Core-shell compounds, photosensitive resin compositions containing the same, photosensitive resin films, color filters, and CMOS image sensors.

Abstract

One embodiment of the present invention provides a core-shell compound that constitutes a green pixel in a color filter for a CMOS image sensor. Another embodiment of the present invention provides a photosensitive resin composition comprising the compound. Yet another embodiment of the present invention provides a photosensitive resin film manufactured using the photosensitive resin composition. [Solution] A core-shell compound, a photosensitive resin composition containing the same, 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 are provided.

Description

Technical Field

[0001] The present invention relates to a core-shell compound, a photosensitive resin composition containing the same, a photosensitive resin film produced using the photosensitive resin composition, a color filter containing the photosensitive resin film, and a CMOS image sensor containing the color filter.

Background Art

[0002] Recently, with the rapid development of advanced information and communication processing technologies and the entire electronics industry, there is a need for next-generation detection devices capable of quickly transmitting and receiving large amounts of information, and the development of new concept elements and systems is required. In particular, as video processing of mobile terminals has emerged, the technology of ultra-small and ultra-power-saving video image sensors has been rapidly accelerating around existing CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor).

[0003] An image sensor is a semiconductor that can convert photons into electrons for display on a display or storage in a storage device, and is composed of a light-receiving element that converts a light-receiving signal into an electrical signal, a pixel circuit portion that amplifies and compresses the converted electrical signal, and an ASIC portion that processes the analog signal pre-processed in this way into a digital signal to process an image signal, and there are 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 at 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 processability during pattern manufacturing compared to pigments. In particular, problems arise 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 in combination is relatively low, making it difficult to improve the developability of dyes. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 8642014 [Overview of the project] [Problems that the invention aims to solve]

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

[0008] Another embodiment of the present invention provides a photosensitive resin composition comprising a compound.

[0009] Yet another embodiment of the present invention provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0010] Yet another embodiment of the present invention provides a color filter comprising a photosensitive resin film.

[0011] Yet another embodiment of the present invention 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. [Chemical formula 1] [ka] [Chemical formula 2] [ka] 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 substituted or unsubstituted C1-C20 alkyl group, an unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group. R 2 and R 3 are either linked to each other or condensed to form a ring, or do not form a ring, L 1 and L 4 are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or represented by the following chemical formula L, provided that not all of L 1 ~L 4 are simultaneously single bonds, [Chemical formula L] [Chemical formula] In the above chemical formula L, L 5 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, n is an integer from 1 to 10, L a and L b are each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R a is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or * -C(=O)OR 4 (R 4 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R b ~R e are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, provided that not all of R a ~R e are simultaneously hydrogen atoms, m1 is an integer from 0 to 3, m2 is an integer from 1 to 10. [[ID=六十五]]

[0013] [[ID=六十六]] [[ID=六十七]] [[ID=六十八]]The thermosetting group can include a substituted or unsubstituted epoxy group, a substituted or unsubstituted oxetane group, or a combination thereof.[[ID=六十九]]

[0014] [[ID=七十]] In chemical formula 2, m1 is an integer of 0, and R b ~R e Each of these may independently be a halogen atom.

[0015] In chemical formula 1, L 1 L is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. 2 ~L 4 Each of these can be independent and may even be a single bond.

[0016] In chemical formula 1, R 2 and R 3 These can be linked together or condensed to form substituted or unsubstituted cycloalkane rings or substituted or unsubstituted benzene rings.

[0017] The core represented by chemical formula 1 can have a maximum absorption wavelength in the range of 660 nm to 680 nm.

[0018] The shell represented by chemical formula 2 is shown in chemical formula 2-1 below. [Chemical formula 2-1] [ka] In the above chemical formula 2-1, R a is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or * -C(=O)OR 4 (R 4 (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) R b ~R e Each of these is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. However, R a ~R e All of them are not hydrogen atoms at the same time, m1 is an integer between 0 and 3.

[0019] Core-shell compounds are represented by one of the following chemical formulas A through E. [Chemical formula A] [ka] [Chemical formula B] [ka] [Chemical formula C] [ka] [Chemical formula D] [ka] [Chemical formula E] [ka] Core shell compounds may also be used as green dyes.

[0020] Another embodiment provides a photosensitive resin composition comprising a core-shell compound.

[0021] The photosensitive resin composition may further comprise a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent.

[0022] The photosensitive resin composition may also be used for CMOS image sensors.

[0023] Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0024] Another embodiment provides a color filter including a photosensitive resin film.

[0025] Another embodiment provides a CMOS image sensor including a color filter.

[0026] Other specific aspects of the present invention are included in the following detailed description. [Effects of the Invention]

[0027] A core-shell compound according to one embodiment includes a shell containing a halogen group, alkyl group, or ester group as a substituent, and the absorption region shifts to the long-wavelength region, making it easy to control transmission in the near-infrared region. A photosensitive resin composition containing this as a dye can provide a green color filter for CMOS image sensors or an OLEDos(on silicon) element with excellent color characteristics. [Brief explanation of the drawing]

[0028] [Figure 1] This graph shows the absorbance of compounds synthesized in Synthesis Example 1, Synthesis Example 2, and Comparative Synthesis Example 1. [Modes for carrying out the invention]

[0029] 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; the present invention is defined solely within the scope of the claims described later.

[0030] Unless otherwise specified herein, “substituted” or “substituted” means that one or more hydrogen atoms in the functional group of the present invention 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 202This means that the group is substituted with one or more substituents selected from the group consisting of the following: (which are identical or different from each other, and are each independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

[0031] 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.

[0032] 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.

[0033] Unless otherwise defined herein, “combination” means mixing or copolymerization. “Copolymerization” means block copolymerization or random copolymerization, and “copolymer” means block copolymerization or random copolymerization.

[0034] 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.

[0035] Furthermore, unless otherwise defined herein, "*" means a portion linked to the same or different atoms or chemical formulas.

[0036] 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. [Chemical formula 1] [ka] [Chemical formula 2] [ka] 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 substituted or unsubstituted C1-C20 alkyl group, an unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group. R 2 and R 3 They are linked to each other or condense to form a ring, or do not form a ring. L 1 and L 4 Each of these is independently represented by a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or by the following chemical formula L, where L 1 ~L 4 Not all of them are single bonds at the same time, [Chemical formula L] [ka] In the above chemical formula L, L 5 This is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. n is an integer from 1 to 10. L a and L b Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. R a is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or * -C(=O)OR 4 (R 4 (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) R b ~R e Each of these is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. However, R a ~R e All of them are not hydrogen atoms at the same time, m1 is an integer between 0 and 3. m2 is an integer between 1 and 10.

[0037] Liquid crystal displays (LCDs), a type of display device, have advantages such as being lightweight, thin, inexpensive, low-power, and having excellent compatibility with integrated circuits, leading to an expansion of their application range 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, and an upper substrate on which an active circuit section consisting of a liquid crystal layer, thin-film transistors, and an energy storage capacitor layer, and 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 with multiple colors [usually the three primary colors of red (R), green (G), and blue (B)] to form each pixel, are sequentially stacked. 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: coating a photopolymerizable composition containing a colorant onto a transparent substrate provided with a black matrix, exposing the pattern in the form to be formed, removing the unexposed areas with a solvent, and then thermally curing the mixture. The colored photosensitive resin compositions used in the manufacture of color filters by the pigment dispersion method generally contain alkali-soluble resins, photopolymerizable monomers, photopolymerization initiators, epoxy resins, solvents, and other additives. Pigment dispersion methods with the above characteristics are actively applied to the manufacture of LCDs in mobile phones, laptops, monitors, TVs, and other devices.

[0038] An image sensor refers to a component used to generate images in mobile phone cameras and digital still cameras (DSCs). Based on their 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 employ color filters on their light-receiving elements, each containing filter segments for the additively mixed primary colors of red, green, and blue, to achieve color separation. 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. Therefore, increasing resolution and reducing residual image are crucial factors affecting the performance of the sensor.

[0039] On the other hand, color filters manufactured from pigment-type photosensitive resin compositions suffer from color mixing problems and limitations in thin-film thinning, stemming from the size of the pigment particles. 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 long been made to improve resolution by introducing dyes that do not form particles instead of pigments and manufacturing photosensitive resin compositions suitable for dyes.

[0040] This invention relates to a green dye to be used in color filters for CMOS image sensors or OLEDos (OLED on silicon) color filters. As pixel size decreases, there are limitations to manufacturing fine patterns using pigments, and the development of dyes is necessary to compensate for this. Compared to pigments, dyes have problems in terms of processability during pattern manufacturing, and in particular they are very inferior in terms of developability, making it very difficult to form fine patterns after curing and heat processes. Furthermore, if the dye, which is a coloring agent, is contained in only a small amount relative to the total amount of the composition, it is not a big problem even if the developability of the dye itself is slightly inferior. However, in the case of photosensitive resin compositions for CMOS image sensors or OLEDos (OLED on silicon), the dye is contained in excess (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 that has excellent developability on its own.

[0041] After numerous trials and errors, the inventors of the present invention synthesized a core-shell compound by introducing a thermosetting group to the end of a squarylium-based compound forming the core, and ensuring that the shell surrounding the core always contains a specific substituent. They confirmed that the core-shell compound according to this embodiment possesses an intramolecular encapsulation structure, i.e., the specific shell structure causes the absorption region to shift from 660 nm to 680 nm (red shift, bathochromic shift). Therefore, the compound according to this embodiment is very suitable for use in CMOS image sensors or as a green color filter for OLEDos (OLED on silicon) because transmission in the near-infrared region is easily controlled.

[0042] In other words, the present invention aims to provide a squarylium-based dye for controlling transmission in the near-infrared region (650 nm to 950 nm).

[0043] While metal phthalocyanine pigments are commonly used to control the wavelength range of 650nm to 700nm during the manufacture of green color filters, the inventors spent considerable time and effort developing a dye structure optimized for improving transmittance in the main transmission region (500nm to 600nm), and finally succeeded in developing this core-shell structured dye.

[0044] For example, the thermosetting group may include a substituted or unsubstituted epoxy group, a substituted or unsubstituted oxetane group, or a combination thereof. For example, it may be an epoxy group substituted with a substituted or unsubstituted oxetane group, or an oxetane group substituted with a substituted or unsubstituted epoxy group.

[0045] The thermosetting group may be further substituted with alkyl groups or the like.

[0046] For example, in a compound represented by chemical formula 1, L 1 L is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. 2 ~L 4 Each of these may independently be a compound with a single bond.

[0047] For example, in a compound represented by chemical formula 1, R 2 and R 3 These may be compounds that are linked to each other or condensed to form substituted or unsubstituted cycloalkane rings or substituted or unsubstituted benzene rings.

[0048] For example, in the compound represented by chemical formula 2, m1 is an integer of 0, and R b ~R e Each of these may independently be a compound containing a halogen atom.

[0049] For example, the 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 thermosetting groups at their ends are structurally difficult to synthesize (low yield), and even if their synthesis is successful, applying them to actual production lines would be costly and undesirable from an economic standpoint.

[0050] Furthermore, the core represented by Chemical Formula 1 is superior in terms of developability when it has 6 terminal thermosetting groups (i.e., 3 molecules of the core represented by Chemical Formula 1) compared to when it has 4 terminal thermosetting groups (i.e., 2 molecules of the core represented by Chemical Formula 1), and is superior in terms of chemical resistance when it has 4 terminal thermosetting groups (i.e., 2 molecules of the core represented by Chemical Formula 1) compared to when it has 2 terminal thermosetting groups (i.e., 1 molecule of the core represented by Chemical Formula 1). In other words, considering only the chemical resistance of the compound, it is preferable for the core structure represented by Chemical Formula 1 to have 4 terminal thermosetting groups (i.e., 2 molecules of the core represented by Chemical Formula 1) rather than 2 terminal thermosetting groups (i.e., 1 molecule of the core represented by Chemical Formula 1), and it is preferable for it to have 6 terminal thermosetting groups (i.e., 3 molecules of the core represented by Chemical Formula 1) rather than 4 terminal thermosetting groups (i.e., 2 molecules of the core represented by Chemical Formula 1). However, when considering the structure represented by Chemical Formula 1, it is most preferable in terms of synthesis to have 2 terminal thermosetting groups, one at each end.

[0051] Furthermore, the shell represented by chemical formula 2 has a substituent R a R b ~R e Being located in this position is advantageous for realizing the red shift effect to the long wavelength region, and also R b ~R e In both cases, substitution with the same substituent is advantageous for achieving the red shift effect in the long-wavelength region.

[0052] For example, a core represented by chemical formula 1 can have a maximum absorption wavelength in the 660nm to 680nm range. 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 660nm to 680nm range, it is difficult to control transmission in the near-infrared region, making it unsuitable for use as a green photosensitive resin composition for CMOS image sensors or OLEDos (OLED on silicon).

[0053] The shell represented by chemical formula 2 is represented by the following chemical formula 2-1. [Chemical formula 2-1] [ka] In the above chemical formula 2-1, R a is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or * -C(=O)OR 4 (R 4 (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) R b ~R e Each of these is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. However, R a ~R e All of them are not hydrogen atoms at the same time, m1 is an integer between 0 and 3.

[0054] For example, a core-shell compound can be represented by any one of the following chemical formulas A to E, but is not necessarily limited to these. [Chemical formula A] [ka] The core and shell that make up chemical formula A are shown below. [ka] [ka] [Chemical formula B] [ka] The core and shell that make up chemical formula B are shown below. [ka] [ka] [Chemical formula C] [ka] The core and shell that make up chemical formula C are shown below. [ka] [ka] [Chemical formula D] [ka] The core and shell that make up chemical formula D are shown below. [ka] [ka] [Chemical formula E] [ka] The core and shell that make up chemical formula E are shown below. [ka] [ka]

[0055] For example, the core-shell compound may be a green dye.

[0056] According to another embodiment, a photosensitive resin composition comprising a core-shell compound according to one embodiment is provided.

[0057] 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.

[0058] 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, the developability can be maximized. That is, the core-shell compound according to one embodiment may be a hybrid dye used together with a pigment.

[0059] For example, the pigments may further include yellow pigments, green pigments, or combinations thereof.

[0060] 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.

[0061] Green pigments include CI Pigment Green 36, CI Pigment Green 58, and CI Pigment Green 59 in the Color Index, and these can be used individually or in mixtures of two or more.

[0062] The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

[0063] A pigment dispersion may contain solid pigment components, a solvent, and a dispersant for uniformly dispersing the pigment within the solvent.

[0064] 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.

[0065] 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.

[0066] Examples of commercially available dispersants include BYK's DISPERBYK(registered trademark)-101, DISPERBYK(registered trademark)-130, DISPERBYK(registered trademark)-140, DISPERBYK(registered trademark)-160, DISPERBYK(registered trademark)-161, DISPERBYK(registered trademark)-162, DISPERBYK(registered trademark)-163, DISPERBYK(registered trademark)-164, DISPERBYK(registered trademark)-165, DISPERBYK(registered trademark)-166, and DISPERBYK (Registered Trademark)-170, DISPERBYK(Registered Trademark)-171, DISPERBYK(Registered Trademark)-182, DISPERBYK(Registered Trademark)-2000, DISPERBYK(Registered Trademark)-2001, etc.; EFKA(Registered Trademark)-47, EFKA(Registered Trademark)-47EA, EFKA(Registered Trademark)-48, EFKA(Registered Trademark)-49, EFKA(Registered Trademark)-100, EFKA(Registered Trademark)-400, EFKA(Registered Trademark)-450, etc. from EFKA Chemicals; Solsperse(Registered Trademark) from Zeneka. Examples include 5000, Solsperse® 12000, Solsperse® 13240, Solsperse® 13940, Solsperse® 17000, Solsperse® 20000, Solsperse® 24000GR, Solsperse® 27000, Solsperse® 28000, etc.; or Ajinomoto's PB711, PB821, etc.

[0067] The dispersant may be included in an amount of 1% to 20% by weight relative to the total volume of the pigment dispersion. When the dispersant is included within the above range, an appropriate viscosity can be maintained, the dispersibility of the photosensitive resin composition is excellent, and thereby the optical, physical, and chemical quality can be maintained when the product is applied.

[0068] 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.

[0069] 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 results in excellent color reproduction and light-to-dark ratio.

[0070] The binder resin may be an acrylic binder resin.

[0071] The acrylic binder 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.

[0072] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0073] 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.

[0074] Examples of the second ethylenically unsaturated monomer 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.

[0075] 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.

[0076] The weight-average molecular weight of the binder resin may be between 3,000 g / mol and 150,000 g / mol, for example, between 5,000 g / mol and 50,000 g / mol, or for example, between 20,000 g / mol and 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 superior adhesion to the substrate during the manufacture of color filters.

[0077] The acid value of the binder resin may be between 15 mg KOH / g and 60 mg KOH / g, for example, between 20 mg KOH / g and 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.

[0078] 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, improved crosslinking properties, and excellent surface smoothness can be obtained during the manufacture of the color filter.

[0079] The photopolymerizable monomer can be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0080] 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.

[0081] 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.

[0082] Examples of commercially available photopolymerizable monomers are as follows: Examples of monofunctional esters of (meth)acrylic acid include Aronix® M-101, M-111, and M-114 from Toagosei Co., Ltd.; KAYARAD® TC-110S and TC-120S from Nippon Kayaku Co., Ltd.; and V-158® and V-2311® from Osaka Organic Chemical Industry Co., Ltd. Examples of difunctional esters of (meth)acrylic acid include Aronix® M-210, M-240, and M-6200 from Toagosei Co., Ltd.; KAYARAD® HDDA, HX-220, and R-604 from Nippon Kayaku Co., Ltd.; and V-260®, V-312®, and V-335 HP® from Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include Aronix® M-309, M-400, M-405, M-450, M-710, M-8030, and M-8060 from Toagosei Co., Ltd.; KAYARAD® TMPTA, DPCA-20, -30, -60, and -120 from Nippon Kayaku Co., Ltd.; and V-295®, -300®, -360®, -GPT®, -3PA®, and -400® from Osaka Organic Chemical Industry Co., Ltd. The products can be used individually or in combination of two or more.

[0083] Photopolymerizable monomers can also be treated with acid anhydrides before use to impart better developability.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0089] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0090] 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.

[0091] 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.

[0092] In addition to the compound, other photopolymerization initiators that can be used include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and fluorene compounds.

[0093] Photopolymerization initiators can also be used in conjunction with photosensitizers, which absorb light, become excited, and then transfer that energy to initiate a chemical reaction.

[0094] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0095] 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, excellent reliability can be obtained, the pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiators can be prevented.

[0096] The solvent can be a substance that is compatible with and does not react with the core-shell compound, pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, and pigment according to one embodiment.

[0097] 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.

[0098] Among these, considering compatibility and reactivity, preferably, 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.

[0099] The solvent may be included in the remainder of the total amount of the photosensitive resin composition, for example, 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 processability during the manufacture of the color filter.

[0100] Another embodiment of the photosensitive resin composition may further contain an epoxy compound to improve adhesion to the substrate and other properties.

[0101] Examples of epoxy compounds include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0102] 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.

[0103] Furthermore, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a carboxyl group, methacryloyl group, isocyanate group, or epoxy group in order to improve adhesion to the substrate.

[0104] 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.

[0105] The silane coupling agent may be included in an amount of 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.

[0106] Furthermore, the photosensitive resin composition may further contain a surfactant as needed to improve coating properties and prevent the formation of defects.

[0107] Examples of surfactants that can be used include BM-1000 (registered trademark), BM-1100 (registered trademark) from BM Chemie, etc.; Megafac (registered trademark) F 142D, F 172, F 173, F 183, etc. from DIC Corporation; Florard FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark) from 3M Japan Limited, etc.; Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark) from Asahi Glass Co., Ltd.; and fluorine-based surfactants that are commercially available under names such as DOWSIL (registered trademark) SH-28PA, -190, -193, SZ-6032, SF-8428 from Dow / Toray Industries, Inc.

[0108] The surfactant can be used in an amount of 0.001 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.

[0109] Furthermore, the photosensitive resin composition may also contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0110] Furthermore, according to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to one embodiment is provided.

[0111] In yet another embodiment, a color filter including a photosensitive resin film is provided.

[0112] The process for forming a pattern within the color filter is as follows:

[0113] 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 to light; 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 conditions of the process are widely known in the art, a detailed explanation is omitted in this specification.

[0114] Another embodiment provides a CMOS image sensor or OLEDos(on silicon) element including a color filter. [Examples]

[0115] 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.

[0116] (Synthesis of compounds) (Synthesis Example 1: Synthesis of a compound represented by chemical formula A) (Reaction Equation 1) [ka]

[0117] 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, concentrated under reduced pressure, and then compound 1c was obtained using column chromatography (eluent: n-Hex / siRNA).

[0118] (Reaction Equation 2) [ka]

[0119] Compound 1c (10 mmol) and compound 1d (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 mixture was refluxed overnight. After cooling to room temperature, the organic layer was separated. The organic layer was passed through MgSO4 and concentrated under reduced pressure, and compound 1e was obtained by column chromatography (eluent: n-Hex / SiO).

[0120] (Reaction Equation 3) [ka]

[0121] Compound 1e (10 mmol) and compound 1f (7 mmol) 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. The resulting solid was obtained by vacuum filtration, and then washed with n-hexane and dried to obtain 1 g of the compound.

[0122] (Reaction Equation 4) [ka] The core and shell that make up compound 1j are shown below. [ka] [ka]

[0123] A solution of 1 g (10 mmol) of the compound dissolved in chloroform was cooled to 0°C, and two solutions were prepared: (Solution A) compound 1h (30 mmol) and triethylamine (60 mmol) dissolved in chloroform, and (Solution B) compound 1i (30 mmol) dissolved in chloroform. The two solutions were slowly added to the 1 g solution of the compound in the order of Solution A and Solution B, and the mixture was 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 step was repeated two more times. The substance corresponding to compound 1j was obtained by purification using column chromatography (eluent: DCM-siRNA).

[0124] (Reaction Equation 5) [ka] The core and shell that make up compound 1k are shown below. [ka] [ka]

[0125] 1 joule (10 mmol) of compound was dissolved in THF, and 1 M TBAF (tetrabutylammonium fluoride, 22 mmol) was added to the solution and stirred at room temperature for 2 hours. After confirming that all of compound 1 joule had been consumed using thin-layer chromatography, the solvent was removed under reduced pressure. Acetone / H2O (v / v=1 / 1) was added and the mixture was stirred at 0°C for 30 minutes, after which the resulting solid was separated by vacuum filtration. After washing with distilled water, compound 1 k was dried overnight in a vacuum oven at 40°C to obtain compound 1 k.

[0126] (Reaction Equation 6) [ka] Chemical formula A The core and shell that make up chemical formula A are shown below. [ka] [ka]

[0127] A solution of 1k (10 mmol) of compound was dissolved in DMSO (dimethyl sulfoxide), to which KOH (50 mmol) and ECH (epichlorohydrin, 100 mmol) were added, and the mixture was stirred at 60°C for 2 hours. After adding distilled water, the mixture was extracted using DCM. The organic layer was washed with brine, then dried and concentrated. The mixture was purified using column chromatography (developing agent: DCM-siRNA) to obtain the substance corresponding to chemical formula A.

[0128] The HRMS analysis results for chemical formula A are as follows: m / z calcd for C78H75F8N8O10([M+H] + ), 1435.5473;found, 1435.5473.

[0129] (Synthesis Example 2: Synthesis of the compound represented by chemical formula B) (Reaction Equation 7) [ka] The core and shell that make up compound 2b are shown below. [ka] [ka]

[0130] Compound 2b was synthesized in the same manner as compound 1j, except that compound 2a was used instead of compound 1i.

[0131] (Reaction Equation 8) [ka] The core and shell that make up compound 2c are shown below. [ka] [ka]

[0132] Compound 2c was synthesized in the same manner as compound 1k, except that compound 2b was used instead of compound 1j.

[0133] (Reaction Equation 9) [ka] Chemical formula B The core and shell that make up chemical formula B are shown below. [ka] [ka]

[0134] Except for using compound 2c instead of compound 1k, the substance corresponding to chemical formula B was synthesized using the same method as the substance corresponding to chemical formula A.

[0135] The HRMS analysis results of Chemical Formula B are as follows. m / z calcd for C78H75Cl8N8O10([M+H] + )、1563.3109;found、1563.3108。

[0136] (Synthesis Example 3: Synthesis of the compound represented by Chemical Formula C) (Reaction Formula 10)

Chemical Structure

[0137] Compound 3b was synthesized in the same manner as the synthesis of Compound 1c, except that Compound 3a was used instead of Compound 1b.

[0138] (Reaction Formula 11)

Chemical Structure

[0139] Compound 3c was synthesized in the same manner as the synthesis of Compound 1e, except that Compound 3b was used instead of Compound 1c.

[0140] (Reaction Formula 12)

Chemical Structure

[0141] Compound 3d was synthesized in the same manner as the synthesis of Compound 1g, except that Compound 3c was used instead of Compound 1e.

[0142] (Reaction Formula 13)

Chemical Structure

Chemical Structure

Chem.

[0143] Compound 3e was synthesized in the same manner as compound 1j, except that compound 3d was used instead of compound 1g.

[0144] (Reaction Scheme 14)

Chem.

Chem.

Chem.

[0145] Compound 3f was synthesized in the same manner as compound 1k, except that compound 3e was used instead of compound 1j.

[0146] (Reaction Scheme 15)

Chem.

Chem.

Chem.

[0147] Except for using compound 3f instead of compound 1k, the substance corresponding to chemical formula C was synthesized using the same method as the substance corresponding to chemical formula A.

[0148] The HRMS analysis results for chemical formula C are as follows: m / z calcd for C74H67F8N8O10([M+H] + ), 1379.4847;found, 1379.4847.

[0149] (Synthesis Example 4: Synthesis of a compound represented by chemical formula D) (Reaction Equation 16) [ka]

[0150] Compound 4b was synthesized in the same manner as compound 1e, except that compound 4a was used instead of compound 1c.

[0151] (Reaction Equation 17) [ka]

[0152] Compound 4c was synthesized in the same manner as compound 1g, except that compound 4b was used instead of compound 1e.

[0153] (Reaction Equation 18) [ka] The core and shell that make up compound 4d are shown below. [ka] [ka]

[0154] Compound 4d was synthesized in the same manner as compound 1j, except that compound 4c was used instead of compound 1g.

[0155] (Reaction Equation 19) [ka] The core and shell that make up compound 4e are shown below. [ka] [ka]

[0156] Compound 4e was synthesized in the same manner as compound 1k, except that compound 4d was used instead of compound 1j.

[0157] (Reaction Equation 20) [ka] Chemical formula D The core and shell that make up chemical formula D are shown below. [ka] [ka]

[0158] Except for using compound 4e instead of compound 1k, the substance corresponding to chemical formula D was synthesized using the same method as the substance corresponding to chemical formula A.

[0159] The HRMS analysis results for chemical formula D are as follows: m / z calcd for C76H55F8N8O10([M+H] + ), 1391.3908;found, 1391.3908.

[0160] (Synthesis Example 5: Synthesis of a compound represented by chemical formula E) (Reaction Equation 21) [ka]

[0161] Compound 5b was synthesized in the same manner as compound 1c, except that compound 5a was used instead of compound 1b.

[0162] (Reaction Equation 22) [ka]

[0163] Compound 5c was synthesized in the same manner as compound 1e, except that compound 5b was used instead of compound 1c.

[0164] (Reaction Equation 23) [ka]

[0165] Compound 5d was synthesized in the same manner as compound 1g, except that compound 5c was used instead of compound 1e.

[0166] (Reaction Equation 24) [ka] The core and shell that make up compound 5e are shown below. [ka] [ka]

[0167] Compound 5e was synthesized in the same manner as compound 1j, except that compound 5d was used instead of compound 1g.

[0168] (Reaction Equation 25) [ka] The core and shell that make up compound 5f are shown below. [ka] [ka]

[0169] Compound 5f was synthesized in the same manner as compound 1k, except that compound 5e was used instead of compound 1j.

[0170] (Reaction Equation 26) [ka] Chemical formula E The core and shell that make up chemical formula E are shown below. [ka] [ka]

[0171] Except for using compound 5f instead of compound 1k, the substance corresponding to chemical formula E was synthesized using the same method as the substance corresponding to chemical formula A.

[0172] The HRMS analysis results for chemical formula E are as follows: m / z calcd for C76H67F8N8O10([M+H] + ), 1403.4847;found, 1403.4848.

[0173] (Comparative synthesis example 1: Synthesis of a compound represented by chemical formula F) (Reaction Equation 27) [ka] The core and shell that make up compound 6b are shown below. [ka] [ka]

[0174] Compound 6b was synthesized in the same manner as compound 1j, except that compound 6a was used instead of compound 1i.

[0175] (Reaction Equation 28) [ka] The core and shell that make up compound 6c are shown below. [ka] [ka]

[0176] Compound 6c was synthesized in the same manner as compound 1k, except that compound 6b was used instead of compound 1j.

[0177] (Reaction Equation 29) [ka] Chemical formula F The core and shell that make up chemical formula F are shown below. [ka] [ka]

[0178] Except for using compound 6c instead of compound 1k, the substance corresponding to chemical formula F was synthesized using the same method as the substance corresponding to chemical formula A.

[0179] The HRMS analysis results for chemical formula F are as follows: m / z calcd for C78H83N8O10([M+H] + ), 1291.6227;found, 1291.6228.

[0180] (Comparative synthesis example 2: Synthesis of a compound represented by chemical formula G) (Reaction Equation 30) [ka]

[0181] Compound 7a (10 mmol) was dissolved in MeOH along with tin(II) chloride dehydrate (4 mmol) and compound 5b. PMHS (polymethylhydrosiloxane, 15 mmol) was added to this solution, and the mixture was stirred overnight at 60°C. Thin-layer chromatography was used to confirm that all of compound 7a had been consumed, and by-products were removed by vacuum filtration. Distilled water was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. The resulting solid was separated by vacuum filtration. After washing with distilled water, compound 7c was obtained by drying overnight in a vacuum oven at 40°C.

[0182] (Reaction Equation 31) [ka]

[0183] Compounds 7c (10 mmol) and 7d (15 mmol) were dissolved in DMF with Cs2CO3 (20 mmol) and stirred overnight at 80°C. After adding distilled water, the mixture was extracted with SiO2. The organic layer was washed with brine, dried, and concentrated, and compound 7e was obtained by column chromatography (eluent: n-Hex / SiO2).

[0184] (Reaction Equation 32) [ka]

[0185] Compound 7f (50 mmol) was added dropwise at 0°C to a solution of compound 7e (10 mmol) and TEA (trimethylamine, 50 mmol) dissolved in DCM. After adding all of compound 7f, the mixture was stirred at room temperature for 2 hours. The TEA-HCl salt was removed by vacuum filtration, and the organic layer was washed with 1 N HCl aqueous solution, then dried and concentrated. 7 g of compound was obtained by column chromatography (eluent: n-Hex / siRNA).

[0186] (Reaction Equation 33) [ka]

[0187] Compound 7i was synthesized in the same manner as compound 1g, except that compound 7g was used instead of compound 1e.

[0188] (Reaction Equation 34) [ka] chemical formula G The core and shell that make up chemical formula G are shown below. [ka] [ka]

[0189] The substance corresponding to chemical formula G was synthesized using the same method as the synthesis of compound 1j, except that compound 7i was used instead of compound 1g.

[0190] The HRMS analysis results for chemical formula G are as follows: m / z calcd for C88H83F8N8O16([M+H] + ), 1659.5794;found, 1659.5795.

[0191] (Comparative synthesis example 3: Synthesis of compounds represented by chemical formula H) (Reaction Equation 35) [ka]

[0192] To a solution of compound 8a (10 mmol) and compound 8b (10 mmol) dissolved in DMF, K2CO3 (10 mmol) was added dropwise over 2 hours. The mixture was then heated to 80°C and stirred for 12 hours. The reaction mixture was added to distilled water at 0°C to form a precipitate, which was separated by vacuum filtration. After drying in a vacuum oven, compound 8c was obtained using column chromatography (developing medium: DCM).

[0193] (Reaction Equation 36) [ka] Chemical formula H

[0194] Compound 8c (40 mmol) was placed in n-pentanol with Zn(OAc)2 (10 mmol) and DBU (1,8-Diazabicyclo(5.4.0)undec-7-ene, 50 mmol) and heated at 140°C with stirring. After the reaction was complete, methanol and a 10% NaCl aqueous solution were added to form a precipitate, which was separated by vacuum filtration and then washed. The precipitate was dried in a vacuum oven at 40°C to obtain the substance corresponding to chemical formula H.

[0195] The MALDI-TOF analysis results for chemical formula H are as follows: m / z calcd for C72H53Cl12N8O4Zn([M+H] + ), 1576.97;found, 1576.99.

[0196] (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.

[0197] Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Then, the binder resin and photopolymerizable monomer were added and stirred at room temperature for 2 hours. Next, the compound produced in Synthesis Example 4 (the compound represented by chemical formula A) was added to the resulting reaction product as a colorant and stirred at room temperature for 1 hour. Finally, the product was filtered three times to remove impurities, thereby producing a photosensitive resin composition.

[0198] [Table 1]

[0199] Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Synthesis Example 2 (represented by chemical formula B) was used instead of the compound from Synthesis Example 1 (represented by chemical formula A).

[0200] 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).

[0201] Example 4 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Synthesis Example 4 (the compound represented by chemical formula D) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0202] Example 5 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound from Synthesis Example 5 (the compound represented by chemical formula E) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0203] 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 F) was used instead of the compound from Synthesis Example 1 (the compound represented by chemical formula A).

[0204] Comparative Example 2 A photosensitive resin composition was produced in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 2 (compound represented by Chemical Formula G) was used instead of the compound of Synthesis Example 1 (compound represented by Chemical Formula A).

[0205] Comparative Example 3 A photosensitive resin composition was produced in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 3 (compound represented by Chemical Formula H) was used instead of the compound of Synthesis Example 1 (compound represented by Chemical Formula A).

[0206] Evaluation 1: Spectral Measurement Each of the compounds obtained in Synthesis Example 1, Synthesis Example 2, and Comparative Synthesis Example 1 was dissolved in cyclohexanone at a concentration of 0.001 wt%, and the spectral spectrum in the wavelength region corresponding to 380 - 780 nm was measured using a UV-Vis spectrometer, and the results are shown in Fig. 1.

[0207] From Fig. 1, it can be confirmed that the compounds obtained in Synthesis Example 1 and Synthesis Example 2 have a better red shift than the compound obtained in Comparative Synthesis Example 1 and have a maximum absorption wavelength in the wavelength region of 660 nm - 680 nm, enabling control of the transmittance in the infrared region.

[0208] Evaluation 2: Measurement of Color Characteristics of the Composition Using the photosensitive resin compositions produced in Examples 1 to 5 and Comparative Examples 1 to 3, spin coating was performed on a glass test piece (10 × 10 cm 2 ) to a thickness of 0.6 μm, and then prebaked on a hot plate at 100 °C for 3 minutes. Next, using a UV exposure apparatus, 200 mJ / cm 2After exposure, the specimens were post-baked on a 230°C hot plate for 5 minutes. The spectra of the completed elongated test specimens were measured using a chromatometer (MPCD-1, Otsuka Corporation), and the thickness was measured using a contact-type thickness analyzer (Tencor P-16). The measured values ​​were calculated to obtain transmittance values ​​corresponding to each wavelength at a thickness of 0.5 μm, and the transmittance information at 680 nm in particular is shown in Table 2 below.

[0209] [Table 2]

[0210] From Table 2 above, it can be confirmed that the photosensitive resin compositions of Examples 1 to 5, which include a core-shell compound according to one embodiment, have superior color characteristics compared to the compositions of Comparative Examples 1 to 3, and are highly suitable for use in CMOS image sensors or OLEDos elements.

[0211] 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 A core-shell compound comprising a shell represented by the following chemical formula 2 surrounding the aforementioned core: [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 substituted or unsubstituted C1-C20 alkyl group, an unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group. R ２ and R ３ They are linked to each other or condense to form a ring, or do not form a ring. L １ and L ４ are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or represented by the following chemical formula L, provided that the L １ to L ４ are not all single bonds at the same time, [Chemical formula L] 【Transformation 3】 In the above chemical formula L, L ５ This is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. n is an integer between 1 and 10. L ａ and L ｂ Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. R ａ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or ＊ -C (=O) OR ４ (R ４ (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) R ｂ ~R ｅ Each of these is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. However, R ａ ~R ｅ All of them are not hydrogen atoms at the same time, m1 is an integer between 0 and 3. m² is an integer between 1 and 10.

2. The 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 m1 is an integer of 0, and the aforementioned R ｂ ~R ｅ The compound according to claim 1, wherein each of them is independently a halogen atom.

4. Said L １ This is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. Said L ２ ~L ４ The compound according to claim 3, wherein each of them is independently a single bond.

5. The aforementioned R ２ and R ３ The compound according to claim 1, wherein the elements are linked to each other or condensed to form a substituted or unsubstituted cycloalkane ring or a substituted or unsubstituted benzene ring.

6. The compound according to claim 1, wherein the core represented by the chemical formula 1 has a maximum absorption wavelength of 660 nm to 680 nm.

7. The shell represented by the chemical formula 2 is the compound according to claim 1, represented by the following chemical formula 2-1: [Chemical formula 2-1] 【Chemistry 4】 In the above chemical formula 2-1, R ａ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or ＊ -C (=O) OR ４ (R ４ (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) R ｂ ~R ｅ Each of these is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. However, R ａ ~R ｅ All of them are not hydrogen atoms at the same time, m1 is an integer between 0 and 3.

8. The core-shell compound is the compound according to claim 1, represented by any one of the following chemical formulas A to E. [Chemical formula A] 【Transformation 5】 [Chemical formula B] 【Transformation 6】 [Chemical formula C] 【Transformation 7】 [Chemical formula D] 【Transformation 8】 [Chemical formula E] 【Chemistry 9】

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

10. A photosensitive resin composition comprising the compound described in 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 described in claim 10.

14. A color filter comprising the photosensitive resin film described in claim 13.

15. A CMOS image sensor comprising the color filter described in claim 14.

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