (3) Synthesis of compound D-3

[0216] [ka]

[0217] Compound D-3 was used instead of Compound A-2 in the synthesis of Compound A-3, and the rest of the synthesis was carried out in the same manner as Compound A-3.

[0218] (4) Synthesis of the core-shell dye represented by formula 6-3-2 The compound D-3 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and tetrafluoro-p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 6-3-2.

[0219] [ka]

[0220] Synthesis Example 8: Synthesis of core-shell dye represented by chemical formula 6-3-3 (1) Synthesis of compound E-1

[0221] [ka]

[0222] The compound D-1 (10 mmol) was dissolved in DMF solvent, and then imidazole (30 mmol) was added and stirred at room temperature for 30 minutes. Tert-butyldimethylsilyl chloride (25 mmol) was added and stirred at 40°C for 3 hours. After washing several times with ethyl acetate / water, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound E-1 as an intermediate.

[0223] (2) Synthesis of compound E-2

[0224] [ka]

[0225] Compound A-2 was replaced with compound E-1 in the synthesis method for compound A-3, and the synthesis was otherwise the same as that for compound A-3.

[0226] (3) Synthesis of compound B-3

[0227] [ka]

[0228] The compound E-2 (5 mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20 mmol) and tetrafluoro-p-xylylenediamine (20 mmol) were dissolved in chloroform and dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound E-3 as an intermediate.

[0229] (4) Synthesis of compound E-4

[0230] [ka]

[0231] The compound E-3 (5 mmol) was dissolved in tetrahydrofuran solvent, and then tetrabutylammonium fluoride (11 mmol) was added at room temperature. After 30 minutes, the mixture was separated by column chromatography to obtain the compound E-4 as an intermediate.

[0232] (4) Synthesis of core-shell dye represented by chemical formula 6-3-3 The compound E-4 (5 mmol), KOH (25 mmol), and epichlorohydrin (50 mmol) were reacted in 25 mL of dimethyl sulfoxide solvent for 2 hours, and then the mixture was diluted with 10% NH 4 Extract with Cl2 aqueous solution and ethyl acetate. Separate with column chromatography to obtain the core-shell dye represented by the following formula 6-3-3.

[0233] [ka]

[0234] Synthesis Example 9: Synthesis of core-shell dye represented by chemical formula 6-4-1 (1) Synthesis of compound F-1

[0235] [ka]

[0236] 1,8-diaminonaphthalene (6mmol), 1-phenyl-2butanone (6mmol), p-toluene sulfonic acid (0.6mmol) and toluene were placed in a round-bottom flask and refluxed. After about 15 hours, the mixture was washed several times with ethyl acetate (EA) and water. After vacuum distillation, the mixture was separated by column chromatography to obtain the compound F-1 as an intermediate.

[0237] (2) Synthesis of compound F-2

[0238] [ka]

[0239] Compound A-1 was replaced with compound F-1 in the synthesis method for compound A-2, and the synthesis was otherwise the same as that for compound A-2.

[0240] (3) Synthesis of compound F-3

[0241] [ka]

[0242] Compound F-2 was used instead of Compound A-2 in the synthesis of Compound A-3, and the synthesis was otherwise the same as that of Compound A-3.

[0243] (4) Synthesis of the core-shell dye represented by formula 6-4-1 The compound F-2 (5mmol) was dissolved in chloroform, and then pyridine-2,6-dicarbonyl dichloride (20mmol) and tetrafluoro-p-xylylenediamine (20mmol) were dissolved in chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell dye represented by the following formula 6-4-1.

[0244] [ka]

[0245] Comparative synthesis example 1: Synthesis of a dye containing only the core represented by the chemical formula G (1) Synthesis of compound G-1

[0246] [ka]

[0247] N-methylaniline (6mmol), 2-octanone (6mmol), p-toluenesulfonic acid (0.6mmol) and toluene were placed in a round-bottom flask and refluxed. After about 15 hours, the mixture was washed several times with ethyl acetate (EA) and water. After vacuum distillation, the mixture was separated by column chromatography to obtain the compound G-1 as an intermediate.

[0248] (2) Synthesis of dyes containing only the core represented by formula G The same synthesis procedure was followed as in the synthesis of intermediate A-3, except that intermediate A-2 was replaced with intermediate G-1, to obtain a dye having only a core represented by the following chemical formula G.

[0249] [ka]

[0250] Comparative synthesis example 2: Synthesis of a core-shell dye represented by the chemical formula H The compound A (5 mmol) was dissolved in chloroform, and then isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in chloroform and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by the following formula H.

[0251] [ka]

[0252] (Production of near infrared absorbing resin composition) The specifications of the components used in the production of the near infrared absorbing resin composition are as follows.

[0253] (A) Colorant (A-1) Core-shell dye prepared in Synthesis Example 1 (Chemical Formula 3-1-1) (A-2) Core-shell dye (chemical formula 4-1-1) prepared in Synthesis Example 2 (A-3) Core-shell dye (chemical formula 5-1-1) prepared in Synthesis Example 3 (A-4) Core-shell dye (chemical formula 6-1-1) prepared in Synthesis Example 4 (A-5) Core-shell dye (chemical formula 6-2-1) prepared in Synthesis Example 5 (A-6) Core-shell dye prepared in Synthesis Example 6 (Chemical Formula 6-3-1) (A-7) Core-shell dye (chemical formula 6-3-2) prepared in Synthesis Example 7 (A-8) Core-shell dye (chemical formula 6-3-3) prepared in Synthesis Example 8 (A-9) Core-shell dye (chemical formula 6-4-1) prepared in Synthesis Example 9 (A-10) Core-shell dye (chemical formula G) prepared in Comparative Synthesis Example 1 (A-11) Core-shell dye (chemical formula H) prepared in Comparative Synthesis Example 2 (A-12) The following pigment CI, Pigment green 7

[0254] [ka]

[0255] (B) Binder resin Methacrylic acid / benzyl methacrylate copolymer (mixture weight ratio 15wt% / 85wt%) with a weight average molecular weight of 22,000g / mol (C) Solvent (C-1) Cyclohexanone (C-2) Propylene glycol methyl ether acetate Examples 1 to 8 and Comparative Examples 1 to 3 Photosensitive resin compositions were prepared by mixing the components according to the compositions shown in Tables 1 to 3 below. Specifically, a colorant was added to a solvent and stirred for 30 minutes, and then a binder resin was added and stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities, and a near-infrared absorbing resin composition was obtained.

[0256] [Table 1]

[0257] [Table 2]

[0258] [Table 3]

[0259] (evaluation) Evaluation 1: Wavelength compatibility evaluation The near infrared absorbing resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were used to prepare optical filter specimens.

[0260] Specifically, each of the near infrared absorbing resin compositions was applied to a thickness of 1 μm to 3 μm on a degreased and washed glass substrate having a thickness of 1 mm, and dried on a hot plate at 90° C. for 2 minutes to obtain an optical filter specimen having a near infrared absorbing film formed thereon.

[0261] The wavelength matching of each optical filter sample was confirmed through the maximum absorption wavelength (λmax). Specifically, the maximum absorption wavelength (λmax) of each optical filter sample was confirmed using a Shimadzu UV-3600 Plus UV-Vis-NIR spectrometer, and the absorbance at that wavelength was measured. The measured maximum absorption wavelengths are shown in Table 4 below.

[0262] [Table 4]

[0263] It can be seen from Table 4 above that the core-shell dyes of Examples 1 to 8 are suitable for near infrared absorption, compared to the dyes of Comparative Examples 1 to 3. Specifically, the core-shell dyes of Examples 1 to 8 include a core represented by Chemical Formula 1. The core represented by Chemical Formula 1 is a compound having a structure in which the aniline moiety in a squalene (SQ)-based compound is replaced with a diamine naphthalene moiety, and the maximum absorption peak can be shifted to a longer wavelength region compared to squalene-based compounds.

[0264] Therefore, the core-shell dyes of Examples 1 to 8, which contain a core represented by Chemical Formula 1, are more suitable for near-infrared absorption than the commonly known green pigment (Comparative Example 3), as well as the squalene-based compound core (Comparative Example 1) or core-shell compound (Comparative Example 2) containing an aniline moiety.

[0265] On the other hand, in Examples 1 to 8, the effects of the core structure are largely similar, but the maximum absorption wavelength changes depending on whether or not a halogen group (specifically, F) is introduced into the shell.

[0266] Specifically, when the core structure is the same, the introduction of a halogen group into the shell shifts the wavelength to a longer wavelength region by about 20 nm, thereby achieving better compatibility with the near-infrared absorption wavelength band.

[0267] However, introduction of a halogen group into the shell is optional.

[0268] In summary, the core-shell dye of one embodiment is shown to have excellent compatibility with the near infrared absorption wavelength band, either due to the effect of the core represented by Chemical Formula 1 alone or due to the enhanced effect of the core represented by Chemical Formula 1 and the shell represented by Chemical Formula 2.

[0269] Evaluation 2: Light and chemical resistance evaluation (1) Light resistance evaluation: An optical filter specimen obtained under the same conditions as in evaluation 1 was exposed to light using a high-pressure mercury lamp having a dominant wavelength of 365 nm, and then dried in an oven at 230° C. for 60 minutes.

[0270] The absorbance of the substrate after the exposure treatment was measured at the maximum absorption wavelength (λmax) by the method described above. The measured value and the measured value of Evaluation 1 were substituted into the following mathematical formula 1 to convert the light resistance into a numerical value, and the results are shown in Table 5 below.

[0271]

number

[0272] (2) Chemical resistance evaluation: An optical filter specimen obtained under the same conditions as in evaluation 1 was immersed in an NMP (N-methylpyrrolidone) solution at room temperature for 10 minutes.

[0273] The absorbance of the substrate after the chemical treatment was measured at the maximum absorption wavelength (λmax) by the method described above. The measured value and the measured value of Evaluation 1 were substituted into the following Equation 2 to quantify the chemical resistance, and the results are shown in Table 5 below.

[0274]

number

[0275] (3) Heat resistance evaluation: The optical filter specimen obtained under the same conditions as in evaluation 1 was treated at 230° C. for 60 minutes in a convection oven.

[0276] The absorbance of the substrate after the high-temperature treatment was measured at the maximum absorption wavelength (λmax) by the method described above. The measured value and the measured value of Evaluation 1 were substituted into the following formula 3 to convert the heat resistance into a numerical value, and the results are shown in Table 5 below.

[0277]

number

[0278] [Table 5]

[0279] It can be seen from Table 5 above that the core-shell dyes of Examples 1 to 8 have significantly improved durability (light resistance, chemical resistance, and heat resistance) compared to Comparative Example 1. Specifically, compared to the dyes of Comparative Examples 1 and 2 which are composed only of a core, the core-shell dyes of Examples 1 to 8 further include a shell represented by Chemical Formula 2, thereby making up for the lack of durability of the core represented by Chemical Formula 1.

[0280] On the other hand, the dye of Comparative Example 2 has a core-shell structure, and has improved durability (light resistance, chemical resistance, and heat resistance) compared to the dye of Comparative Example 1 which is composed of only a core.

[0281] However, the core-shell dyes of Examples 1 to 8 are compounds having a structure in which the aniline moiety in a squalene (SQ)-based compound is replaced with a diamine naphthalene moiety, and have improved durability (light resistance, chemical resistance, and heat resistance) compared to Comparative Example 2.

[0282] In Examples 1 to 8, the effects of the shell structure are largely similar, but durability varies depending on whether or not an epoxy group and / or a (meth)acrylate group is introduced into the core.

[0283] Specifically, the (meth)acrylate group is a functional group that contributes to improving heat resistance, and the -O- (epoxy) group is a functional group that contributes to improving chemical resistance. 1 In contrast to when unsubstituted, when substituted with one or more (meth)acrylate groups, *-O-*(epoxy) groups, or a combination thereof, the chemical resistance, heat resistance, etc. of the core can be appropriately improved.

[0284] The present invention is not limited to the above-mentioned embodiments, and can be manufactured in various different forms, and a person skilled in the art to which the present invention belongs can understand that the present invention can be embodied in other specific forms without changing the technical concept or essential features of the present invention. Therefore, it should be understood that the above-mentioned embodiments are illustrative and not limiting in all respects.

Claims

1. A core-shell dye comprising a core represented by any one of 1-1 to 1-4 below; and a shell surrounding the core and represented by the following chemical formula 2: 【Chemistry 1】 【Chemistry 2】 In the above chemical formulas 1-1 to 1-4, R 11 , R 12 , R 13 , R 21 , R 31 , R 32 , R 33 , R 41 and R 42 are each independently the same or different and are an alkyl group having 1 to 10 carbon atoms; L 31 , L 32 , L 41 and L 42 are each independently the same or different and are an alkylene group having 1 to 10 carbon atoms; R 5 , R 6 , R 8 and R 10 are each independently the same or different and each independently represent an alkyl group having 1 to 10 carbon atoms; R 7 and R 9 are each independently the same or different and are a (meth)acrylate group or a *-O-* (epoxy) group; c, d, e, f and g are each independently an integer from 0 to 5; 【Chemistry 3】 In the above chemical formula 2, L １ and L ２ each independently represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Z １ and Z ２ are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; X １ and X ２ each independently represents a halogen group or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a1 and a2 each independently represent an integer of 0 to 4; n is an integer of 2 or more.

2. A core-shell dye comprising a core represented by any one of the following groups; and a shell surrounding the core and represented by the following chemical formula 2: 【Chemistry 4】 【Chemistry 5】 In the above chemical formula 1-1-1, o and p are each independently an integer from 0 to 5; 【Chemistry 6】 In the above chemical formula 2, L 1 and L 2 each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Z 1 and Z 2 each independently represent *-CR-* or a nitrogen atom, where R represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; X 1 and X 2 each independently represent a halogen group or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a1 and a2 each independently represent an integer of 0 to 4; n is an integer of 2 or more.

3. Said Z １ and Z ２ 3. The core-shell dye according to claim 1, wherein one of is *--CH--* or a nitrogen atom, and the other is *--CH--*.

4. The X １ and X ２ The core-shell dye according to claim 1 or 2, wherein each independently represents a halogen group, and a1+a2 represents an integer of 1 to 8.

5. The core-shell dye according to claim 1 or 2, wherein n is 2.

6. Said L １ and L ２ The core-shell dye according to claim 1 or 2, wherein each of the groups is independently an alkylene group having 1 to 10 carbon atoms.

7. The core-shell dye according to claim 1 or 2, wherein the shell is represented by any one of the following formulas 2-1 to 2-4: 【Chemistry 7】 【Chemistry 8】

8. The core-shell dye of claim 1 or 2, wherein the core-shell dye comprises the core and the shell in a molar ratio of 1:

1.

9. A core-shell dye represented by any one selected from the group consisting of: 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 In the above chemical formulas 3-1-1, 4-1-1, 5-1-1 and 6-1-1, o and p each independently represent an integer of 0 to 5.

10. The core-shell dye according to claim 1 or 2, wherein the core has a maximum absorption peak at a wavelength of 700 nm to 850 nm.

11. The core-shell dye of claim 10, wherein the core-shell dye has a maximum absorption peak at a wavelength of 700 nm to 1,000 nm.

12. The core-shell dye according to any one of claims 1, 2 and 9, wherein the core-shell dye is a near infrared absorbing dye.

13. A near infrared absorbing resin composition comprising the core-shell dye according to any one of claims 1, 2 and 9.

14. The near infrared absorbing resin composition according to claim 13, further comprising a binder resin and a solvent.

15. The near infrared absorbing resin composition according to claim 13, wherein the near infrared absorbing resin composition is for a CMOS image sensor.

16. A near infrared absorbing film produced by using the near infrared absorbing resin composition of claim 13.

17. 17. An optical filter comprising the near infrared absorbing film of claim 16.

18. 20. A CMOS image sensor comprising the optical filter of claim 17.

Images