Core-shell compounds, photosensitive resin compositions, photosensitive resin films, color filters, and CMOS image sensors

Abstract

The present invention provides core-shell compounds, photosensitive resin compositions containing the same, films, and filters. [Solution] The core-shell compound is, for example, a core represented by the following formula JPEG2026081081000067.jpg3982 and the shell represented by the following formula JPEG2026081081000068.jpg29101 It consists of.

Description

[Technical Field]

[0001] This disclosure relates to a core-shell compound, a photosensitive resin composition containing the core-shell compound, a photosensitive resin film manufactured using the photosensitive resin composition, a color filter containing the photosensitive resin film, and a CMOS image sensor containing the color filter. [Background technology]

[0002] Recently, the rapid development of advanced information and communication processing technologies and the electronics industry as a whole has created a need for next-generation detectors capable of rapidly transmitting and receiving large amounts of information, and has necessitated the development of new concepts in elements and systems. In particular, with the rise of video processing in mobile devices, the technology for ultra-miniaturized and ultra-power-saving video image sensors is rapidly accelerating, centered on existing CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) technologies.

[0003] An image sensor is a semiconductor that converts photons into electrons so that they can be displayed on a screen or stored in a storage device. It consists of a photodetector that converts a received light signal into an electrical signal, a pixel circuit that amplifies and compresses the converted electrical signal, and an ASIC that processes the image signal by converting the pre-processed analog signal into digital. There are various types such as CCD, CMOS, and CIS (Contact Image Sensor).

[0004] CCD and CMOS image sensors use the same light-receiving element. In a CCD image sensor, the charge generated at the light-receiving section moves sequentially through a series of connected MOS capacitors and is converted into a voltage by a source follower connected to the end. On the other hand, in a CMOS image sensor, the charge is converted into a voltage by a source follower built into each pixel and output externally. More specifically, a CCD image sensor moves electrons generated by light directly to the output section using a gate pulse, while a CMOS image sensor converts electrons generated by light into a voltage within each pixel and then outputs it through multiple CMOS switches. The application fields of such image sensors are extremely wide-ranging, from consumer products such as digital cameras and mobile phones to endoscopes used in hospitals and telescopes on artificial satellites orbiting the Earth.

[0005] In CMOS image sensor technology trends, the number of pixels is increasing and the size is decreasing in order to achieve high image quality and miniaturization of devices. As pixel size decreases, there are limitations to manufacturing fine patterns using pigments, and the development of dyes is necessary to compensate for this. However, dyes have problems in terms of the pattern manufacturing process compared to pigments. In particular, there are problems in terms of developability. This is because pigments are fine particles, have crystalline properties and poor solubility, so they do not dissolve in solvents such as PGMEA after baking, whereas dyes are amorphous solids and have the disadvantage of dissolving in the solvent after the baking process. Especially in the case of CMOS image sensors, the colorant content is high and the ratio of binder resins and monomers used together is relatively low, making it difficult to improve the developability of dyes. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Korean Published Patent Publication No. 10-2020-0127198 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] One embodiment provides a core-shell compound that constitutes a green pixel in a color filter for a CMOS image sensor.

[0008] Another embodiment provides a photosensitive resin composition comprising a core-shell compound.

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

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

[0011] Another embodiment provides a CMOS image sensor including a color filter. [Means for solving the problem]

[0012] One embodiment of the present invention provides a core-shell compound comprising a core represented by the following chemical formula 1 and a shell surrounding the core, represented by the following chemical formula 2.

[0013] [Chemical formula 1] [ka]

[0014] [Chemical formula 2] [ka]

[0015] In the above chemical formulas 1 and 2, R 1 It is a thermosetting group, R 2 and R 3 Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group. L 1 and L 6 are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or represented by the following chemical formula L, provided that L 1 and L 6 at least one of which is represented by the following chemical formula L,

[0016] [Chemical formula L]

Chemical formula

[0017] In the above chemical formula L, L 7 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, m is an integer of 2 to 10, L 2 , L 4 , L a , and L b are each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 3 is a single bond or an ester group (*-C(=O)O-* or *-OC(=O)-*), L 5 is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, n is an integer of 2 or more.

[0018] The thermosetting group can include a substituted or unsubstituted epoxy group, a substituted or unsubstituted oxetane group, or a combination thereof.

[0019] In Chemical formula 1, R 1 is a thermosetting group, R 2 and R 3 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 and L 5 are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 2 ~L 4Each of them is an independent single bond, L 6 It can be represented by the chemical formula L.

[0020] In chemical formula 1, R 1 R is a thermosetting group, 2 and R 3 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 It is represented by the chemical formula L, L 2 , L 4 , and L 6 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 3 L is an ester group (*-C(=O)O-* or *-OC(=O)-*), 5 This may be a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0021] In chemical formula 1, R 1 R is a thermosetting group, 2 and R 3 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 and L 6 Each is independently represented by the chemical formula L, L 2 and L 4 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 3 L is an ester group (*-C(=O)O-* or *-OC(=O)-*), 5 This may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0022] The core represented by chemical formula 1 can have a maximum absorption wavelength in the range of 610 nm to 640 nm.

[0023] The shell represented by chemical formula 2 can be represented by the following chemical formula 2-1.

[0024] [Chemical formula 2-1] [ka]

[0025] Core-shell compounds can be represented by any one of the following chemical formulas A through C.

[0026] [Chemical formula A] [ka]

[0027] [Chemical formula B] [ka]

[0028] [Chemical formula C] [ka]

[0029] Core shell compounds may also be green dyes.

[0030] Another embodiment provides a photosensitive resin composition comprising a core-shell compound.

[0031] The photosensitive resin composition may further comprise a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent.

[0032] The photosensitive resin composition may also be used for CMOS image sensors.

[0033] Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0034] Another embodiment provides a color filter including a photosensitive resin film.

[0035] Another embodiment provides a CMOS image sensor including a color filter.

[0036] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0037] The core-shell compound according to one embodiment has excellent developability itself, and therefore can maintain excellent developability even after curing and heat processing. Furthermore, a photosensitive resin composition containing this as a dye can form fine patterns and can provide a green color filter for CMOS image sensors. [Modes for carrying out the invention]

[0038] Embodiments of the present invention will be described in detail below. However, these are presented as examples only and do not limit the present invention, which is defined only within the scope of the claims described below.

[0039] Unless otherwise specified herein, “substituted” and “substituted” mean that one or more hydrogen atoms in a functional group are replaced by halogen atoms (F, Br, Cl, or I), hydroxyl groups, nitro groups, cyano groups, amino groups (NH2, NH(R)). 200 ), or N(R 201 )(R 202 ) and here R 200 , R 201 , and R 202 This means that the group is substituted with one or more substituents selected from the group consisting of (which are identical or different from each other and are each an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group.

[0040] Unless otherwise specified herein, “alkyl group” means an alkyl group having 1 to 20 carbon atoms, specifically an alkyl group having 1 to 15 carbon atoms; “cycloalkyl group” means a cycloalkyl group having 3 to 20 carbon atoms, specifically a cycloalkyl group having 3 to 18 carbon atoms; “alkoxy group” means an alkoxy group having 1 to 20 carbon atoms, specifically an alkoxy group having 1 to 18 carbon atoms; “aryl group” means an aryl group having 6 to 20 carbon atoms, specifically an aryl group having 6 to 18 carbon atoms; “alkenyl group” means an alkenyl group having 2 to 20 carbon atoms, specifically an alkenyl group having 2 to 18 carbon atoms; “alkylene group” means an alkylene group having 1 to 20 carbon atoms, specifically an alkylene group having 1 to 18 carbon atoms; and “arylene group” means an arylene group having 6 to 20 carbon atoms, specifically an arylene group having 6 to 16 carbon atoms.

[0041] Unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means that both "acrylic acid" and "methacrylic acid" are possible.

[0042] Unless otherwise defined herein, “combination” means mixing or copolymerization. “Copolymer” means block copolymerization or random copolymerization, and “copolymer” means block copolymer or random copolymer.

[0043] Unless otherwise defined in the chemical formulas herein, the absence of a chemical bond at a position where one should be depicted means that a hydrogen atom is bonded at that position.

[0044] Furthermore, unless otherwise defined herein, "*" means a portion linked to the same or different atoms or chemical formulas.

[0045] One embodiment provides a core-shell compound comprising a core represented by the following chemical formula 1 and a shell surrounding the core, represented by the following chemical formula 2.

[0046] [Chemical formula 1] [ka]

[0047] [Chemical formula 2] [ka]

[0048] In the above chemical formulas 1 and 2, R 1 It is a thermosetting group, R 2 and R 3 Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group. L 1 and L 6 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or represented by the following chemical formula L, where L 1 and L 6 At least one of them is represented by the following chemical formula L,

[0049] [Chemical formula L] [ka]

[0050] In the above chemical formula L, L 7 This is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. m is an integer between 1 and 10, for example, an integer between 2 and 10. L 2 , L 4 , L a , and L b Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. L 3These are single bonds or ester groups (*-C(=O)O-* or *-OC(=O)-*), L 5 This is a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. n is an integer greater than or equal to 2.

[0051] Liquid crystal display (LCD) devices, a type of display device, have advantages such as being lightweight, thin, inexpensive, low-power, and having excellent compatibility with integrated circuits, and their range of use is expanding for laptops, monitors, and TV images. Such an LCD device comprises a lower substrate on which a black matrix, color filters, and ITO pixel electrodes are formed, an active circuit section consisting of a liquid crystal layer, thin-film transistors, and an energy storage capacitor layer, and an upper substrate on which ITO pixel electrodes are formed. The color filter has a structure in which a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundaries between pixels and pixel sections arranged in a predetermined order to form each pixel. One method for realizing a color filter is the pigment dispersion method, in which a colored thin film is formed by repeating a series of processes in which a photopolymerizable composition containing a colorant is coated onto a transparent substrate provided with a black matrix, the pattern in the form to be formed is exposed, and then the unexposed areas are removed with a solvent and the film is heat-cured. The colored photosensitive resin compositions used in the manufacture of color filters by the pigment dispersion method generally consist of alkali-soluble resins, photopolymerizable monomers, photopolymerization initiators, epoxy resins, solvents, and other additives. Pigment dispersion methods with the characteristics described above are actively applied to the manufacture of LCDs for mobile phones, laptops, monitors, TVs, and other devices.

[0052] An image sensor is a component used to generate images in mobile phone cameras and digital still cameras (DSCs). Based on its manufacturing process and application, image sensors can be broadly classified into charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors. Color image sensors used in solid-state or complementary metal oxide semiconductors typically utilize color filters, each containing a filter segment for the additive mixing primary colors red, green, and blue, on their light-receiving element to separate colors. Recently, the pattern size of these color filters is less than 2 μm, which is 1 / 100 to 1 / 200 times smaller than existing LCD color filter patterns. This has led to increased resolution and reduced residual image, which are crucial factors affecting the sensor's performance.

[0053] On the other hand, color filters manufactured from pigment-type photosensitive resin compositions suffer from color mixing problems due to the size of the pigment particles and limitations in thin-film thinning. Furthermore, in the case of color image sensors for image sensors, even smaller dispersion particle sizes are required to form fine patterns. To meet these demands, efforts have been ongoing for a long time to improve resolution by introducing dyes that do not form particles instead of pigments and manufacturing photosensitive resin compositions suitable for dyes.

[0054] This invention relates to a green dye to be added to a color filter for a CMOS image sensor or a color filter for OLEDos (OLED on silicon). As pixel size decreases, there are limitations to manufacturing fine patterns using pigments, and the development of dyes is necessary to compensate for this. Dyes have problems in terms of the pattern manufacturing process compared to pigments, and in particular they are very inferior in terms of developability, making it very difficult to form fine patterns after the curing and heat processes. Furthermore, when the dye, which is a coloring agent, is contained in small amounts relative to the total amount of the composition, a slight inferiority in the developability of the dye itself is not a major problem. However, in the case of photosensitive resin compositions for CMOS image sensors or OLEDos (OLED on silicon), the dye is contained in excessive amounts (about 15% to 30% by weight, for example, about 16% to 27% by weight relative to the total amount of the photosensitive resin composition), so there is a very great need to develop a dye with excellent developability on its own.

[0055] After numerous trials and errors, the inventors of the present invention synthesized a core-shell compound by inserting an alkylene oxide linking group into a core-forming squarylium-based compound and simultaneously introducing a thermosetting group at its terminal, enclosing the core with a shell. The core-shell compound synthesized in this manner according to one embodiment exhibits excellent developability, and a photosensitive resin composition containing an excess amount of this compound as a green dye suppresses the decrease in developability even after curing and heat processes, making it highly suitable for use in green color filters for CMOS image sensors or OLEDos (OLED on silicon).

[0056] In other words, the present invention aims to provide a squarylium-based core-shell dye with improved developability. As mentioned above, when color filters are manufactured using compositions containing dyes, there is a problem of bottom residue formation, and the cause of this has been attributed to the low solubility of the dye in the alkaline aqueous solution used during the development process. As a result of efforts to solve this problem, the inventors have confirmed that bottom residue can be reduced by including alkylene oxide linking groups such as ethylene oxide in the dye structure and introducing thermosetting groups at the ends, thereby completing the present invention.

[0057] For example, the thermosetting group may include a substituted or unsubstituted epoxy group, a substituted or unsubstituted oxetane group, or a combination thereof.

[0058] The thermosetting group may be further substituted with alkyl groups or the like.

[0059] For example, the compound represented by chemical formula 1 is 1)R 1 R is a thermosetting group, 2 and R 3 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 and L 5 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 2 ~L 4 Each of them is an independent single bond, L 6 1) A compound represented by the chemical formula L, 2) R 1 R is a thermosetting group, 2 and R 3 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 It is represented by the chemical formula L, L 2 , L 4 , and L 6 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 3 L is an ester group (*-C(=O)O-* or *-OC(=O)-*),5 3)R is a compound in which a single bond, substituted or unsubstituted alkylene group has 1 to 10 carbon atoms, or 1 R is a thermosetting group, 2 and R 3 Each is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L 1 and L 6 Each is independently represented by the chemical formula L, L 2 and L 4 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L 3 L is an ester group (*-C(=O)O-* or *-OC(=O)-*), 5 These compounds can be classified into substituted or unsubstituted alkylene groups with 1 to 10 carbon atoms, and all three types of compounds can provide dyes with improved developability.

[0060] For example, a core represented by chemical formula 1 can contain two, four, or six thermosetting groups at its ends. Cores represented by chemical formula 1 with one, three, or five end thermosetting groups are structurally difficult to synthesize (low yield), and even if synthesis is successful, applying them to a production line can be costly and undesirable from an economic standpoint.

[0061] Furthermore, the core represented by chemical formula 1 exhibits superior developability when it has 6 terminal thermosetting groups compared to when it has 4, and superior developability when it has 4 terminal thermosetting groups compared to when it has 2. In other words, considering only the developability of the compound, the core structure represented by chemical formula 1 is better with 4 terminal thermosetting groups than with 2, and better with 6 than with 4.

[0062] Furthermore, the core represented by chemical formula 1 is more advantageous in terms of solubility the more alkylene oxide linking groups it has. Examples of alkylene oxide linking groups include ethylene oxide linking groups or propylene oxide linking groups. Of these, the ethylene oxide linking group is a more hydrophilic linking group, and therefore, using the ethylene oxide linking group may be even more advantageous in terms of solubility.

[0063] On the other hand, in the case of a core represented by chemical formula 1, if the number of terminal thermosetting groups is one, not only is synthesis difficult as described above, but the developability is actually lower than when there are two terminal thermosetting groups. Therefore, it is preferable that the core represented by chemical formula 1 contains two or more terminal thermosetting groups.

[0064] For example, a core represented by chemical formula 1 can have a maximum absorption wavelength in the range of 610 nm to 640 nm. Even if a dye compound has excellent solubility with a solubility of 10% or more in organic solvents, if it does not have a maximum absorption wavelength in the range of 610 nm to 640 nm, its transmittance may be low, making it unsuitable for use as a green photosensitive resin composition for CMOS image sensors or OLEDos (OLED on silicon).

[0065] The shell represented by chemical formula 2 can be represented by the following chemical formula 2-1.

[0066] [Chemical formula 2-1] [ka]

[0067] For example, a core-shell compound can be represented by any one of the following chemical formulas A to C, but is not necessarily limited to these.

[0068] [Chemical formula A] [ka]

[0069] [Chemical formula B] [ka]

[0070] [Chemical formula C] [ka]

[0071] For example, the core-shell compound may be a green dye.

[0072] According to another embodiment, a photosensitive resin composition comprising a core-shell compound according to one embodiment is provided.

[0073] For example, the photosensitive resin composition may have a transmittance of 90% or more at 540 nm, a transmittance of 10% or less at 600 nm to 640 nm, and a transmittance of 5% or less at 450 nm, and may be suitable for realizing a green color filter for high-transmittance CIS. In other words, the photosensitive resin composition may be for high-transmittance CMOS image sensors or OLEDos (OLED on silicon).

[0074] The photosensitive resin composition may further comprise a core-shell compound, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent.

[0075] The core-shell compound according to one embodiment is a dye that plays the role of a colorant in a photosensitive resin composition, and when the colorant is used in a hybrid form of core-shell dye and pigment rather than when the core-shell dye is used alone, it can exhibit maximum developability. That is, the core-shell compound according to one embodiment may be a hybrid dye used together with a pigment.

[0076] For example, the pigments may further include yellow pigments, green pigments, or combinations thereof.

[0077] Yellow pigments include CI Pigment Yellow 138, CI Pigment Yellow 139, and CI Pigment Yellow 150 in the Color Index, and these can be used individually or in mixtures of two or more.

[0078] Green pigments include CI Green 36, CI Green 58, and CI Green 59 in the Color Index, and these can be used individually or in mixtures of two or more.

[0079] The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

[0080] A pigment dispersion may contain solid pigment components, a solvent, and a dispersant for uniformly dispersing the pigment within the solvent.

[0081] The solid pigment may be present in an amount of 1% to 20% by weight, for example, 8% to 20% by weight, for example, 8% to 15% by weight, for example, 10% to 20% by weight, for example, 10% to 15% by weight, based on the total amount of the pigment dispersion.

[0082] Nonionic dispersants, anionic dispersants, cationic dispersants, etc., can be used as dispersants. Specific examples of dispersants include polyalkylene glycols and their esters, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts, alkylamines, etc., which can be used individually or in combination of two or more.

[0083] Examples of commercially available dispersants include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA Chemical's EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc.; and Zeneka's Solsperse 5000, Solsperse Examples include the 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or Ajinomoto's PB711, PB821, etc.

[0084] The dispersant may be included in an amount of 1% to 20% by weight relative to the total amount of the pigment dispersion. When the dispersant is included within the above range, an appropriate viscosity can be maintained, and the dispersibility of the photosensitive resin composition is excellent, thereby maintaining the optical, physical, and chemical quality when the product is applied.

[0085] As solvents for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like can be used.

[0086] The pigment dispersion may be included in an amount of 10% to 20% by weight, for example, 12% to 18% by weight, relative to the total amount of the photosensitive resin composition. When the pigment dispersion is included within the above range, it is advantageous for securing process margins and improves color reproduction and light-to-dark ratio.

[0087] The binder resin may be an acrylic binder resin.

[0088] The acrylic binder resin is a copolymer of a primary ethylenically unsaturated monomer and a secondary ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

[0089] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups. Specific examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0090] The first ethylenically unsaturated monomer may be present in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, relative to the total amount of the acrylic binder resin.

[0091] Examples of secondary ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; vinyl carboxylic acid ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These can be used individually or in combination of two or more.

[0092] Specific examples of acrylic binder resins include (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, and (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited to these, and can be used individually or in combination of two or more types.

[0093] The weight-average molecular weight of the binder resin may be in the range of 3,000 g / mol to 150,000 g / mol, for example, 5,000 g / mol to 50,000 g / mol, or for example, 20,000 g / mol to 30,000 g / mol. When the weight-average molecular weight of the binder resin is within the above range, the photosensitive resin composition exhibits excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate during the manufacture of color filters.

[0094] The acid value of the binder resin may be in the range of 15 mg KOH / g to 60 mg KOH / g, for example, 20 mg KOH / g to 50 mg KOH / g. When the acid value of the binder resin is within the above range, the resolution of the pixel pattern is excellent.

[0095] The binder resin may be included in an amount of 1% to 30% by weight, for example, 1% to 20% by weight, relative to the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent developability during color filter manufacturing is improved, and excellent crosslinking properties are obtained, resulting in superior surface smoothness.

[0096] The photopolymerizable monomer can be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0097] Photopolymerizable monomers, by possessing ethylenically unsaturated double bonds, can undergo sufficient polymerization during exposure in the pattern formation process, thereby forming patterns with excellent heat resistance, light resistance, and chemical resistance.

[0098] Specific examples of photopolymerizable monomers 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, and pentaerythritol tetra(meth)acrylate. Examples include acrylates, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy(meth)acrylate.

[0099] Examples of commercially available photopolymerizable monomers include: monofunctional esters of (meth)acrylic acid such as Aronix M-101 (registered trademark), M-111 (registered trademark), and M-114 (registered trademark) from Toagosei Co., Ltd.; KAYARAD TC-110S (registered trademark) and TC-120S (registered trademark) from Nippon Kayaku Co., Ltd.; and V-158 (registered trademark) and V-2311 (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of (meth)acrylic acid difunctional esters include Aronix M-210(registered trademark), M-240(registered trademark), and M-6200(registered trademark) from Toagosei Co., Ltd.; KAYARAD HDDA(registered trademark), HX-220(registered trademark), and R-604(registered trademark) from Nippon Kayaku Co., Ltd.; and V-260(registered trademark), V-312(registered trademark), and V-335HP(registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include Aronix M-309 (registered trademark), M-400 (registered trademark), M-405 (registered trademark), M-450 (registered trademark), M-710 (registered trademark), M-8030 (registered trademark), and M-8060 (registered trademark) from Toagosei Co., Ltd.; KAYARAD TMPTA (registered trademark), DPCA-20 (registered trademark), -30 (registered trademark), -60 (registered trademark), and -120 (registered trademark) from Nippon Kayaku Co., Ltd.; and V-295 (registered trademark), -300 (registered trademark), -360 (registered trademark), -GPT (registered trademark), -3PA (registered trademark), and -400 (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. The products can be used individually or in combination of two or more.

[0100] Photopolymerizable monomers can also be treated with acid anhydrides before use to impart better developability.

[0101] The photopolymerizable monomer may be included in an amount of 1% to 15% by weight, for example, 5% to 10% by weight, relative to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability and excellent developability in alkaline developers.

[0102] The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, and may include, for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0103] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0104] Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0105] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0106] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0107] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine. Examples include din, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 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.

[0108] Examples of oxime compounds include O-acyl oxime compounds, 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one. Specific examples of O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0109] In addition to compounds, photopolymerization initiators can also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and fluorene compounds.

[0110] The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits that energy to initiate a chemical reaction.

[0111] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0112] The photopolymerization initiator may be included in an amount of 0.01% to 10% by weight, for example, 0.1% to 5% by weight, relative to the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, excellent resolution and adhesion, and prevention of a decrease in transmittance due to unreacted initiators.

[0113] The solvent can be a substance that is compatible with but does not react with the core-shell compound, pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, and pigment according to one embodiment.

[0114] Examples of solvents 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 methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Ketones such as methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylate alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; alkyl 3-oxypropionates such as methyl 3-oxypropionate and ethyl 3-oxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;Alkyl 2-alkoxypropionate esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionate esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; Alkyl monooxymonocarboxylate esters of alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, 2-hydroxy Examples include esters such as methyl xy-3-methylbutanoate; ketonic acid esters such as ethyl pyruvate; and 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.

[0115] Of these, considering compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and / or ketones such as cyclohexanone can be used.

[0116] The solvent may be included in the remainder of the total amount of the photosensitive resin composition, for example, in the range of 30% to 80% by weight. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, resulting in excellent manufacturability of color filters.

[0117] Another embodiment of the photosensitive resin composition may further contain an epoxy compound to improve adhesion to the substrate and other properties.

[0118] Examples of epoxy compounds include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0119] The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight, per 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, excellent adhesion, storage properties, etc., are obtained.

[0120] Furthermore, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group in order to improve adhesion to the substrate.

[0121] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(epoxycyclohexyl)ethyltrimethoxysilane, which can be used individually or in combination of two or more.

[0122] The silane coupling agent may be included in an amount ranging from 0.01 to 10 parts by weight per 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, excellent adhesion, storage properties, etc., are obtained.

[0123] Furthermore, the photosensitive resin composition may further contain a surfactant as needed to improve coating properties and prevent the formation of defects.

[0124] Examples of surfactants include BM-1000 (registered trademark) and BM-1100 (registered trademark) from BM Chemie; and Megafac F 142D (registered trademark), F 172 (registered trademark), F 173 (registered trademark), and F 142D (registered trademark), F 172D (registered trademark), F 173 (registered trademark), and F 173D (registered trademark) from Dainippon Ink and Chemicals, Inc. Fluorine-based surfactants that are commercially available under names such as 183 (registered trademark), etc.; Sumitomo 3M Limited's Florard FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark), etc.; Asahi Glass Co., Ltd.'s Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark), etc.; Toray Silicon Corporation's SH-28PA (registered trademark), SH-28PA-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc. can be used.

[0125] The surfactant can be used in an amount ranging from 0.001 parts by weight to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, staining does not occur, and excellent wetting properties for the glass substrate are obtained.

[0126] Furthermore, the photosensitive resin composition may contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0127] Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition according to one embodiment.

[0128] Another embodiment provides a color filter including a photosensitive resin film.

[0129] The process for forming a pattern within the color filter is as follows:

[0130] The process includes the steps of: applying a photosensitive resin composition onto a support substrate by spin coating, slit coating, inkjet printing, etc.; drying the applied photosensitive resin composition to form a photosensitive resin composition film; exposing the photosensitive resin composition film; developing the exposed photosensitive resin composition film with an alkaline aqueous solution to produce a photosensitive resin film; and heat-treating the photosensitive resin film. Since the process conditions and other related matters are widely known in the art, a detailed explanation is omitted in this specification.

[0131] Another embodiment provides a CMOS image sensor or OLEDos(on silicon) element including a color filter.

[0132] The present invention will be described in more detail below with reference to examples, but the following examples are merely preferred embodiments of the present invention, and the present invention is not limited to the following examples. [Examples]

[0133] (Synthesis of compounds) (Synthesis Example 1: Synthesis of a compound represented by chemical formula A) (Reaction Equation 1) [ka]

[0134] Compound 1a (12 mmol) and compound 1b (10 mmol) were dissolved in 2-propanol with CuCl (0.5 mmol) and NaOH (20 mmol), and the reaction was carried out at a temperature of 90°C for 12 hours. After cooling to room temperature, distilled water was added, and the mixture was extracted with DCM (dichloromethane). The organic layer was passed through MgSO4 and concentrated under reduced pressure, and then compound 1c was obtained by column chromatography (eluent: n-Hex / siRNA).

[0135] (Reaction Equation 2) [ka]

[0136] To a solution of compound 1c (10 mmol) dissolved in THF (tetrahydrofuran), NaH (60% in mineral oil, 15 mmol) was added dropwise at 0°C for 30 minutes. After adding compound 1d (10.5 mmol), the reaction temperature was raised to room temperature and the reaction was carried out overnight. The aqueous layer was extracted using diethyl ether. The organic layer was passed through MgSO4 and concentrated under reduced pressure, and then compound 1e was obtained by column chromatography (eluent: n-Hex / siRNA).

[0137] (Reaction Equation 3) [ka]

[0138] Compound 1e (10 mmol) and compound 1f (11 mmol) were placed in a 1,4-dioxane / H2O (v / v=4 / 1) mixed solution with K2CO3 (15 mmol) and Pd(PPh3)4 (1.0 mmol), and the reflux reaction was carried out overnight. After cooling to room temperature, the organic layer was separated. The organic layer was passed through MgSO4 and concentrated under reduced pressure, and then 1 g of the above compound was obtained by column chromatography (eluent: n-Hex / SiO).

[0139] (Reaction Equation 4) [ka]

[0140] 1 g (10 mmol) of the above compound and 1 h (7 mmol) of the compound were dissolved in n-butanol at room temperature, then triethylorthoformate (30 mmol) was added, and the temperature was raised to 90°C and the reaction was carried out for 4 hours. After removing the solvent under reduced pressure, n-hexane was added to the remaining reaction mixture and stirred at 0°C for 15 minutes. After obtaining the solid produced by vacuum filtration, the mixture was washed with water and dried to obtain compound 1i.

[0141] (Reaction Equation 5) [ka]

[0142] After cooling a solution of compound 1i (10 mmol) dissolved in chloroform to 0°C, two solutions were prepared: (Solution A) compound 1k (30 mmol) and triethylamine (60 mmol) dissolved in chloroform, and (Solution B) compound 1j (30 mmol) dissolved in chloroform. The two solutions were gradually added to the compound 1i solution in the order of Solution A and Solution B, and stirred at room temperature for 2 hours. After removing the solvent under reduced pressure, the polymer byproduct was precipitated by redissolving in EtOAC. After removing the byproduct by vacuum filtration, the solvent was removed under reduced pressure. This was then dissolved again in chloroform, and the above steps were repeated two more times. The substance corresponding to compound 1L was obtained by purification by column chromatography (eluent: DCM-siRNA).

[0143] (Reaction Equation 6) [ka]

[0144] A solution of the above compound 1l (10 mmol) dissolved in THF was added with 1M TBAF (tetrabutylammonium fluoride, 22 mmol), and stirred at room temperature for 2 hours. After confirming through thin-layer chromatography that all of compound 1l had been consumed, the solvent was removed under reduced pressure. Acetone / H2O (v / v = 1 / 1) was added and stirred at 0 °C for 30 minutes, and then the resulting solid was separated by filtration under reduced pressure. After washing with distilled water, it was dried overnight in a vacuum oven at 40 °C to obtain compound 1m.

[0145] (Reaction Scheme 7)

Chemical Formula

[0146] To a solution of the above compound 1m (10 mmol) dissolved in DMSO (dimethylsulfoxide) were added KOH (50 mmol) and ECH (epichlorohydrin, 100 mmol), and stirred at 60 °C for 2 hours. After adding distilled water, extraction was performed using DCM. The organic layer was washed with brine, followed by drying and concentration. Purification was carried out through column chromatography (developing solution: DCM-EtOAc) to obtain a substance corresponding to the above Chemical Formula A.

[0147] The HRMS analysis results of Chemical Formula A are as follows. m / z calcd for C 80 H 87 N8O 14 ([M+H] + )、1383.6336;found、1383.6336。

[0148] (Synthesis Example 2: Synthesis of the compound represented by Chemical Formula B) (Reaction Scheme 8)

Chemical Formula

[0149] Compound 2b was synthesized in the same manner as compound 1c, except that compound 2a was used instead of compound 1b.

[0150] (Reaction Equation 9) [ka]

[0151] Compound 2c was synthesized in the same manner as compound 1g, except that compound 2b was used instead of compound 1e.

[0152] (Reaction Equation 10) [ka]

[0153] Compound 2d was synthesized in the same manner as compound 1i, except that compound 2c was used instead of compound 1g.

[0154] (Reaction Equation 11) [ka]

[0155] Compound 2e was synthesized in the same manner as compound 1l, except that compound 2d was used instead of compound 1i.

[0156] (Reaction Equation 12) [ka]

[0157] 2f (10 mmol) of the above compound was dissolved in acetone, and NaI (50 mmol) was added to the solution and stirred overnight at 50°C. The solvent was removed under reduced pressure, distilled water was added, and the mixture was extracted using DCM. The organic layer was washed with brine, dried, and concentrated to obtain 2 g of the above compound.

[0158] (Reaction Equation 13) [ka]

[0159] Compound 2h was synthesized in the same manner as compound 1m, except that compound 2e was used instead of compound 1l.

[0160] (Reaction Equation 14) [ka]

[0161] 2 g (43.6 mmol) of the above compound was added to a solution prepared by dissolving 2 h (4.36 mmol) of the above compound and K2CO3 (43.6 mmol) in DMSO, and the temperature was raised to 80°C. After stirring overnight, the temperature was gradually cooled to room temperature. Diethyl ether was added to the reaction mixture to produce a solid, which was separated by vacuum filtration. The solid was washed with water using a 10% aqueous sodium chloride solution, and then dried overnight in a 40°C vacuum oven to obtain compound 2i.

[0162] (Reaction Equation 15) [ka]

[0163] Compound 2i (2.1 mmol) was dissolved in THF, to which 1N NaOH aqueous solution (20 mmol) was added and the mixture was stirred overnight at room temperature. After gradually adding 1N HCl aqueous solution to the reaction mixture, it was extracted using DCM. The organic layer was passed through MgSO4, and the solvent was removed under reduced pressure to obtain compound 2j, which was used in the next reaction without any further purification. Compound 2j (1.0 mmol) was dissolved in DMSO, to which KOH (5.0 mmol) and ECH (epichlorohydrin, 10 mmol) were added and the mixture was stirred at 60°C for 2 hours. After adding distilled water, it was extracted using DCM. The organic layer was washed with brine, dried, and concentrated. The mixture was purified by column chromatography (developing agent: DCM-siRNA) to obtain the substance corresponding to chemical formula B.

[0164] The HRMS analysis results for chemical formula B are as follows: m / z calcd for C 82 H 87 N8O 16 ([M+H] + ), 1439.6235;found, 1439.6236.

[0165] (Synthesis Example 3: Synthesis of a compound represented by chemical formula C) (Reaction Equation 16) [ka]

[0166] Compound 3b was synthesized in the same manner as the synthesis of compound 1c, except that compound 3a was used instead of compound 1b.

[0167] (Reaction Equation 17) [ka]

[0168] Compound 3c was synthesized in the same manner as compound 1e, except that compound 3b was used instead of compound 1c.

[0169] (Reaction Equation 18) [ka]

[0170] Compound 3d was synthesized in the same manner as compound 1g, except that compound 3c was used instead of compound 1e.

[0171] (Reaction Equation 19) [ka]

[0172] Compound 3e was synthesized in the same manner as compound 1i, except that compound 3d was used instead of 1 g of compound 1i.

[0173] (Reaction Equation 20) [ka]

[0174] Compound 3f was synthesized in the same manner as compound 1l, except that compound 3e was used instead of compound 1i.

[0175] (Reaction Equation 21) [ka]

[0176] Compound 3g was synthesized in the same manner as compound 1m, except that compound 3f was used instead of compound 1l.

[0177] (Reaction Equation 22) [ka]

[0178] Compound 3h was synthesized in the same manner as the synthesis of compound 2i, except that the above compound 3g was used instead of compound 2h.

[0179] (Reaction Scheme 23) [Chemical formula]

[0180] Compound corresponding to Chemical formula C was synthesized in the same manner as the synthesis of the substance corresponding to Chemical formula B, except that the above compound 3h was used instead of compound 2i.

[0181] The HRMS analysis results of Chemical formula C are as follows. m / z calcd for C 90 H 103 N8O 20 ([M+H] + )、1615.7283;found、1615.7283.

[0182] (Comparative Synthesis Example 1: Synthesis of the compound represented by Chemical formula D) (Reaction Scheme 24) [Chemical formula]

[0183] Compound 4b was synthesized in the same manner as the synthesis of compound 1c, except that the above compound 4a was used instead of compound 1b.

[0184] (Reaction Scheme 25) [Chemical formula]

[0185] Compound 4c was synthesized in the same manner as the synthesis of compound 1g, except that the above compound 4b was used instead of compound 1e.

[0186] (Reaction Scheme 26) [Chemical formula]

[0187] Compound 4d was synthesized in the same manner as compound 1i, except that compound 4c was used instead of 1g of compound 1i.

[0188] (Reaction Equation 27) [ka]

[0189] Compound 4e was synthesized in the same manner as the synthesis of compound 1l, except that compound 4d was used instead of compound 1i.

[0190] (Reaction Equation 28) [ka]

[0191] Compound 4f was synthesized in the same manner as compound 1m, except that compound 4e was used instead of compound 1l.

[0192] (Reaction Equation 29) [ka]

[0193] The substance corresponding to chemical formula D was synthesized in the same manner as the substance corresponding to chemical formula A, except that compound 4f was used instead of compound 1m.

[0194] The HRMS analysis results for chemical formula D are as follows: m / z calcd for C 78 H 83 N8O 10 ([M+H] + ), 1291.6227;found, 1291.6228.

[0195] (Comparative Synthesis Example 2: Synthesis of the Compound Represented by Chemical Formula E) (Reaction Formula 30)

Chem.

[0196] The above compound 5b was synthesized in the same manner as the synthesis of compound 1c, except that the above compound 5a was used instead of compound 1b.

[0197] (Reaction Formula 31)

Chem.

[0198] The above compound 5d was synthesized in the same manner as the synthesis of compound 1e, except that the above compound 5b was used instead of compound 1c and the above compound 5c was used instead of compound 1d.

[0199] (Reaction Formula 32)

Chem.

[0200] The above compound 5e was synthesized in the same manner as the synthesis of compound 1g, except that the above compound 5d was used instead of compound 1e.

[0201] (Reaction Formula 33)

Chem.

[0202] The above compound 5f was synthesized in the same manner as the synthesis of compound 1i, except that the above compound 5e was used instead of compound 1g.

[0203] (Reaction Formula 34)

Chem.

[0204] Compound 5g was synthesized in the same manner as compound 1l, except that compound 5f was used instead of compound 1i.

[0205] (Reaction Equation 35) [ka]

[0206] Compound 5h was synthesized in the same manner as compound 1m, except that 5g of the above compound was used instead of 1l of compound 1m.

[0207] (Reaction Equation 36) [ka]

[0208] The substance corresponding to chemical formula E was synthesized in the same manner as the substance corresponding to chemical formula A, except that compound 5h was used instead of compound 1m.

[0209] The HRMS analysis results for chemical formula E are as follows: m / z calcd for C 74 H 75 N8O 12 ([M+H] + ), 1267.5499;found, 1267.5499.

[0210] (Comparative synthesis example 3: Synthesis of a compound represented by chemical formula F) (Reaction Equation 37) [ka]

[0211] To a solution of compound 6a (10 mmol) dissolved in DMF (N,N-dimethylformamide), NaH (60% in mineral oil, 15 mmol) was added dropwise at room temperature for 30 minutes. After adding compound 6b (10.5 mmol), the reaction temperature was raised to 90°C and the reaction was carried out overnight. The aqueous layer was extracted using DCM. The organic layer was passed through MgSO4 and concentrated under reduced pressure, and then compound 6c was obtained by column chromatography (developing agent: n-Hex / siRNA).

[0212] (Reaction Equation 38) [ka]

[0213] Compound 6e was synthesized in the same manner as compound 1e, except that compound 6c was used instead of compound 1c and compound 6d was used instead of compound 1d.

[0214] (Reaction Equation 39) [ka]

[0215] Compound 6f was synthesized in the same manner as compound 1i, except that compound 6e was used instead of 1 g of compound 1i.

[0216] (Reaction Equation 40) [ka]

[0217] The substance corresponding to chemical formula F was synthesized in the same manner as the synthesis of compound 1l, except that compound 6f was used instead of compound 1i.

[0218] The HRMS analysis results for chemical formula F are as follows: m / z calcd for C 84 H 95 N8O12 ([M+H] + ), 1407.7064;found, 1407.7065.

[0219] (Comparative synthesis example 4: Synthesis of a compound represented by chemical formula G) (Reaction Equation 41) [ka]

[0220] Compound 7b was synthesized in the same manner as the synthesis of compound 1e, except that compound 6c was used instead of compound 1c and compound 7a was used instead of compound 1d.

[0221] (Reaction Equation 42) [ka]

[0222] Compound 7c was synthesized in the same manner as compound 1i, except that compound 7b was used instead of 1 g of compound 1i.

[0223] (Reaction Equation 43) [ka]

[0224] The substance corresponding to chemical formula G was synthesized in the same manner as the synthesis of compound 1l, except that compound 7c was used instead of compound 1i.

[0225] The HRMS analysis results for chemical formula G are as follows: m / z calcd for C 88 H 103 N8O 14 ([M+H] + ), 1495.7588;found, 1495.7588.

[0226] (Synthesis of photosensitive resin composition) <Example 1> The components mentioned below were mixed in the composition shown in Table 1 to produce the photosensitive resin composition according to Example 1.

[0227] Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 2 hours. Then, the binder resin and photopolymerizable monomer were added and stirred at room temperature for another 2 hours. Next, the compound produced in Synthesis Example 4 (represented by chemical formula A) was added as a colorant to the resulting reaction product and stirred at room temperature for 1 hour. Finally, the product was filtered three times to remove impurities, thereby producing a photosensitive resin composition.

[0228] [Table 1] (Unit: weight %)

[0229] <Example 2> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Synthesis Example 2 (the compound represented by chemical formula B) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0230] <Example 3> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Synthesis Example 3 (the compound represented by chemical formula C) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0231] <Comparative Example 1> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Comparative Synthesis Example 1 (the compound represented by chemical formula D) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0232] <Comparative Example 2> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Comparative Synthesis Example 2 (the compound represented by chemical formula E) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0233] <Comparative Example 3> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Comparative Synthesis Example 3 (the compound represented by chemical formula F) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0234] <Comparative Example 4> A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Comparative Synthesis Example 4 (the compound represented by chemical formula G) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0235] <Evaluation: Measurement of developability of the composition> The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were spin-coated onto silicon wafers to a thickness of 0.6 μm, and then pre-baked on a 100°C hot plate for 3 minutes. The formed thin films were exposed to 200 mJ / cm² using a KrF scanner exposure machine (248 nm). 2 Exposure was performed. Next, the unexposed areas were removed with 0.2% TMAH (tetramethylammonium hydroxide) in a developing machine (SVS, SSP-200) to form a colored pattern. After that, it was post-baked on a 230°C hot plate for 5 minutes.

[0236] The developability of the obtained colored patterns was evaluated by checking for pattern formation and surrounding residue using Hitachi's CD-SEM (scanning electron microscopy), and the results are shown in Table 2 below.

[0237] [Table 2] (Category) ◎: No residue; ○: Slight residue present only around the pattern; △: Residue present throughout the entire area; X: Not developed.

[0238] Table 2 confirms that the photosensitive resin compositions of Examples 1 to 3, which contain a high content of the core-shell compound according to one embodiment, exhibit excellent developability and are highly suitable for use in CMOS image sensors or OLEDos elements.

[0239] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented in various ways within the scope of the claims, the detailed description of the invention, and the attached drawings, and these also naturally fall within the scope of the present invention.

Claims

1. The core represented by the following chemical formula 1 and The shell surrounding the aforementioned core is represented by the following chemical formula 2. Core-shell compounds consisting of: [Chemical formula 1] 【Chemistry 1】 [Chemical formula 2] 【Chemistry 2】 In the above chemical formulas 1 and 2, R １ It is a thermosetting group, R ２ and R ３ Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group. L １ and L ６ Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or represented by the following chemical formula L, however L １ and L ６ At least one of them is represented by the following chemical formula L, [Chemical formula L] 【Transformation 3】 In the above chemical formula L, L ７ This is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. m is an integer between 2 and 10. L ２ 、 L ４ 、 L ａ 、 and L ｂ are each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, L ３ These are single bonds or ester groups (*-C(=O)O-* or *-OC(=O)-*), L ５ This is a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. n is an integer greater than or equal to 2.

2. The core-shell compound according to claim 1, wherein the thermosetting group includes a substituted or unsubstituted epoxy group, a substituted or unsubstituted oxetane group, or a combination thereof.

3. The aforementioned R １ It is a thermosetting group, The aforementioned R ２ and R ３ Each of these is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Said L １ and L ５ Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. Said L ２ ~L ４ Each of them is an independent single bond, Said L ６ The core-shell compound according to claim 1, wherein is represented by the chemical formula L.

4. The aforementioned R １ It is a thermosetting group, The aforementioned R ２ and R ３ Each of these is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Said L １ It is represented by the above chemical formula L, Said L ２ , L ４ , and L ６ Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. Said L ３ is an ester group (*-C(=O)O-* or *-OC(=O)-*), Said L ５ The core-shell compound according to claim 1, wherein is a single bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms.

5. The aforementioned R １ It is a thermosetting group, The aforementioned R ２ and R ３ Each of these is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Said L １ and L ６ Each of these is independently represented by the aforementioned chemical formula L, Said L ２ and L ４ Each of these is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. Said L ３ is an ester group (*-C(=O)O-* or *-OC(=O)-*), Said L ５ The core-shell compound according to claim 1, wherein is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

6. The core-shell compound according to claim 1, wherein the core represented by chemical formula 1 has a maximum absorption wavelength in the range of 610 nm to 640 nm.

7. The core-shell compound according to claim 1, wherein the shell represented by chemical formula 2 is represented by the following chemical formula 2-1. [Chemical formula 2-1] 【Chemistry 4】

8. The core-shell compound according to claim 1, wherein the core-shell compound is represented by any one of the following chemical formulas A to C. [Chemical formula A] 【Transformation 5】 [Chemical formula B] 【Transformation 6】 [Chemical formula C] 【Transformation 7】

9. The core-shell compound according to claim 1, wherein the compound is a green dye.

10. A photosensitive resin composition comprising the compound according to any one of claims 1 to 9.

11. The photosensitive resin composition according to claim 10, further comprising a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent.

12. The photosensitive resin composition according to claim 10, wherein the photosensitive resin composition is for use in a CMOS image sensor.

13. A photosensitive resin film manufactured using the photosensitive resin composition of claim 10.

14. A color filter comprising a photosensitive resin film according to claim 13.

15. A CMOS image sensor including the color filter of claim 14.

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