Compound, pigment dispersion comprising same, photosensitive resin composition, photosensitive resin layer, and color filter

Abstract

Provided are a compound or a salt thereof, a pigment dispersion comprising same, a photosensitive resin composition, a photosensitive resin layer, and a color filter.

Description

Compound, pigment dispersion containing the same, photosensitive resin composition, photosensitive resin film and color filter

[0001] The present invention relates to a pigment synergist compound or a salt thereof, a pigment dispersion containing the same, a photosensitive resin composition containing the pigment synergist as a colorant, a photosensitive resin film which is a cured product of the photosensitive resin composition, and a color filter containing the photosensitive resin film.

[0002]

[0003] Liquid crystal display devices, which are one type of display devices, have advantages such as being lightweight, thin, low-cost, low-power driveability, and excellent compatibility with integrated circuits, and their range of use is expanding for laptop computers, monitors, and TV images. Such liquid crystal display devices are composed of a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, and an active circuit portion composed of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which the ITO pixel electrode is formed. The color filter has a structure in which a black matrix layer is formed in a set pattern on a transparent substrate to block light at the boundary between pixels, and a pixel portion in which a plurality of colors, typically the three primary colors of red (R), green (G), and blue (B), are arranged in a set order to form each pixel, are sequentially stacked.

[0004] The pigment dispersion method, which is one of the methods for implementing a color filter, is a method in which a colored thin film is formed by coating a photopolymerizable composition containing a coloring agent on a transparent substrate provided with a black matrix, exposing a pattern of a desired shape, removing the unexposed area with a solvent, and repeating a series of processes such as thermal curing. The colored photosensitive resin composition used in the manufacture of a color filter according to the pigment dispersion method is generally composed of an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method is actively applied in the manufacture of LCDs for mobile phones, laptops, monitors, TVs, etc.

[0005] Image sensors are image capturing components that generate images in mobile phone cameras and digital still cameras (DSCs). Depending on their manufacturing process and application, they can be broadly classified into solid-state image sensors (charge-coupled device (CCD)) and complementary metal oxide semiconductor (CMOS) image sensors. Color image capturing devices used in solid-state image sensors or complementary metal oxide semiconductors typically install color filters with filter segments of red, green, and blue additive primary colors on the light-receiving element to perform color separation. Recently, the pattern size of the color filters mounted on these color image capturing devices is 2㎛ or less, which is 1 / 100 to 1 / 200 times the size of the color filter pattern for existing LCDs. Accordingly, increasing the resolution and reducing residue are important factors that determine the performance of the device.

[0006] Meanwhile, color filters manufactured using pigment-type photosensitive resin compositions suffer from limitations in brightness and contrast ratio due to the size of the pigment particles. Furthermore, color imaging elements for image sensors require a smaller particle size to form fine patterns. To address these needs, attempts have been made to introduce non-particle dyes instead of pigments, creating photosensitive resin compositions suitable for the dyes, thereby achieving color filters with improved brightness and contrast ratio. However, dyes, compared to pigments, have lower durability in light and heat resistance, raising concerns about reduced brightness.

[0007]

[0008] One embodiment is to provide a novel structural synergistic compound or salt thereof capable of implementing ultra-thin, ultra-fine patterning.

[0009] Another embodiment is to provide a pigment dispersion comprising the compound or a salt thereof.

[0010] Another embodiment is to provide a photosensitive resin composition comprising the compound or a salt thereof.

[0011] Another embodiment is to provide a photosensitive resin film manufactured using the photosensitive resin composition.

[0012] Another embodiment is to provide a color filter including the photosensitive resin film.

[0013]

[0014] One embodiment provides a compound represented by the following chemical formula 1 or a salt thereof.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0019] n1 to n4 are each independently integers from 1 to 4,

[0020] A, B, C and D are each independently represented by the following chemical formula 1-1A or chemical formula 1-1B, provided that any one of A, B, C and D is different from at least any one of the remaining three,

[0021] [Chemical Formula 1-1A]

[0022]

[0023] In the above chemical formula 1-1A,

[0024] L 1 is a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

[0025] L 2 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0026] R 1 is an acidic group,

[0027] [Chemical Formula 1-1B]

[0028]

[0029] In the above chemical formula 1-1B,

[0030] L 1 is a substituted or unsubstituted C1 to C20 alkylene group, ether group, amide group (*-C(=O)NRa -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof,

[0031] R 1 is a basic group.

[0032] The acid group above is *-SO3 - , which may be a carboxyl group, a phosphoric acid group, or a phosphonic acid group.

[0033] The above basic group is *-NR b R c (R b and R c Each independently represents a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), and may be represented by the following chemical formula B-1, the following chemical formula B-2, the following chemical formula B-3, the following chemical formula B-4, or the following chemical formula B-5.

[0034] [Chemical Formula B-1]

[0035]

[0036] [Chemical Formula B-2]

[0037]

[0038] [Chemical Formula B-3]

[0039]

[0040] [Chemical Formula B-4]

[0041]

[0042] [Chemical Formula B-5]

[0043]

[0044] In the above chemical formulas B-1 to B-5,

[0045] R d Inland R lare each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0046] Above *-N(R a )-* can be represented by the following chemical formula N.

[0047] [Chemical formula N]

[0048]

[0049] In the above chemical formula N,

[0050] L 5 is a substituted or unsubstituted C1 to C10 alkylene group,

[0051] R 5 is an acidic group.

[0052] In the above chemical formulas B-3 and B-4, R f Inland R i Each may independently be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0053] The above compound can be represented by the following chemical formula 2A or chemical formula 2B.

[0054] [Chemical Formula 2A]

[0055]

[0056] In the above chemical formula 2A,

[0057] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0058] L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R ais a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

[0059] L 2a , L 2b , L 2c and L 2d are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0060] R 1a , R 1b , R 1c and R 1d are each independently acidic,

[0061] [Chemical Formula 2B]

[0062]

[0063] In the above chemical formula 2B,

[0064] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0065] L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, ether group, amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof,

[0066] R 1a , R 1b , R1c and R 1d are each independently basic groups.

[0067] The compound or its salt may be represented by any one of the following chemical formulas 3A to 6A and 3B to 8B.

[0068] [Chemical Formula 3A]

[0069]

[0070] [Chemical Formula 4A]

[0071]

[0072] [Chemical Formula 5A]

[0073]

[0074] [Chemical Formula 6A]

[0075]

[0076] [Chemical Formula 3B]

[0077]

[0078] [Chemical Formula 4B]

[0079]

[0080] [Chemical Formula 5B]

[0081]

[0082] [Chemical Formula 6B]

[0083]

[0084] [Chemical Formula 7B]

[0085]

[0086] [Chemical Formula 8B]

[0087]

[0088] The above compound or salt thereof may be a pigment synergist.

[0089] The above compound or salt thereof may be a blue pigment synergist.

[0090] Another embodiment provides a pigment dispersion comprising the compound or a salt thereof and a pigment.

[0091] The above pigment may be a blue pigment.

[0092] The above pigment may be a blue pigment or a purple pigment.

[0093] The above pigment dispersion may further include a dispersant, a dispersing resin, and a solvent.

[0094] The pigment dispersion may include 0.5 to 5 wt% of the compound or its salt; 5 to 20 wt% of the pigment; 1 to 5 wt% of the dispersant; 3 to 10 wt% of the dispersion resin; and the remainder of the solvent, based on the total amount of the pigment dispersion.

[0095] Another embodiment provides a photosensitive resin composition comprising the compound or its salt and pigment as a colorant, and further comprising a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.

[0096] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0097] Another embodiment provides a color filter including the photosensitive resin film.

[0098] Specific details of other embodiments of the present invention are included in the detailed description below.

[0099]

[0100] The compound or salt thereof according to one embodiment can be used as a blue pigment synergist to ultimately implement a color resist and CMOS image sensor capable of ultra-thin, ultra-fine patterning.

[0101]

[0102] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0103] Unless otherwise specified herein, "substitution" means that at least one hydrogen atom in a compound is substituted with a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, It means substituted with a C2 to C20 heterocycloalkynyl group or a combination thereof.

[0104] Unless otherwise specified herein, 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 compound of cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene, respectively.

[0105] Unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”.

[0106] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0107] Unless otherwise defined in the chemical formulas herein, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

[0108] Additionally, unless otherwise specified herein, “*” means a portion connected to the same or different atoms or chemical formulas.

[0109]

[0110] A compound or a salt thereof according to one embodiment is represented by the following chemical formula 1.

[0111] [Chemical Formula 1]

[0112]

[0113] In the above chemical formula 1,

[0114] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0115] n1 to n4 are each independently integers from 1 to 4,

[0116] A, B, C and D are each independently represented by the following chemical formula 1-1A or chemical formula 1-1B, provided that any one of A, B, C and D is different from at least any one of the remaining three,

[0117] [Chemical Formula 1-1A]

[0118]

[0119] In the above chemical formula 1-1A,

[0120] L 1 is a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

[0121] L 2 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0122] R 1 is an acidic group,

[0123] [Chemical Formula 1-1B]

[0124]

[0125] In the above chemical formula 1-1B,

[0126] L 1 is a substituted or unsubstituted C1 to C20 alkylene group, ether group, amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof,

[0127] R 1 is a basic group.

[0128] To facilitate the stable dispersion and miniaturization of pigment dispersions, various studies are being conducted to create pigments with particles of a certain size through processes such as salt milling using synthetically obtained pigments. However, as mentioned above, color filters manufactured with pigment-type photosensitive resin compositions have limitations in brightness and contrast ratio due to the size of the pigment particles. Furthermore, color imaging elements for image sensors require a smaller particle size to form fine patterns. To meet these needs, there is a growing need for compounds necessary for finely dispersing pigment particles and creating dispersions containing pigments that do not reaggregate, and for manufacturing photosensitive resin compositions for color filters using dispersions containing such compounds.

[0129] Color filters manufactured from pigment-type photosensitive resin compositions have limitations in their tinting power due to the size of the pigment particles. Furthermore, for applications in image sensors, resin compositions comprising smaller particles are required for fine pattern formation. Furthermore, for applications in KrF exposure, further improvement in the tinting properties of existing materials is necessary. Under these circumstances, the inventors have conducted extensive research and have developed a pigment derivative, i.e., a novel synergist (dispersing agent), thereby enabling the introduction of a coloring agent to which the dispersing agent is applied and a curing system suitable for KrF, ultimately providing a composition capable of implementing ultra-thin, ultra-fine patterning.

[0130] Specifically, the compound represented by the above chemical formula 1 or a salt thereof has a total of four acidic groups at the terminal, and the acidic groups are highly polar groups, L 2 Introduced at a specific position of the compound represented by the above chemical formula 1 in a state connected to a linker represented by L, i.e., the above L 2 L connected to an oxygen atom that forms a direct bond with the phthalocyanine-based parent structure through a linker indicated by 1By being connected with a linker represented by the above-described formula 1, the above-described effect can be more effectively implemented. That is, since the dispersion agent represented by the above-described formula 1, in which the above-described highly polar acidic group is introduced, is advantageous in terms of stacking when used with a pigment, specifically a blue pigment, and a dispersant, re-aggregation of the blue pigment can be prevented, and dispersion stability can be maximized by making the particle size of the blue pigment smaller. In addition, even if it has a structure like the above-described formula 1, the L 1 If the connecting group represented by is not provided, it may be disadvantageous in terms of heat resistance. In addition, the compound represented by the above chemical formula 1 has terminal functional groups represented by A, B, C, and D, and if these terminal functional groups are all the same, it is excluded from the scope of the above chemical formula 1. That is, since any one of the above A, B, C, and D is different from at least any one of the remaining three, the compound according to one embodiment may have better durability, coloring power, and spectral characteristics than when the above A, B, C, and D are all the same.

[0131] On the other hand, the compound represented by the above chemical formula 1 or its salt has a total of four basic groups at the terminal, and the basic groups are highly polar groups, L 1 By introducing into a specific position of the compound represented by the above chemical formula 1 in a state of being connected to a linking group represented by, that is, by being connected to an oxygen atom that forms a direct bond with the phthalocyanine-based parent structure via the linking group, the aforementioned effect can be more effectively implemented. That is, since the dispersion agent represented by the above chemical formula 1 in which the high polar basic group is introduced is advantageous in terms of stacking when used with a pigment, specifically a blue pigment and a dispersant, re-aggregation of the blue pigment can be prevented, and dispersion stability can be maximized by making the particle size of the blue pigment smaller. In addition, even if it has a structure like the above chemical formula 1, the L 1If a linker other than the linkers listed in the definition is used, it may be disadvantageous in terms of heat resistance. Meanwhile, the compound represented by the above chemical formula 1 or a salt thereof has terminal functional groups represented by A, B, C and D, and if these terminal functional groups are all the same, they are excluded from the scope of the above chemical formula 1. That is, since any one of the above A, B, C and D is different from at least any one of the remaining three, the compound according to one embodiment may have better durability, coloring power and spectral characteristics than when the above A, B, C and D are all the same.

[0132] For example, the acidic group is *-SO3 - , which may be a carboxyl group, a phosphoric acid group, or a phosphonic acid group.

[0133] For example, the basic group is *-NR b R c (R b and R c Each independently represents a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), and may be represented by the following chemical formula B-1, the following chemical formula B-2, the following chemical formula B-3, the following chemical formula B-4, or the following chemical formula B-5.

[0134] [Chemical Formula B-1]

[0135]

[0136] [Chemical Formula B-2]

[0137]

[0138] [Chemical Formula B-3]

[0139]

[0140] [Chemical Formula B-4]

[0141]

[0142] [Chemical Formula B-5]

[0143]

[0144] In the above chemical formulas B-1 to B-5,

[0145] R d Inland R l are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0146] For example, in the chemical formulas B-3 and B-4, R f Inland R i Each of may independently be a C1 to C20 alkyl group substituted or unsubstituted with a hydrogen atom. In this case, even when the organic pigment described below is finely dispersed, good fluidity and dispersion stability can be maintained, and it may be easier to provide a pigment dispersion agent that is advantageous for implementing ultra-thin film ultra-fine patterning.

[0147] For example, the above *-N(R a )-* can be represented by the following chemical formula N.

[0148] [Chemical formula N]

[0149]

[0150] In the above chemical formula N,

[0151] L 5 is a substituted or unsubstituted C1 to C10 alkylene group,

[0152] R 5 is an acidic group.

[0153] Above *-N(R a )-* is represented by the chemical formula N, the number of sites where the acid group can be introduced in the compound according to one embodiment increases, so that even in a state where the organic pigment described below is finely dispersed, good fluidity and dispersion stability can be maintained, and it can be easier to provide a pigment dispersion agent that is advantageous for implementing ultra-thin, ultra-fine patterning.

[0154] For example, the compound or its salt may be represented by the following chemical formula 2A or chemical formula 2B.

[0155] [Chemical Formula 2A]

[0156]

[0157] In the above chemical formula 2A,

[0158] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0159] L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

[0160] L 2a , L 2b , L 2c and L 2d are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0161] R 1a , R 1b , R 1c and R 1d are each independently acidic,

[0162] [Chemical Formula 2B]

[0163]

[0164] In the above chemical formula 2B,

[0165] M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr,

[0166] L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, an ether group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof,

[0167] R 1a , R 1b , R 1c and R 1d are each independently basic groups.

[0168] In the above chemical formula 1 and chemical formula 1-1A, *-OL 1 -L 2 -R 1 By specifying the position of the substituent represented by as in the above chemical formula 2A, the fluidity and dispersion stability of the organic pigment, particularly the blue organic pigment and / or the purple organic pigment, can be greatly improved.

[0169] In the above chemical formula 1 and chemical formula 1-1B, *-L 1 -R 1 By specifying the position of the substituent represented by as in the chemical formula 2B, the fluidity and dispersion stability of the organic pigment, particularly the blue organic pigment, can be greatly improved.

[0170] For example, the compound or its salt may be represented by any one of the following chemical formulas 3A to 6A and 3B to 8B, but is not necessarily limited thereto.

[0171] [Chemical Formula 3A]

[0172]

[0173] [Chemical Formula 4A]

[0174]

[0175] [Chemical Formula 5A]

[0176]

[0177] [Chemical Formula 6A]

[0178]

[0179] [Chemical Formula 3B]

[0180]

[0181] [Chemical Formula 4B]

[0182]

[0183] [Chemical Formula 5B]

[0184]

[0185] [Chemical Formula 6B]

[0186]

[0187] [Chemical Formula 7B]

[0188]

[0189] [Chemical Formula 8B]

[0190]

[0191] For example, the compound or salt thereof may be a pigment synergist, i.e. a pigment dispersing agent.

[0192] For example, the compound or salt thereof may be a blue pigment synergist, i.e., a blue pigment dispersing agent.

[0193] For example, the compound or salt thereof may be a purple pigment synergist, i.e., a purple pigment dispersion agent.

[0194] Another embodiment provides a pigment dispersion comprising a pigment synergist, such as the compound or a salt thereof, and a pigment. The compound or salt thereof may be present in an amount of 0.5 to 5 wt% based on the total weight of the pigment dispersion. This minimizes reaggregation of the pigment, thereby maximizing dispersion stability.

[0195] For example, the pigment may be a blue pigment. For example, the blue pigment may be a phthalocyanine pigment such as, but not limited to, 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 16, etc.

[0196] For example, the pigment may further include a purple pigment together with the blue pigment. For example, the purple pigment may include, for example, CI Violet Pigment 1, CI Violet Pigment 19, CI Violet Pigment 23, CI Violet Pigment 27, CI Violet Pigment 29, CI Violet Pigment 30, CI Violet Pigment 32, CI Violet Pigment 37, CI Violet Pigment 40, CI Violet Pigment 42, CI Violet Pigment 50, and the like.

[0197] For example, the pigment may further include a green pigment, a red pigment, a yellow pigment, etc. in addition to the blue pigment and the purple pigment, and for example, isoindoline pigments such as CI Green Pigment 7, CI Green Pigment 36, CI Green Pigment 58, CI Green Pigment 59, 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, CI Yellow Pigment 185, CI Yellow Pigment 139, quinophthalone pigments such as CI Yellow Pigment 138, nickel complex pigments such as CI Yellow Pigment 150, etc. may be used, but is not limited thereto.

[0198] For example, the pigment may be an organic pigment, and the organic pigment may be a finely divided one. The finely divided organic pigment may be a salt-milled organic pigment. Specifically, in order to increase the transmittance and contrast ratio of color filters or inkjet printing, it may be preferable for the organic pigment to be a finely divided one. In addition, it may be more preferable to salt-mill the organic pigment by grinding it with an inorganic salt using a kneader or a mixing device that rotates and revolves three stirring blades respectively, so that the primary particle diameter of the organic pigment becomes even finer. Among these, it may be preferable to use an organic pigment obtained by salt-milling using a mixing device that rotates and revolves three stirring blades respectively. In this case, the salt-milling treatment may be performed so that the primary particle diameter of the pigment becomes even finer and more uniform.

[0199] The pigment may be included in an amount of 5 to 20 wt% based on the total weight of the pigment dispersion. In this case, the interaction between the pigment synergist and the pigment is maximized, thereby minimizing reaggregation of the pigment and maximizing dispersion stability.

[0200] For example, the pigment dispersion may further include a dispersant, a dispersing resin, and a solvent.

[0201] For example, as the dispersant, a polymer pigment dispersant that has been conventionally used in printing ink, paint, pigment dispersion resist composition for color filters, ink for inkjet printing, etc. can be used, and its type can be appropriately selected depending on the type of organic pigment used together or the type of organic solvent described later. Specifically, the dispersant helps the pigment to be uniformly dispersed in the dispersion, and any nonionic, anionic, or cationic dispersant can be used. More specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide adduct, alkyl amine, quaternary amine, etc. can be used, and these can be used alone or in combination of two or more.

[0202] The dispersant may be included in an amount of 1 to 5 wt% based on the total amount of the pigment dispersion. If the content of the dispersant is less than 1 wt%, pigment dispersibility may be reduced, and if it exceeds 20 wt%, there may be concerns such as reduced developability.

[0203] For example, the dispersion resin may use an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patternability of the pixels.

[0204] The above dispersion resin may be included in an amount of 3 wt% to 10 wt% based on the total amount of the pigment dispersion.

[0205] As the above solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used, and among these, propylene glycol methyl ether acetate can be preferably used.

[0206] Considering the solubility, pigment dispersibility, and applicability of the dispersion resin, it may be preferable for these solvents to be included as a remainder, for example, 60 wt% to 90 wt%, of the total amount of the pigment dispersion.

[0207] Another embodiment provides a photosensitive resin composition further comprising a colorant, a binder resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein the colorant comprises the pigment synergist and the pigment.

[0208] The above binder resin may include an acrylic resin.

[0209] The above acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

[0210] The above first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0211] The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example, 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

[0212] The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, etc.; an unsaturated carboxylic acid ester compound such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl(meth)acrylate, etc.; an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl(meth)acrylate, 2-dimethylaminoethyl(meth)acrylate, etc.; a carboxylic acid vinyl ester compound such as vinyl acetate, vinyl benzoate, etc.; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl(meth)acrylate, etc. Examples include cyanide vinyl compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; etc., and these may be used alone or in combination of two or more.

[0213] Specific examples of the above acrylic resin include, but are not limited to, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., and these may be used alone or in combination of two or more.

[0214] The above binder resin may include an epoxy-based binder resin.

[0215] The above binder resin can improve heat resistance by further including an epoxy-based binder resin. Examples of the epoxy-based binder resin include, but are not limited to, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, alicyclic epoxy resin, or combinations thereof.

[0216] Furthermore, the binder resin including the above epoxy-based binder resin ensures dispersion stability of a coloring agent such as a pigment, which will be described later, and helps form pixels of a desired resolution during the developing process.

[0217] The above epoxy-based binder resin may be included in an amount of 1 wt% to 10 wt%, for example, 5 wt% to 10 wt%, based on the total amount of the binder resin. When the epoxy-based binder resin is included in the above range, the film remaining rate and chemical resistance can be significantly improved.

[0218] The epoxy equivalent weight of the above epoxy binder resin may be 150 g / eq to 200 g / eq. When an epoxy binder resin having an epoxy equivalent weight within the above range is included in the binder resin, there is a beneficial effect of improving the curing degree of the formed pattern and fixing the colorant within the structure in which the pattern is formed.

[0219] The above binder resin can be dissolved in a solvent described below in a solid form to form a photosensitive resin composition. In this case, the binder resin in solid form may be present in an amount of about 0.1 wt% to 30 wt%, for example, 20 wt% to 30 wt%, based on the total amount of the binder resin solution dissolved in the solvent.

[0220] In addition, the binder resin may be included in an amount of 0.1 wt% to 20 wt%, specifically 0.5 wt% to 15 wt%, for example 1 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, the developability is excellent during the manufacture of a color filter, and the crosslinking property is improved, thereby obtaining excellent surface smoothness.

[0221] The above polymerizable compound may be a photopolymerizable compound, for example, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond may be used as the photopolymerizable compound.

[0222] The above photopolymerizable compound has the above ethylenically unsaturated double bond, and thus can form a pattern with excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization upon exposure in the pattern forming process.

[0223] Specific examples of the above photopolymerizable compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol Examples thereof include penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy (meth)acrylate.

[0224] Examples of commercially available products of the above photopolymerizable compounds are as follows. An example of the monofunctional ester of (meth)acrylic acid is Aronix M-101 from Toagosei Chemical Industry Co., Ltd. ® , East M-111 ® , East M-114 ® KAYARAD TC-110S from Nihon Kayaku Co., Ltd. ® , Dong TC-120S® Back; V-158 of Osaka Yuki Kagaku Kogyo Co., Ltd. ® , V-2311 ® Examples of the bifunctional ester of the above (meth)acrylic acid include Aronix M-210 from Toagosei Chemical Co., Ltd. ® , East M-240 ® , East M-6200 ® KAYARAD HDDA from Nihon Kayaku Co., Ltd. ® , Dong HX-220 ® , East R-604 ® Back; V-260 from Osaka Yuki Kagaku Kogyo Co., Ltd. ® , V-312 ® , V-335 HP ® Examples of the trifunctional ester of the above (meth)acrylic acid include Aronix M-309 from Toagosei Chemical Co., Ltd. ® , East M-400 ® , East M-405 ® , East M-450 ® , East M-710 ® , East M-8030 ® , East M-8060 ® KAYARAD TMPTA from Nihon Kayaku Co., Ltd. ® , East DPCA-20 ® , East-30 ® , East-60 ® , East-120 ® Back; V-295 of Osaka Yuki Kayaku High School Co., Ltd. ® , East-300 ® , East-360 ® , Dong-GPT ® , Dong-3PA ® , East-400 ® The above products can be used alone or in combination of two or more.

[0225] The above photopolymerizable compound may be used by treating it with an acid anhydride to provide better developing properties.

[0226] The photopolymerizable compound may be included in an amount of 0.1 wt% to 10 wt%, specifically 1 wt% to 10 wt%, for example 3 wt% to 7 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs upon exposure in the pattern forming process, resulting in excellent reliability and excellent developability in an alkaline developer.

[0227] The polymerization initiator may be a photopolymerization initiator, and for example, the photopolymerization initiator may be an initiator generally used in a photosensitive resin composition, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof.

[0228] Examples of the above acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0229] Examples of the above benzophenone compounds include benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0230] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0231] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0232] Examples of the above triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, Examples thereof include 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0233] Examples of the above oxime compounds include O-acyloxime compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime-O-acetate.

[0234] In addition to the above compound, the photopolymerization initiator may also include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene compound, etc.

[0235] The above photopolymerization initiator may also be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy.

[0236] Examples of the above photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like.

[0237] The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, sufficient curing occurs upon exposure in the pattern formation process, thereby obtaining excellent reliability, and the pattern has excellent heat resistance, light resistance, and chemical resistance, and also excellent resolution and adhesion, and can prevent a decrease in transmittance due to unreacted initiator.

[0238] The solvent may be a substance that is compatible with, but does not react with, the colorant, the binder resin, the polymerizable compound, and the polymerization initiator.

[0239] Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate;2-oxy-2-methyl propionic acid esters such as methyl 2-oxy-2-methyl propionic acid, ethyl 2-oxy-2-methyl propionic acid, etc., monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as methyl 2-methoxy-2-methyl propionic acid, ethyl 2-ethoxy-2-methyl propionic acid, etc.; esters such as ethyl 2-hydroxypropionic acid, ethyl 2-hydroxy-2-methylpropionic acid, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, etc.; Ketone acid esters such as ethyl pyruvate, etc., and also high boiling point solvents such as 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, and phenyl cellosolve acetate can be mentioned.;

[0240] Considering compatibility and reactivity among these, the solvent may be propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof.

[0241] The solvent may be included as a remainder, for example, 40 wt% to 90 wt%, for example, 45 wt% to 70 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has excellent applicability and a coating film with excellent flatness can be obtained.

[0242] The photosensitive resin composition may further include at least one additive selected from malonic acid; 3-amino-1,2-propanediol; a coupling agent containing a vinyl group or a (meth)acryloxy group; a leveling agent; a surfactant; and a radical polymerization initiator to prevent stains or spots during application, improve leveling performance, and prevent the generation of residue due to non-development.

[0243] The above additives can be easily adjusted according to the desired properties.

[0244] The above coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-(epoxycyclohexyl)ethyl trimethoxysilane, etc., and these may be used alone or in combination of two or more.

[0245] The above silane coupling agent can be specifically used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

[0246] In addition, the photosensitive resin composition for the color filter may further include a surfactant, such as a fluorinated surfactant, as needed.

[0247] Examples of the above fluorinated surfactants include, but are not limited to, DIC's F-482, F-484, and F-478.

[0248] The above surfactant is preferably included in an amount of 0.01 wt% to 5 wt%, and more preferably 0.01 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If the amount exceeds the above range, the problem of foreign substances being generated after development may arise, which is not preferable.

[0249] In addition, the photosensitive resin composition may have a certain amount of other additives such as antioxidants and stabilizers added to it, as long as the physical properties are not impaired.

[0250] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition. For example, the photosensitive resin film may be a cured film obtained by curing the photosensitive resin composition.

[0251] Another embodiment provides a color filter including the photosensitive resin film.

[0252] Another embodiment provides a display device including the color filter, such as an LCD or CIS.

[0253]

[0254] Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0255]

[0256] (Manufacture of pigment dispersion preparation)

[0257] (Preparation Example 1A: Synthesis of a compound represented by Chemical Formula 3A)

[0258] (Reaction Scheme 1A)

[0259]

[0260] The compound 1a (1.73 g, 10.0 mmol, 1.0 eq) and the compound 1b (2.40 g, 15.0 mmol, 1.5 eq) were dissolved in 20.0 mL of dimethylsulfoxide (DMSO) together with 2.76 g, 20.0 mmol, 2.0 eq, of K2CO3, and the mixture was heated to 80°C and stirred overnight. The reaction was monitored by thin-layer chromatography (TLC) to observe the disappearance of the compound 1a. Then, 200 mL of distilled water was added and the mixture was extracted with ethyl acetate (2 x 80 mL). The organic layer was passed through MgSO4 and concentrated to obtain 1.37 g, 4.80 mmol, of the compound 1c, which was used in the next reaction without further purification. (Yield 48%)

[0261] The analysis results of the above compound 1c are as follows.

[0262] MALDI-TOF MS: 287.13 m / z

[0263]

[0264] (Reaction Scheme 2A)

[0265]

[0266] Compound 1e was synthesized in the same manner as the synthesis of compound 1c, except that compound 1d was used instead of compound 1b.

[0267] The analysis results of the above compound 1e are as follows.

[0268] MALDI-TOF MS: 303.13 m / z

[0269]

[0270] (Reaction Scheme 3A)

[0271]

[0272] 1.43 g (5.00 mmol, 2.0 eq) of the above compound 1c and 1.51 g (5.00 mmol, 2.0 eq) of the above compound 1e were dissolved in 7.50 mL of n-amyl alcohol together with 248 mg (2.50 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 1.90 g (12.5 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and diluted with 32.0 mL of methanol. 32.0 mL of brine was added to generate a precipitate, which was then separated through filtration under reduced pressure. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, and as a result, 3.01 g (2.43 mmol) of the compound 1f was obtained. (Yield 97%)

[0273] The analysis results of the above compound 1f are as follows.

[0274] MALDI-TOF MS: 1240.45 m / z

[0275]

[0276] (Reaction Scheme 4A)

[0277]

[0278] The compound 1f3.01 g (2.43 mmol, 1.0 eq) was dissolved in 10.0 mL of ethanol and 1.0 mL of THF, and 10.0 mL of 1 N NaOH aqueous solution was added. The temperature was raised to 80°C and refluxed overnight. After removing ethanol under reduced pressure, 10.0 mL of 1 N HCl (solvent: 1,4-dioxane) was added to the reaction mixture. After stirring at room temperature for 2 hours, the solvent was removed under reduced pressure, and the resulting solid was separated by filtration under reduced pressure after adding 10 wt% brine to the residual material. This was washed several times with distilled water and dried overnight in a vacuum oven to obtain 2.37 g (2.21 mmol) of the compound represented by the chemical formula 3. (Yield: 91%)

[0279] The analysis results of the compound represented by the above chemical formula 3A are as follows.

[0280] MALDI-TOF MS: 1072.26 m / z

[0281]

[0282] (Preparation Example 2A: Synthesis of a compound represented by Chemical Formula 4A)

[0283] (Reaction Scheme 5A)

[0284]

[0285] Compound 2a was synthesized in the same manner as the synthesis of compound 1f, except that 1.0 eq was used instead of 2.0 eq of compound 1c, and 3.0 eq was used instead of 2.0 eq of compound 1e.

[0286] The analysis results of the above compound 2a are as follows.

[0287] MALDI-TOF MS: 1256.44 m / z

[0288]

[0289] (Reaction Scheme 6A)

[0290]

[0291] A compound represented by the above chemical formula 4A was synthesized in the same manner as the synthesis of the compound represented by the above chemical formula 3, except that the above compound 2a was used instead of the above compound 1f.

[0292] The analysis results of the compound represented by the above chemical formula 4A are as follows.

[0293] MALDI-TOF MS: 1060.22 m / z

[0294]

[0295] (Preparation Example 3A: Synthesis of a compound represented by Chemical Formula 5A)

[0296] (Reaction Scheme 7A)

[0297]

[0298] Compound 3b was synthesized in the same manner as the synthesis of compound 1c, except that compound 3a was used instead of compound 1b.

[0299] The analysis results of the above compound 3b are as follows.

[0300] MALDI-TOF MS: 335.13 m / z

[0301]

[0302] (Reaction Scheme 8A)

[0303]

[0304] The compound 3b (5.00 g, 15.0 mmol, 1.0 eq) was dissolved in 50 mL of a methanol / dichloromethane (v / v= 1 / 1) solution, and 284 mg (1.50 mmol, 10 mol%) of p-toluenesulfonic acid monohydrate (p-TsOH·H2O) was added. The mixture was stirred overnight at 50°C. After removing the solvent under reduced pressure, 2.84 g (11.4 mmol) of the compound 3c was obtained through column chromatography. (Yield: 76%)

[0305] The analysis results of the above compound 3c are as follows.

[0306] MALDI-TOF MS: 251.07 m / z

[0307]

[0308] (Reaction Scheme 9A)

[0309]

[0310] The above compound 3c 2.84 g (11.4 mmol, 1.0 eq) and the above compound 3d 1.53 g (12.5 mmol, 1.1 eq) were dissolved in NaOH 500 Added to 5.0 mL of isopropyl alcohol with mg (12.5 mmol 1.0 eq) and stirred at 80°C for 3 hours. After cooling to room temperature, the resulting solid was separated by filtration under reduced pressure, thereby obtaining 3.99 g (10.1 mmol) of the compound 3e (yield 89%).

[0311] The analysis results of the above compound 3e are as follows.

[0312] MALDI-TOF MS: 373.08 m / z

[0313]

[0314] (Reaction Scheme 10A)

[0315]

[0316] The compound 1c845 mg (2.95 mmol, 1.0 eq) was dissolved in 3.0 mL of ethanol, and 3.0 mL of 1 N NaOH aqueous solution was added. The temperature was raised to 80°C and stirred under reflux overnight. After removing ethanol under reduced pressure, 6.0 mL of 1 N HCl aqueous solution was added to the reaction mixture. The mixture was extracted with dichloromethane, and the organic layer was passed through MgSO4 and concentrated to obtain 692 mg (2.68 mmol) of the compound 3f (yield 91%).

[0317] The analysis results of the above compound 3f are as follows.

[0318] MALDI-TOF MS: 259.10 m / z

[0319]

[0320] (Reaction Scheme 11A)

[0321]

[0322] A compound represented by the chemical formula 5A was synthesized in the same manner as the synthesis of compound 1f, except that compound 3e was used instead of compound 1c, and compound 3f was used instead of compound 1e.

[0323] The analysis results of the compound represented by the above chemical formula 5 are as follows.

[0324] MALDI-TOF MS: 1324.29 m / z

[0325]

[0326] (Preparation Example 4A: Synthesis of a compound represented by Chemical Formula 6A)

[0327] (Reaction Scheme 12A)

[0328]

[0329] Compound 4b was synthesized in the same manner as the synthesis of compound 1c, except that compound 4a was used instead of compound 1b.

[0330] The analysis results of the above compound 4b are as follows.

[0331] MALDI-TOF MS: 344.19 m / z

[0332]

[0333] (Reaction Scheme 13A)

[0334]

[0335] The compound 4b (1.65 g, 4.80 mmol, 1.0 eq) was dissolved in 9.60 mL of a 1 / 1 solution of trifluoroacetic acid (TFA) and dichloromethane (DCM), and stirred at room temperature for 1 hour. The reaction was monitored by thin-layer chromatography (TLC) to observe the disappearance of the compound 4b. After all volatile components were removed under reduced pressure, the compound 4c (1.71 g, 4.79 mmol) was obtained, which was used in the next reaction without further purification. (Yield 99%)

[0336] The analysis results of the above compound 4c are as follows.

[0337] MALDI-TOF MS: 244.14 m / z

[0338]

[0339] (Reaction Scheme 14A)

[0340]

[0341] The compound 4c (9.50 g, 26.6 mmol, 1.0 eq) and the compound 3d (32.5 g, 266 mmol, 10.0 eq) were added to 65.0 mL of acetone together with 3.19 g (79.8 mmol, 3.0 eq) of NaOH and stirred overnight at 80°C. After cooling to room temperature, the resulting solid was separated by filtration under reduced pressure, thereby obtaining the compound 4d.

[0342] The analysis results of the above compound 4d are as follows.

[0343] MALDI-TOF MS: 488.14 m / z

[0344]

[0345] (Reaction Scheme 15A)

[0346]

[0347] 1.06 g (2.68 mmol, 1.0 eq) of the above compound 3e, 1.38 g (5.36 mmol, 2.0 eq) of the above compound 3f, and 1.42 g (2.68 mmol, 1.0 eq) of the above compound 4d were dissolved in 7.50 mL of n-amyl alcohol together with 265 mg (2.68 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 2.04 g (13.4 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and then diluted by adding 32.0 mL of methanol. Here, 32.0 mL of salt water was added to form a precipitate, which was then separated by vacuum filtration. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, yielding 3.70 g (2.60 mmol) of the compound represented by the chemical formula 6A (yield: 97%).

[0348] The analysis results of the compound represented by the above chemical formula 6A are as follows.

[0349] MALDI-TOF MS: 1425.34 m / z

[0350]

[0351] (Preparation Example 1B: Synthesis of a compound represented by Chemical Formula 3B)

[0352] (Reaction Scheme 1B)

[0353]

[0354] 548 mg (3.80 mmol, 1.0 eq) of the compound 1a and 2.46 g (6.84 mmol, 1.8 eq) of the compound 1b were dissolved in 10 mL of N,N-dimethylformamide (DMF) together with 1.58 g (11.4 mmol, 3.0 eq) of K2CO3, and stirred overnight at room temperature. After removing the solvent under reduced pressure, the residue was dissolved in chloroform and washed four times with distilled water. The organic layer was passed through MgSO4, concentrated, and purified through column chromatography to obtain 1.06 g (3.19 mmol) of the compound 1c. (Yield 84%)

[0355] The analysis results of the above compound 1c are as follows.

[0356] MALDI-TOF MS: 332.15 m / z

[0357]

[0358] (Reaction Scheme 2B)

[0359]

[0360] Compound 1e was synthesized in the same manner as the synthesis of compound 1c, except that compound 1d was used instead of compound 1b.

[0361] The analysis results of the above compound 1e are as follows.

[0362] MALDI-TOF MS: 344.19 m / z

[0363]

[0364] (Reaction Scheme 3B)

[0365]

[0366] 1.66 g (5.00 mmol, 2.0 eq) of the above compound 1c and 1.72 g (5.00 mmol, 2.0 eq) of the above compound 1e were dissolved in 7.50 mL of n-amyl alcohol together with 248 mg (2.50 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 1.90 g (12.5 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and diluted with 32.0 mL of methanol. 32.0 mL of brine was added to generate a precipitate, which was then separated through filtration under reduced pressure. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, and as a result, 3.43 g (2.43 mmol) of the compound 1f was obtained. (Yield 97%)

[0367] The analysis results of the above compound 1f are as follows.

[0368] MALDI-TOF MS: 1412.62 m / z

[0369]

[0370] (Reaction Scheme 4B)

[0371]

[0372] The compound 1f3.43 g (2.43 mmol, 1.0 eq) was dissolved in 4.80 mL of a 1 / 1 solution of trifluoroacetic acid (TFA) and dichloromethane (DCM), and stirred at room temperature for 1 hour. All volatile components were removed under reduced pressure to obtain 3.53 g (2.41 mmol) of the compound represented by the chemical formula 3B. (Yield: 99%)

[0373] The analysis results of the compound represented by the above chemical formula 3B are as follows.

[0374] MALDI-TOF MS: 1012.41 m / z

[0375]

[0376] (Preparation Example 2B: Synthesis of a compound represented by Chemical Formula 4B)

[0377] (Reaction Scheme 5B)

[0378]

[0379] The compound 2a (1.73 g, 10.0 mmol, 1.0 eq) and the compound 2b (2.18 g, 15.0 mmol, 1.5 eq) were dissolved in 20.0 mL of dimethylsulfoxide (DMSO) together with 2.76 g, 20.0 mmol, 2.0 eq, of K2CO3, and the mixture was heated to 80°C and stirred overnight. The reaction was monitored by thin-layer chromatography (TLC) to observe the disappearance of the compound 2a. 200 mL of distilled water was added and the mixture was extracted with ethyl acetate (2 x 80 mL). The organic layer was passed through MgSO4 and concentrated to obtain 1.37 g, 4.80 mmol, of the compound 2c, which was used in the next reaction without further purification. (Yield 48%)

[0380] The analysis results of the above compound 2c are as follows.

[0381] MALDI-TOF MS: 272.17 m / z

[0382]

[0383] (Reaction Scheme 6B)

[0384]

[0385] Compound 2e was synthesized in the same manner as the synthesis of compound 2c, except that compound 2d was used instead of compound 2b.

[0386] The analysis results of the above compound 2e are as follows.

[0387] MALDI-TOF MS: 374.14 m / z

[0388]

[0389] (Reaction Scheme 7B)

[0390]

[0391] 2.04 g (7.50 mmol, 3.0 eq) of the above compound 2c and 34 mg (2.50 mmol, 1.0 eq) of the above compound 2e were dissolved in 7.50 mL of n-amyl alcohol together with 248 mg (2.50 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 1.90 g (12.5 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and diluted with 32.0 mL of methanol. 32.0 mL of brine was added to generate a precipitate, which was then separated through filtration under reduced pressure. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, and as a result, 3.00 g (2.40 mmol) of the compound represented by the chemical formula 4B was obtained. (Yield: 96%)

[0392] The analysis results of the compound represented by the above chemical formula 4B are as follows.

[0393] MALDI-TOF MS: 1250.58 m / z

[0394]

[0395] (Preparation Example 3B: Synthesis of a compound represented by Chemical Formula 5B)

[0396] (Reaction Scheme 8B)

[0397]

[0398] Compound 3b was synthesized in the same manner as the synthesis of compound 2c, except that compound 3a was used instead of compound 2b.

[0399] The analysis results of the above compound 3b are as follows.

[0400] MALDI-TOF MS: 260.13 m / z

[0401]

[0402] (Reaction Scheme 9B)

[0403]

[0404] Compound 3d was synthesized in the same manner as the synthesis of compound 2c, except that compound 3c was used instead of compound 2b.

[0405] The analysis results of the above compound 3d are as follows.

[0406] MALDI-TOF MS: 316.16 m / z

[0407]

[0408] (Reaction Scheme 10B)

[0409]

[0410] The compound 3d (1.51 g, 4.80 mmol, 1.0 eq) was dissolved in 9.60 mL of a 1 / 1 solution of trifluoroacetic acid (TFA) and dichloromethane (DCM), and stirred at room temperature for 1 hour. The reaction was monitored by thin-layer chromatography (TLC) to observe the disappearance of the compound 3d. After all volatile components were removed under reduced pressure, the compound 3e (1.58 g, 4.79 mmol) was obtained, which was used in the next reaction without further purification. (Yield 99%)

[0411] The analysis results of the above compound 3e are as follows.

[0412] MALDI-TOF MS: 216.11 m / z

[0413]

[0414] (Reaction Scheme 11B)

[0415]

[0416] The compound 3e (1.58 g, 4.79 mmol, 1.5 eq) and the compound 3f (822 mg, 3.19 mmol, 1.0 eq) were dissolved in 60.0 mL of 1,4-dioxane together with 969 mg (9.58 mmol, 3.0 eq) of triethylamine, and the mixture was heated to 90°C and stirred overnight. The reaction was monitored by thin-layer chromatography (TLC) to observe the disappearance of the compound 3f. Then, 200 mL of distilled water was added and the mixture was extracted with ethyl acetate (2 x 80 mL). The organic layer was passed through MgSO4, concentrated, and purified by column chromatography to obtain 1.27 g (2.91 mmol) of the compound 3g. (Yield 91%)

[0417] The analysis results of the above compound 3g are as follows.

[0418] MALDI-TOF MS: 437.27 m / z

[0419]

[0420] (Reaction Scheme 12B)

[0421]

[0422] 27 mg (2.68 mmol, 1.0 eq) of the above compound 2c, 1.39 g (5.36 mmol, 2.0 eq) of the above compound 3b, and 1.17 g (2.68 mmol, 1.0 eq) of the above compound 3g were dissolved in 7.50 mL of n-amyl alcohol together with 265 mg (2.68 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 2.04 g (13.4 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and then diluted with 32.0 mL of methanol. Here, 32.0 mL of salt water was added to form a precipitate, which was then separated by vacuum filtration. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, yielding 3.35 g (2.60 mmol) of the compound represented by the chemical formula 5B (yield: 97%).

[0423] The analysis results of the compound represented by the above chemical formula 5B are as follows.

[0424] MALDI-TOF MS: 1289.63 m / z

[0425]

[0426] (Preparation Example 4B: Synthesis of a compound represented by chemical formula 6B)

[0427] (Reaction Scheme 13B)

[0428]

[0429] Compound 4a was synthesized in the same manner as the synthesis of compound 3e, except that compound 1c was used instead of compound 3d.

[0430] The analysis results of the above compound 4a are as follows.

[0431] MALDI-TOF MS: 232.10 m / z

[0432]

[0433] (Reaction Scheme 14B)

[0434]

[0435] Compound 4c was synthesized in the same manner as the synthesis of compound 3g, except that compound 4a was used instead of compound 3e, and compound 4b was used instead of compound 3f.

[0436] The analysis results of the above compound 4c are as follows.

[0437] MALDI-TOF MS: 511.32 m / z

[0438]

[0439] (Reaction Scheme 15B)

[0440]

[0441] Compound 4d was synthesized in the same manner as the synthesis of compound 3e, except that compound 1e was used instead of compound 3d.

[0442] The analysis results of the above compound 4d are as follows.

[0443] MALDI-TOF MS: 244.14 m / z

[0444]

[0445] (Reaction Scheme 16B)

[0446]

[0447] Compound 4e was synthesized in the same manner as the synthesis of compound 3g, except that compound 4d was used instead of compound 3e.

[0448] The analysis results of the above compound 4e are as follows.

[0449] MALDI-TOF MS: 465.30 m / z

[0450]

[0451] (Reaction Scheme 17B)

[0452]

[0453] 727 mg (2.68 mmol, 1.0 eq) of the above compound 2c, 1.00 g (2.68 mmol, 1.0 eq) of the above compound 2e, 1.37 g (2.68 mmol, 1.0 eq) of the above compound 4c, and 1.25 g (2.68 mmol, 1.0 eq) of the above compound 4e were dissolved in 7.50 mL of n-amyl alcohol together with 265 mg (2.68 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 2.04 g (13.4 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was raised to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and diluted with 32.0 mL of methanol. 32.0 mL of brine was added to form a precipitate, which was then isolated by vacuum filtration. The resulting solid was washed several times with distilled water and dried overnight in a vacuum oven, yielding 4.38 g (2.60 mmol) of the compound represented by the chemical formula 6B (yield: 97%).

[0454] The analysis results of the compound represented by the above chemical formula 6B are as follows.

[0455] MALDI-TOF MS: 1682.86 m / z

[0456]

[0457] (Preparation Example 5B: Synthesis of a compound represented by Chemical Formula 7B)

[0458] (Reaction Scheme 18B)

[0459]

[0460] Compound 5b was synthesized in the same manner as the synthesis of compound 2c, except that compound 5a was used instead of compound 2b.

[0461] The analysis results of the above compound 5b are as follows.

[0462] MALDI-TOF MS: 244.14 m / z

[0463]

[0464] (Reaction Scheme 19B)

[0465]

[0466] 2.84 g (20.0 mmol, 2.0 eq) of methyl iodide (MeI) was added to a solution of 2.43 g (10.0 mmol, 1.0 eq) of the above compound 5b in 5.0 mL of acetonitrile, and the reaction was refluxed overnight. After removing all volatile components under reduced pressure, the residue was suspended using a mixed solution of ethyl acetate / n-hexane (v / v= 1 / 1), and the suspension was separated by reduced pressure filtration to obtain 3.78 g (9.80 mmol) of the above compound 5c. (Yield 98%)

[0467] The analysis results of the above compound 5c are as follows.

[0468] MALDI-TOF MS: 258.16 m / z

[0469]

[0470] (Reaction Scheme 20B)

[0471]

[0472] A compound represented by the chemical formula 7B was synthesized in the same manner as the synthesis of the compound represented by the chemical formula 4, except that the compound 4e was used instead of the compound 2c, and the compound 5c was used instead of the compound 2e.

[0473] The analysis results of the compound represented by the above chemical formula 7B are as follows.

[0474] MALDI-TOF MS: 1713.99 m / z

[0475]

[0476] (Preparation Example 6B: Synthesis of a compound represented by chemical formula 8B)

[0477] (Reaction Scheme 21B)

[0478]

[0479] Compound 6a was synthesized in the same manner as the synthesis of compound 3g, except that compound 4a was used instead of compound 3e.

[0480] The analysis results of the above compound 6a are as follows.

[0481] MALDI-TOF MS: 453.26 m / z

[0482]

[0483] (Reaction Scheme 22B)

[0484]

[0485] Compound 6b was synthesized in the same manner as the synthesis of the compound represented by Chemical Formula 5, except that compound 1e was used instead of compound 3b, compound 4e was used instead of compound 2c, and compound 6a was used instead of compound 3g.

[0486] The analysis results of the above compound 6b are as follows.

[0487] MALDI-TOF MS: 1666.87 m / z

[0488]

[0489] (Reaction Scheme 23B)

[0490]

[0491] A compound represented by the chemical formula 8B was synthesized in the same manner as the synthesis of the compound represented by the chemical formula 3, except that the compound 6b was used instead of the compound 1f.

[0492] The analysis results of the compound represented by the above chemical formula 8B are as follows.

[0493] MALDI-TOF MS: 1466.77 m / z

[0494]

[0495] (Comparative Manufacturing Example 1A: Synthesis of a compound represented by chemical formula C-1A)

[0496] (Reaction Scheme 28A)

[0497]

[0498] A compound represented by the chemical formula C-1A was synthesized in the same manner as the synthesis of the material corresponding to compound 1f, except that compound 5g was used instead of compound 1c and compound 1e.

[0499] The analysis results of the compound represented by the above chemical formula C-1A are as follows.

[0500] MALDI-TOF MS: 1120.14 m / z

[0501]

[0502] (Comparative Manufacturing Example 2A: Synthesis of a compound represented by chemical formula C-2A)

[0503] (Reaction Scheme 29A)

[0504]

[0505] Compound 7b was synthesized in the same manner as the synthesis of compound 1c, except that compound 7a was used instead of compound 1b.

[0506] The analysis results of the above compound 7b are as follows.

[0507] MALDI-TOF MS: 301.02 m / z

[0508]

[0509] (Reaction Scheme 30A)

[0510]

[0511] A compound represented by the chemical formula C-2A was synthesized in the same manner as the synthesis of the substance corresponding to compound 1f, except that compound 7b was used instead of compound 1c and compound 1e.

[0512] The analysis results of the compound represented by the above chemical formula C-2A are as follows.

[0513] MALDI-TOF MS: 1264.01 m / z

[0514]

[0515] (Comparative Manufacturing Example 3A: Synthesis of a compound represented by the chemical formula C-3A)

[0516] (Reaction Scheme 31A)

[0517]

[0518] Compound 8b was synthesized in the same manner as the synthesis of compound 1c, except that compound 8a was used instead of compound 1b.

[0519] The analysis results of the above compound 8b are as follows.

[0520] MALDI-TOF MS: 336.13 m / z

[0521]

[0522] (Reaction Scheme 32A)

[0523]

[0524] The above compound 8b 3.35 g (10.0 mmol, 1.0 eq) and NaH (60% in mineral oil) 440 mg (11.0 mmol, 1.1 eq) were dissolved in 30 mL of tetrahydrofuran, and the solution was stirred at 0°C for 30 minutes. After adding 2.09 g (10.0 mmol, 1.0 eq) of the above compound 8c, the mixture was stirred overnight at room temperature. The reaction was monitored through thin-layer chromatography (TLC) to observe the disappearance of the compound 8b, and then 200 mL of distilled water was added and extracted with ethyl acetate (2 x 100 mL). The organic layer was passed through MgSO4, concentrated, and purified through column chromatography. The obtained compound was again dissolved in a 10.0 After dissolving in mL, it was stirred at room temperature for 1 hour. All volatile components were removed under reduced pressure to obtain 2.43 g (7.90 mmol) of the compound 8d, which was used in the next reaction without further purification. (Yield 79%)

[0525] The analysis results of the above compound 8d are as follows.

[0526] MALDI-TOF MS: 308.10 m / z

[0527]

[0528] (Reaction Scheme 33A)

[0529]

[0530] A compound represented by the chemical formula C-3A was synthesized in the same manner as the synthesis of compound 1f, except that compound 7b was used instead of compound 1c and compound 8d was used instead of compound 1e.

[0531] The analysis results of the compound indicated above as C-3A are as follows.

[0532] MALDI-TOF MS: 1278.16 m / z

[0533]

[0534] (Comparative Manufacturing Example 4A: Synthesis of a compound represented by the chemical formula C-4A)

[0535] (Reaction Scheme 34A)

[0536]

[0537] A compound represented by the chemical formula C-4A was synthesized in the same manner as the synthesis of compound 1f, except that compound 7b was used instead of compound 1c and compound 8d was used instead of compound 1e.

[0538] The analysis results of the compound represented by the above chemical formula C-4A are as follows.

[0539] MALDI-TOF MS: 1285.24 m / z

[0540]

[0541] (Comparative Manufacturing Example 1B: Synthesis of a compound represented by chemical formula C-1B)

[0542] (Reaction Scheme 24B)

[0543]

[0544] The compound 3b (2.77 g, 10.7 mmol, 4.0 eq) was dissolved in 7.50 mL of n-amyl alcohol together with 265 mg (2.68 mmol, 1.0 eq) of cuprous chloride (CuCl), and the mixture was heated to 90°C and stirred for 5 minutes. 2.04 g (13.4 mmol, 5.0 eq) of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) was added to the reaction mixture, and the reaction temperature was increased to 140°C and stirred overnight. The reaction mixture was cooled to room temperature and diluted with 32.0 mL of methanol. 32.0 mL of brine was added to form a precipitate, which was then separated by filtration under reduced pressure. The obtained solid was washed several times with distilled water and dried overnight in a vacuum oven, and as a result, 2.86 g (2.60 mmol) of the compound represented by the chemical formula C-1B was obtained. (Yield 97%)

[0545] The analysis results of the compound represented by the above chemical formula C-1B are as follows.

[0546] MALDI-TOF MS: 1100.46 m / z

[0547]

[0548] (Comparative Manufacturing Example 2B: Synthesis of a compound represented by the chemical formula C-2B)

[0549] (Reaction Scheme 25B)

[0550]

[0551] Compound 7b was synthesized in the same manner as the synthesis of compound 2c, except that compound 7a was used instead of compound 2b.

[0552] The analysis results of the above compound 7b are as follows.

[0553] MALDI-TOF MS: 216.11 m / z

[0554]

[0555] (Reaction Scheme 26B)

[0556]

[0557] A compound represented by the chemical formula C-2B was synthesized in the same manner as the synthesis of the compound represented by the chemical formula C-1B, except that the compound 7b was used instead of the compound 3b.

[0558] The analysis results of the compound represented by the above chemical formula C-2B are as follows.

[0559] MALDI-TOF MS: 924.35 m / z

[0560]

[0561] (Comparative Manufacturing Example 3B: Synthesis of a compound represented by the chemical formula C-3B)

[0562] (Reaction Scheme 27B)

[0563]

[0564] Compound 8b was synthesized in the same manner as the synthesis of compound 2c, except that compound 8a was used instead of compound 2b.

[0565] The analysis results of the above compound 8b are as follows.

[0566] MALDI-TOF MS: 288.13 m / z

[0567]

[0568] (Reaction Scheme 28B)

[0569]

[0570] A substance corresponding to compound 8c was synthesized in the same manner as the synthesis of the compound represented by the chemical formula C-1B, except that compound 8b was used instead of compound 3b.

[0571] The analysis results of the above compound 8c are as follows.

[0572] MALDI-TOF MS: 1212.44 m / z

[0573]

[0574] (Reaction Scheme 29B)

[0575]

[0576] The compound 8c2.95 g (2.43 mmol, 1.0 eq) was dissolved in 4.80 mL of a 1 / 1 solution of trifluoroacetic acid (TFA) and dichloromethane (DCM), and stirred at room temperature for 1 hour. All volatile components were removed under reduced pressure, and the precipitate was filtered under reduced pressure and washed with distilled water to obtain 1.96 g (2.41 mmol) of the compound represented by the chemical formula C-3B. (Yield: 99%)

[0577] The analysis results of the compound represented by the above chemical formula C-3B are as follows.

[0578] MALDI-TOF MS: 812.23 m / z

[0579]

[0580] (Manufacture of pigment dispersion)

[0581] (Example 1A)

[0582] A pigment dispersion was prepared by mixing 1.5 wt% of the pigment dispersion preparation of Manufacturing Example 1A, 11 wt% of blue pigment (Pigment Blue 15:6), 4 wt% of dispersant, 4.5 wt% of dispersion resin, and 79 wt% of solvent.

[0583] (Example 2A)

[0584] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Manufacturing Example 2A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0585] (Example 3A)

[0586] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Manufacturing Example 3A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0587] (Example 4A)

[0588] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Manufacturing Example 4A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0589] (Example 1B)

[0590] A pigment dispersion was prepared by mixing 1.5 wt% of the pigment dispersion preparation of Manufacturing Example 1B, 11 wt% of blue pigment (Pigment Blue 15:6), 4 wt% of dispersant, 4.5 wt% of dispersion resin, and 79 wt% of solvent.

[0591] (Example 2B)

[0592] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Manufacturing Example 2B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0593] (Example 3B)

[0594] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Manufacturing Example 3B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0595] (Example 4B)

[0596] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Manufacturing Example 4B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0597] (Example 5B)

[0598] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Manufacturing Example 5B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0599] (Example 6B)

[0600] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Manufacturing Example 6B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0601] (Comparative Example 1A)

[0602] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 1A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0603] (Comparative Example 2A)

[0604] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 2A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0605] (Comparative Example 3A)

[0606] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 3A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0607] (Comparative Example 4A)

[0608] The same procedure as Example 1A was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 4A was used instead of the pigment dispersion preparation of Manufacturing Example 1A.

[0609] (Comparative Example 1B)

[0610] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 1B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0611] (Comparative Example 2B)

[0612] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 2B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0613] (Comparative Example 3B)

[0614] The same procedure as Example 1B was followed, except that the pigment dispersion preparation of Comparative Manufacturing Example 3B was used instead of the pigment dispersion preparation of Manufacturing Example 1B.

[0615]

[0616] (Manufacture of photosensitive resin composition)

[0617] (Example 1-1A)

[0618] A photosensitive resin composition was prepared by mixing 2 wt% of a binder resin (RY92-M10, Showa Denko), 2 wt% of a polymerizable monomer (DPHA, Nippon Gunyaku), 0.5 wt% of a polymerization initiator (SPI-03, Samyang), 6.2 wt% of a blue pigment (Pigment Blue 15:6, Sanyo), 1.8 wt% of a purple pigment (Pigment Violet 23, Sanyo), 4 wt% of the pigment dispersion of Example 1A, 0.02 wt% of a silane coupling agent (KBM-503, ShinEtsu), and 83.48 wt% of a solvent (PGMEA, DAICEL).

[0619] (Example 2-1A)

[0620] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Example 2A was used instead of the pigment dispersion of Example 1A.

[0621] (Example 3-1A)

[0622] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Example 3A was used instead of the pigment dispersion of Example 1A.

[0623] (Example 4-1A)

[0624] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Example 4A was used instead of the pigment dispersion of Example 1A.

[0625] (Example 1-1B)

[0626] A photosensitive resin composition was prepared by mixing 2 wt% of binder resin (RY92-M10, Showa Denko), 2 wt% of polymerizable monomer (DPHA, Nippon Gunyaku), 0.5 wt% of polymerization initiator (SPI-03, Samyang), 8 wt% of purple pigment (Pigment Violet 23, Sanyo), 4 wt% of the pigment dispersion of Example 1B, 0.02 wt% of silane coupling agent (KBM-503, ShinEtsu), and 83.48 wt% of solvent (PGMEA, DAICEL).

[0627] (Example 2-1B)

[0628] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Example 2B was used instead of the pigment dispersion of Example 1B.

[0629] (Example 3-1B)

[0630] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Example 3B was used instead of the pigment dispersion of Example 1B.

[0631] (Example 4-1B)

[0632] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Example 4B was used instead of the pigment dispersion of Example 1B.

[0633] (Example 5-1B)

[0634] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Example 5B was used instead of the pigment dispersion of Example 1B.

[0635] (Example 6-1B)

[0636] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Example 6B was used instead of the pigment dispersion of Example 1B.

[0637] (Comparative Example 1-1A)

[0638] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Comparative Example 1A was used instead of the pigment dispersion of Example 1A.

[0639] (Comparative Example 2-1A)

[0640] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Comparative Example 2A was used instead of the pigment dispersion of Example 1A.

[0641] (Comparative Example 3-1A)

[0642] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Comparative Example 3A was used instead of the pigment dispersion of Example 1A.

[0643] (Comparative Example 4-1A)

[0644] The same procedure as Example 1-1A was followed, except that the pigment dispersion of Comparative Example 4A was used instead of the pigment dispersion of Example 1A.

[0645] (Comparative Example 1-1B)

[0646] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Comparative Example 1B was used instead of the pigment dispersion of Example 1B.

[0647] (Comparative Example 2-1B)

[0648] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Comparative Example 2B was used instead of the pigment dispersion of Example 1B.

[0649] (Comparative Example 3-1B)

[0650] The same procedure as Example 1-1B was followed, except that the pigment dispersion of Comparative Example 3B was used instead of the pigment dispersion of Example 1B.

[0651]

[0652] (evaluation)

[0653] particle size assessment

[0654] The particle size of each pigment dispersion of the photosensitive resin compositions of Examples 1-1A to 4-1A, Comparative Examples 1-1A to 4-1A, Examples 1-1B to 6-1B, and Comparative Examples 1-1B to 3-1B was measured using a dynamic light scattering analyzer (ELS-Z, Otsuka), and the results at D90 are shown in Tables 1 and 2 below.

[0655]

[0656] Comparative Example 1-1A2-1A3-1A4-1A1-1A2-1A3-1A4-1A Particle size (nm) 8886858491939292

[0657]

[0658] Comparative Example 1-1B2-1B3-1B4-1B5-1B6-1B1-1B2-1B3-1B Particle size (nm) 717673757272899390

[0659] From the above Tables 1 and 2, it can be confirmed that the compound according to one embodiment acts as a pigment synergist and can significantly improve dispersion stability by preventing aggregation between pigments used together.

[0660]

[0661] Spectral characteristics and heat resistance evaluation

[0662] The photosensitive resin compositions of Examples 1-1A to 4-1A, Comparative Examples 1-1A to 2-1A, Examples 1-1B to 6-1B and Comparative Examples 1-1B to 3-1B were spin-coated on glass specimens (10 X 10 cm) in 3 sheets each with a thickness of 0.3 to 0.5 ㎛, and then pre-baked on a 100 ℃ hot plate for 3 minutes. Subsequently, a UV exposure device was used to expose the specimens at 200 mJ / cm. 2After exposure to light, it was post-baked on a 230 ℃ hot plate for 5 minutes. The spectrum of the manufactured three specimens was measured using a chromaticity meter (MPCD-1, Otsuka), and the thickness was measured using a contact thickness measuring device (Tencor P-16). The measured results were calculated to obtain the transmittance values ​​(%) corresponding to each wavelength at a thickness of 0.35 ㎛, which are shown in Tables 3 and 4 below. The better the tinting power of the blue color filter composition, the lower the transmittance value at a wavelength of 610 nm based on the same thickness. In addition, the manufactured specimen was baked on a 230 ℃ hot plate for 10 minutes. The color values ​​before and after baking were measured using a chromaticity meter, and the △Eab* value, which is a measure of color change, was calculated using the following [Formula 1], and the results are shown in Tables 3 and 4 below.

[0663] [Formula 1]

[0664] ΔEab* = {(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} x 1 / 2 (the smaller the ΔEab* value, the better the heat resistance)

[0665]

[0666] Example Comparative Example 1-1A2-1A3-1A4-1A1-1A2-1A3-1A4-1A Transmittance (610 nm) 11.6 11.4 10.8 10.6 12.5 12.7 12.8 12.9 Heat resistance (ΔE ab *)0.70.70.90.80.80.81.31.1

[0667]

[0668] Example Comparative Example 1-1B2-1B3-1B4-1B5-1B6-1B1-1B2-1B3-1B Transmittance (610 nm) 8.0 9.9 8.8 9.19 09.3 11.5 12.0 11.8 Heat resistance (ΔEab*) 0.7 0.8 0.8 0.7 0.9 0.8 0.9 1.2 1.2

[0669] From the above Tables 3 and 4, it can be confirmed that the compound according to one embodiment can secure excellent heat resistance as a pigment synergist without reducing the coloring power of the composition.

[0670]

[0671] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A compound represented by the following chemical formula 1 or a salt thereof: [Chemical Formula 1] In the above chemical formula 1, M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr, n1 to n4 are each independently integers from 1 to 4, A, B, C and D are each independently represented by the following chemical formula 1-1A or chemical formula 1-1B, provided that any one of A, B, C and D is different from at least any one of the remaining three, [Chemical Formula 1-1A] In the above chemical formula 1-1A, L 1 is a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), L 2 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof, R 1 is an acidic group, [Chemical Formula 1-1B] In the above chemical formula 1-1B, L 1 is a substituted or unsubstituted C1 to C20 alkylene group, ether group, amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof, R 1 is a basic group.

2. In paragraph 1, The acid group above is *-SO3 - , a carboxyl group, a phosphoric acid group or a phosphonic acid group, The above basic group is *-NR b R c (R b and R c A compound represented by the following chemical formula B-1, the following chemical formula B-2, the following chemical formula B-3, the following chemical formula B-4 or the following chemical formula B-5, or a salt thereof, wherein each independently represents a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group: [Chemical Formula B-1] [Chemical Formula B-2] [Chemical Formula B-3] [Chemical Formula B-4] [Chemical Formula B-5] In the above chemical formulas B-1 to B-5, R d Inland R l are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

3. In paragraph 1, Above *-N(R a )-* is a compound represented by the following chemical formula N or a salt thereof: [Chemical formula N] In the above chemical formula N, L 5 is a substituted or unsubstituted C1 to C10 alkylene group, R 5 is an acidic group.

4. In paragraph 2, In the above chemical formulas B-3 and B-4, R f Inland R i A compound or a salt thereof, each independently representing a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

5. In paragraph 1, The compound is a compound represented by the following chemical formula 2A or chemical formula 2B or a salt thereof: [Chemical Formula 2A] In the above chemical formula 2A, M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr, L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, an amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), L 2a , L 2b , L 2c and L 2d are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, an ether group (*-O-*), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof, R 1a , R 1b , R 1c and R 1d are each independently acidic, [Chemical Formula 2B] In the above chemical formula 2B, M is Cu, Zn, Co, Al, Ga, In, Ca, Mo, Mg or Zr, L 1a , L 1b , L 1c and L 1d are each independently a substituted or unsubstituted C1 to C20 alkylene group, ether group, amide group (*-C(=O)NR a -*; R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), *-N(R a )-*(R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group), a substituted or unsubstituted C6 to C20 arylene group or a combination thereof, R 1a , R 1b , R 1c and R 1d are each independently basic groups.

6. In paragraph 1, The compound or salt thereof is a compound represented by any one of the following chemical formulas 3A to 6A and 3B to 8B, or a salt thereof. [Chemical Formula 3A] [Chemical Formula 4A] [Chemical Formula 5A] [Chemical Formula 6A] [Chemical Formula 3B] [Chemical Formula 4B] [Chemical Formula 5B] [Chemical Formula 6B] [Chemical Formula 7B] [Chemical Formula 8B] 7. In paragraph 1, The compound or salt thereof is a pigment synergist.

8. In paragraph 7, The compound or salt thereof is a compound or salt thereof which is a blue pigment synergist.

9. A pigment dispersion comprising a compound or a salt thereof and a pigment according to any one of claims 1 to 8.

10. In paragraph 9, The above pigment is a pigment dispersion which is a blue pigment.

11. In paragraph 10, The above pigment is a pigment dispersion further containing a purple pigment.

12. In paragraph 9, The above pigment dispersion further comprises a dispersant, a dispersing resin, and a solvent.

13. In paragraph 12, The above pigment dispersion is based on the total amount of the above pigment dispersion. 0.5 to 5 wt% of the compound or its salt; 5 to 20 wt% of the pigment; 1 to 5 wt% of the above dispersant; 3 to 10 wt% of the above dispersion resin; and The above solvent residue A pigment dispersion containing .

14. A coloring agent comprising a compound according to any one of claims 1 to 8 or a salt thereof and a pigment, A photosensitive resin composition further comprising a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.

15. A photosensitive resin film manufactured using the photosensitive resin composition of Article 14.

16. A color filter including the photosensitive resin film of Article 15.

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