Core-shell compound, photosensitive resin composition and layer, color filter and sensor

Abstract

Provided are a core-shell compound, a photosensitive resin composition containing the core-shell compound, a photosensitive resin layer manufactured using the photosensitive resin composition, a color filter including the photosensitive resin layer, and a complementary metal oxide semiconductor image sensor including the color filter, the core-shell compound includes a core represented by Chemical Formula 1 and a shell surrounding the core, the shell being represented by Chemical Formula 2: [Chemical Formula 1] [Chemical Formula 2]

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0153668, filed on November 1, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Various embodiments relate to a core-shell compound, a photosensitive resin composition comprising the core-shell compound, a photosensitive resin layer manufactured using the photosensitive resin composition, a color filter including the photosensitive resin layer, and a complementary metal-oxide-semiconductor image sensor including the color filter. Background Technology

[0004] With the recent advancements in information and communication processing technologies and the rapid development of the entire electronics industry, consideration has been given to next-generation detectors capable of rapidly transmitting and receiving large amounts of information, as well as the development of new concept devices and systems. With the rise of video processing in mobile devices, the development of ultra-downsized and ultra-power-saving image sensors is rapidly accelerating, centered on existing charge-coupled devices (CCDs) and complementary metal-oxide-semiconductor (CMOS) technologies.

[0005] As a semiconductor that converts photons into electrons and displays them on a display or stores them in a storage device, an image sensor may include: a light receiving element that converts light signals into electrical signals; a pixel circuit portion that amplifies and compresses the converted electrical signals; and an application-specific integrated circuit (ASIC) portion that converts these pre-processed analog signals into digital signals to process image signals, and includes, for example, CCD, CMOS, contact image sensor (CIS), etc.

[0006] CCD and CMOS image sensors use the same light-receiving element, but in a CCD image sensor, the charge generated in the light-receiving element moves sequentially through a series-connected metal-oxide-semiconductor (MOS) capacitor and is converted into a voltage in a source follower connected at the final terminal. In a CMOS image sensor, the charge is converted into a voltage in a source follower built into each pixel and output to the outside. CCD image sensors use gate pulses to move light-generated electrons to the output unit as is, while CMOS image sensors convert light-generated electrons into a voltage in each pixel and then output it through several CMOS switches. These image sensors are widely used in everything from consumer products such as digital cameras and mobile phones to endoscopes used in hospitals and telescopes for satellites orbiting the Earth. Summary of the Invention

[0007] These embodiments can be achieved by providing a core-shell compound comprising a core represented by chemical formula 1 and a shell surrounding the core, the shell being represented by chemical formula 2:

[0008] [Chemical Formula 1]

[0009]

[0010] [Chemical Formula 2]

[0011]

[0012] In chemical formulas 1 and 2, R 1 It is a thermosetting group, R 2 and R 3 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, L 1 and L 6 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, or a group represented by the chemical formula L, with the restriction that L is... 1 and L 6 At least one of them is a group represented by the chemical formula L, L 2 L 4 L a and L b Each is independently a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, L 3 For a single bond, or an ester group represented by *-C(=O)O-* or *-OC(=O)-*, L 5It is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and n is an integer greater than or equal to 2.

[0013] [Chemical formula L]

[0014]

[0015] In the chemical formula L, L 7 It is a substituted or unsubstituted C1 to C10 alkylene group, and m is an integer from 2 to 10.

[0016] Thermosetting groups may include substituted or unsubstituted epoxy groups, substituted or unsubstituted oxetyl groups, or combinations thereof.

[0017] R 1 It can be a thermosetting group, R 2 and R 3 Each can be an independent hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 and L 5 Each can be independently a substituted or unsubstituted C1 to C10 alkylene group, L 2 To L 4 Each can be a single bond independently, and L 6 It can be a group represented by the chemical formula L.

[0018] R 1 It can be a thermosetting group, R 2 and R 3 Each can be an independent hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 It can be a group represented by the chemical formula L, L 2 L 4 and L 6 Each can be independently a substituted or unsubstituted C1 to C10 alkylene group, L 3 It can be an ester group represented by *-C(=O)O-* or *-OC(=O)-*, and L 5 It can be a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.

[0019] R 1 It can be a thermosetting group, R 2 and R 3 Each can be an independent hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 and L 6 Each can be an independent group represented by the chemical formula L. 2 and L 4 Each can be independently a substituted or unsubstituted C1 to C10 alkylene group, L 3It can be an ester group represented by *-C(=O)O-* or *-OC(=O)-*, and L 5 It can be a substituted or unsubstituted C1 to C10 alkylene group.

[0020] The nucleus represented by chemical formula 1 can have a maximum absorption wavelength of about 610 nm to about 640 nm.

[0021] The shell represented by chemical formula 2 can also be represented by chemical formula 2-1:

[0022] [Chemical Formula 2-1]

[0023]

[0024] The core-shell compound can be represented by one of the chemical formulas A through C:

[0025] [Chemical Formula A]

[0026]

[0027] [Chemical Formula B]

[0028]

[0029] [Chemical formula C]

[0030]

[0031] The core-shell compound may be a green dye.

[0032] The embodiments can be achieved by providing a photosensitive resin composition comprising a core-shell compound according to the embodiments.

[0033] The photosensitive resin composition may also include an adhesive resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, or a solvent.

[0034] The photosensitive resin composition can be used in CMOS image sensors.

[0035] The embodiments can be achieved by providing a photosensitive resin layer, which is manufactured using a photosensitive resin composition according to the embodiments.

[0036] The embodiments can be implemented by providing a color filter that includes a photosensitive resin layer according to the embodiments.

[0037] The embodiments can be implemented by providing a CMOS image sensor, which includes a color filter according to the embodiments. Detailed Implementation

[0038] Various exemplary embodiments will now be set forth more fully below; however, these exemplary embodiments may be implemented in different forms and should not be construed as limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey exemplary implementation methods to those skilled in the art. The term “or” as used herein is not exclusive; for example, “A or B” will include A, B, or A and B.

[0039] Unless otherwise defined, “substituted” as used herein refers to a group substituted with a substituent selected from the following: halogen (F, Br, Cl, or I), hydroxyl, nitro, cyano, amino (NH2, NH(R)). 200 ) or N(R 201 (R) 202 ), where R 200 R 201 and R 202 The same or different, and each independently being a C1 to C10 alkyl), amidoyl, hydrazine, hydrazone, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclic group.

[0040] Unless otherwise specifically defined, “alkyl” as used herein refers to C1 to C20 alkyl, and particularly C1 to C15 alkyl; “cycloalkyl” refers to C3 to C20 cycloalkyl, and particularly C3 to C18 cycloalkyl; “alkoxy” refers to C1 to C20 alkoxy, and particularly C1 to C18 alkoxy; “aryl” refers to C6 to C20 aryl, and particularly C6 to C18 aryl; “alkenyl” refers to C2 to C20 alkenyl, and particularly C2 to C18 alkenyl; “alkylene” refers to C1 to C20 alkylene, and particularly C1 to C18 alkylene; and “arylene” refers to C6 to C20 arylene, and particularly C6 to C16 arylene.

[0041] Unless otherwise defined, “(meth)acrylate” as used herein refers to “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylic acid”.

[0042] Unless otherwise defined, “combination” as used herein refers to a mixture or copolymerization. Additionally, “copolymerization” refers to block copolymerization or random copolymerization, and “copolymer” refers to block copolymerization or random copolymerization.

[0043] In the chemical formulas of this specification, unless otherwise specifically defined, hydrogen atoms are bonded at positions where chemical bonds should be given but are not shown.

[0044] In this specification, unless otherwise specifically defined, "*" indicates a point where the same or different atoms or chemical formulas are connected.

[0045] Some exemplary embodiments provide a core-shell compound comprising a core represented by chemical formula 1 and a shell surrounding the core represented by chemical formula 2.

[0046] [Chemical Formula 1]

[0047]

[0048] [Chemical Formula 2]

[0049]

[0050] In chemical formulas 1 and 2, R 1 It can be, for example, a thermosetting group.

[0051] R 2 and R 3 Each may be independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group.

[0052] L 1 and L 6 Each group may be, independently or include, for example, substituted or unsubstituted C1 to C10 alkylene groups, or groups represented by the chemical formula L, the limitation being that L... 1 and L 6 At least one of them is represented by the chemical formula L.

[0053] L 2 L 4 L a and L b Each can be independently or include, for example, a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.

[0054] L 3 It may be or include, for example, single bonds or ester groups, such as *-C(=O)O-* or *-OC(=O)-*.

[0055] L 5 It may be or include, for example, single bonds, or substituted or unsubstituted C1 to C10 alkylene groups.

[0056] n can be an integer greater than or equal to 2, for example.

[0057] [Chemical formula L]

[0058]

[0059] In the chemical formula L, L 7 It may be or include, for example, substituted or unsubstituted C1 to C10 alkylene groups.

[0060] m can be an integer from 1 to 10, or an integer from 2 to 10.

[0061] Among many types of displays, liquid crystal displays (LCDs) offer advantages such as lightness, thinness, low cost, low power consumption, and improved adhesion to integrated circuits, and are increasingly used in notebook computers, monitors, and television (TV) screens. An LCD may include a lower substrate on which a black matrix, color filters, and indium tin oxide (ITO) pixel electrodes are formed, and an upper substrate on which active circuitry and ITO pixel electrodes are formed. The active circuitry includes a liquid crystal layer, thin-film transistors, and capacitor layers. Each pixel can be formed by sequentially stacking multiple color filters (e.g., formed from the three primary colors, such as red (R), green (G), and blue (B)) in a predetermined order, and the boundaries between pixels can be formed by setting a black matrix layer in a predetermined pattern on a transparent substrate. Pigment dispersion methods (e.g., a method for forming a color filter) can provide a colored film by repeatedly performing a series of processes, such as coating a photopolymerizable composition containing a colorant onto a transparent substrate including a black matrix, exposing the formed pattern to light, removing unexposed portions using a solvent, and thermally curing it. The coloring photosensitive resin composition used to manufacture the color filter according to the pigment dispersion method may contain an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, etc. The pigment dispersion method can be used to manufacture liquid crystal displays (LCDs) used in, for example, mobile phones, laptops, monitors, and televisions.

[0062] Image sensors can be components used to capture images in portable mobile phone cameras or digital still cameras (DSCs). Image sensors can be classified, for example, as charge-coupled device (CCD) image sensors or complementary metal-oxide-semiconductor (CMOS) image sensors, depending on the manufacturing process and application method. A color imaging device using a CCD or CMOS image sensor may include multiple color filters, each having a filter segment for mixing red, green, and blue primary colors, and the colors can be separated. Some color filters installed in the color imaging device may have a pattern size of 2 μm or less, which may be 1 / 100 to 1 / 200 of the pattern size of other color filter patterns used in LCDs. Therefore, increased resolution and reduced pattern residue can be important factors determining the performance of the device.

[0063] Meanwhile, color filters formed from pigment-based photosensitive resin compositions can suffer from color mixing problems due to limitations in pigment particle size and film-thinning. Furthermore, color imaging devices for image sensors can use smaller dispersion particle sizes to form fine patterns. Therefore, efforts have been considered to improve resolution by introducing non-particulate dyes instead of pigments to prepare photosensitive resin compositions suitable for said dyes.

[0064] The embodiments described may involve the use of green dyes in color filters for CMOS image sensors or for organic light-emitting diodes on silicon (OLEDs). Due to the small size of pixels, there may be limitations in using pigments to create fine patterns, and therefore, dyes can be used to compensate for this. Dyes may present problems with processability during patterning; for example, dyes may exhibit severely degraded developability, making it difficult to form fine patterns after curing and heat treatment. Furthermore, the developability of the dye itself may be slightly insufficient when it contains only a small amount of dye as a colorant in the total composition. When the photosensitive resin composition for CMOS image sensors or organic light-emitting diodes on silicon (OLEDs) contains an excess (about 15% to about 30% by weight, for example, about 16% to about 27% by weight of the total weight of the photosensitive resin composition), a dye with excellent developability can be used.

[0065] The embodiments relate to a core-shell compound synthesized by inserting an epoxy alkyl linker group into a squaric acid cyanine compound forming the core and introducing a thermosetting group at its end, and surrounding the core with a shell. The core-shell compounds synthesized in this manner according to some exemplary embodiments can themselves exhibit excellent developability, and photosensitive resin compositions comprising an excess of the core-shell compound as a green dye do not show a significant reduction in developability even after curing and heat treatment, and are therefore highly suitable for green color filters in CMOS image sensors or organic light-emitting diodes on silicon (OLEDs).

[0066] In other words, some embodiments can provide squaric acid core-shell dyes with improved developability. As mentioned above, when using a dye-containing composition to produce a color filter, a bottom residue problem can occur, which may be due to the low solubility of the dye in the alkaline aqueous solution used in the developing process. By using some embodiments, bottom residue can be reduced by including an epoxide linking group, such as ethylene oxide (which can help increase water solubility), in the dye structure while introducing a thermosetting group at the end.

[0067] In one embodiment, the thermosetting group may include, for example, substituted or unsubstituted epoxy groups, substituted or unsubstituted oxetyl groups, or combinations thereof.

[0068] Thermosetting groups can be further substituted with, for example, alkyl groups.

[0069] In one embodiment, the compound represented by chemical formula 1 may be, for example: 1) a compound represented by chemical formula 1, wherein R 1 It can be, for example, a thermosetting group, R 2 and R 3 Each can be independently, for example, a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 and L 5 Each can be independently, for example, a substituted or unsubstituted C1 to C10 alkylene group, L 2 To L 4 Each can be independently, for example, a single bond, and L 6 It can be, for example, a group represented by chemical formula L, or 2) a compound represented by chemical formula 1, wherein R 1 It can be, for example, a thermosetting group, R 2 and R 3 Each can be independently, for example, a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 It can be, for example, a group represented by the chemical formula L, L 2 L 4 and L 6Each can be independently, for example, a substituted or unsubstituted C1 to C10 alkylene group, L 3 It can be an ester group, such as *-C(=O)O-* or *-OC(=O)-*, and L 5 It may be, for example, a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, or 3) a compound represented by formula 1, wherein R 1 It can be, for example, a thermosetting group, R 2 and R 3 Each can be independently, for example, a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, L 1 and L 6 Each can be an independent group, for example, represented by the chemical formula L. 2 and L 4 Each can be independently, for example, a substituted or unsubstituted C1 to C10 alkylene group, L 3 It can be an ester group, such as *-C(=O)O-* or *-OC(=O)-*, and L 5 It can be, for example, a substituted or unsubstituted C1 to C10 alkylene group, and all three types of compounds can provide dyes with improved developability.

[0070] In one embodiment, the core represented by Formula 1 may include, for example, a total of 2, 4, or 6 thermosetting groups at its ends. Cores represented by Formula 1 with a total of 1, 3, or 5 terminal thermosetting groups may be difficult to synthesize, for example, due to their structure, and even if synthesized, they may be expensive to apply in a practical production line.

[0071] In one embodiment, when the number of terminal thermosetting groups is 6, the core represented by Formula 1 can have better reproducibility than when the number of terminal thermosetting groups is 4, and when the number of terminal thermosetting groups is 4, it can have better reproducibility than when the number of terminal thermosetting groups is 2. That is, if only the reproducibility of the compound is considered, a number of 4 terminal thermosetting groups in the core structure represented by Formula 1 is better than 2, and a number of 6 is better than 4.

[0072] Furthermore, as the number of alkyl oxide bonds increases, the nucleus represented by Formula 1 can be advantageous in terms of solubility, and the alkyl oxide bonds can be, for example, ethylene oxide bonds or propylene oxide bonds. Among alkyl oxide bonds, ethylene oxide bonds are more hydrophilic, and therefore their use is more advantageous in terms of solubility.

[0073] In one embodiment, in the core represented by Formula 1, when the number of terminal thermosetting groups is 1, not only is synthesis difficult as described above, but the developability may also be lower than when the number of terminal thermosetting groups is 2. Therefore, it is desirable for the core represented by Formula 1 to include two or more terminal thermosetting groups.

[0074] In one embodiment, the nucleus represented by Formula 1 may have a maximum absorption wavelength of about 610 nm to about 640 nm. Even if the dye compound has excellent solubility of 10% or more in an organic solvent, it may be unsuitable as a green photosensitive resin composition for CMOS image sensors or organic light-emitting diodes on silicon (OLEDs) due to its low transmittance if it does not have a maximum absorption wavelength of about 610 nm to about 640 nm.

[0075] The shell represented by chemical formula 2 can also be represented by chemical formula 2-1.

[0076] [Chemical Formula 2-1]

[0077]

[0078] In one embodiment, the core-shell compound may be represented by one of the chemical formulas A to C.

[0079] [Chemical Formula A]

[0080]

[0081] [Chemical Formula B]

[0082]

[0083] [Chemical formula C]

[0084]

[0085] In one embodiment, the core-shell compound may be, for example, a green dye.

[0086] According to some exemplary embodiments, a photosensitive resin composition may be provided, the photosensitive resin composition comprising a core-shell compound according to an exemplary embodiment.

[0087] In one embodiment, the photosensitive resin composition may have, for example, a transmittance of about 90% or greater at about 540 nm, a transmittance of, for example, about 10% or less than 10% at about 600 nm to about 640 nm, and a transmittance of, for example, about 5% or less than 5% at about 450 nm, and is suitable for realizing a green color filter for a high-transmittance CIS. In one embodiment, the photosensitive resin composition may be used in a high-transmittance CMOS image sensor or an organic light-emitting diode on silicon (OLEDos).

[0088] The photosensitive resin composition may contain, for example, a core-shell compound, and may also contain an adhesive resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, or a solvent.

[0089] According to some exemplary embodiments, core-shell compounds can act as dyes and colorants in photosensitive resin compositions. Developability is maximized 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. That is, according to some exemplary embodiments, the core-shell compound can be a hybrid dye used in conjunction with a pigment.

[0090] In one embodiment, the pigment may also include, for example, yellow pigment, green pigment, or a combination thereof.

[0091] Yellow pigments can have color index (CI) values ​​such as CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, etc., and these pigments can be used alone or as a mixture of two or more of them.

[0092] Green pigments can have color indices such as CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, etc., and these pigments can be used alone or as a mixture of two or more of them.

[0093] Pigments can be contained in photosensitive resin compositions in the form of pigment dispersions.

[0094] Pigment dispersions may contain, for example, solid pigments, solvents, or dispersants for uniformly dispersing pigments in a solvent.

[0095] The solid pigment may be contained in an amount of about 1% to about 20% by weight, for example about 8% to about 20% by weight, about 8% to about 15% by weight, about 10% to about 20% by weight, or about 10% to about 15% by weight, based on the total weight of the pigment dispersion.

[0096] The dispersant can be a nonionic dispersant, anionic dispersant, cationic dispersant, etc. In one embodiment, the dispersant can be a polyalkylene glycol and its esters, polyoxyalkylene glycol, polyol ester epoxy alkyl addition product, alcohol epoxy alkyl addition product, sulfonate, sulfonate, carboxylic acid ester, carboxylate, alkylamide epoxy alkyl addition product, alkylamine, etc., and these dispersants can be used alone or as a mixture of two or more.

[0097] Commercially available examples of dispersants may include, for example, 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., manufactured by BYK Co., Ltd.; and those manufactured by EFKA Chemicals. Evka-47, Evka-47EA, Evka-48, Evka-49, Evka-100, Evka-400, Evka-450, etc., manufactured by Zeneka Co.; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc., manufactured by Zeneka Co.; or PB711, PB821, etc., manufactured by Ajinomoto Inc.

[0098] The dispersant may be included, for example, in an amount from about 1% to about 20% by weight of the total weight of the pigment dispersion. If a dispersant is included within this range, the dispersibility of the photosensitive resin composition can be improved by appropriate viscosity, and thus the optical, physical and chemical qualities can be maintained when the photosensitive resin composition is applied to a product.

[0099] Solvents used to form pigment dispersions may include, for example, ethylene glycol acetate, ethyl celex, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc.

[0100] The pigment dispersion may be included in an amount of about 10% to about 20% by weight, for example, about 12% to about 18% by weight, based on the total weight of the photosensitive resin composition. Including the pigment dispersion within this range can help ensure process margins and can result in improved color gamut and contrast.

[0101] The adhesive resin may be, for example, an acrylic adhesive resin.

[0102] The acrylic adhesive resin may be, for example, a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer that can copolymerize therewith, and may be, for example, a resin comprising at least one repeating acrylic unit.

[0103] The first olefinic unsaturated monomer may be, for example, an olefinic unsaturated monomer comprising at least one carboxyl group, and examples of the monomer may include, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0104] The first olefinic unsaturated monomer may be contained in an amount of about 5% to about 50% by weight, for example, about 10% to about 40% by weight, based on the total weight of the acrylic adhesive resin.

[0105] The second olefinic unsaturated monomer may be, for example: aromatic vinyl compounds, such as styrene, α-methylstyrene, vinyltoluene, vinyl benzyl methyl ether, etc.; 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, phenyl (meth)acrylate, etc.; unsaturated aminoalkyl carboxylic acid ester compounds, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; vinyl carboxylic acid ester compounds, such as vinyl acetate, vinyl benzoate, etc.; unsaturated glycidyl carboxylic acid ester compounds, such as glycidyl (meth)acrylate, etc.; vinyl cyanide compounds, such as (meth)acrylonitrile, etc.; unsaturated amide compounds, such as (meth)acrylamide, etc.; or similar compounds, and the second olefinic unsaturated monomer may be used alone or as a mixture of two or more.

[0106] In one embodiment, the acrylic adhesive resin may be, for example, a (meth)acrylic acid / benzyl methacrylate copolymer, a (meth)acrylic acid / benzyl methacrylate copolymer, a (meth)acrylic acid / benzyl methacrylate / styrene copolymer, a (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, a (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., and these copolymers may be used alone or as a mixture of two or more.

[0107] The weight-average molecular weight of the adhesive resin can be from about 3,000 g / mol to about 150,000 g / mol, for example from about 5,000 g / mol to about 50,000 g / mol, or from about 20,000 g / mol to about 30,000 g / mol. If the adhesive resin has a weight-average molecular weight within these ranges, the photosensitive resin composition can have good physical and chemical properties, suitable viscosity, and good contact properties with the substrate during the manufacture of the color filter.

[0108] The acid value of the adhesive resin can be from about 15 mg KOH / g to about 60 mg KOH / g, for example, from about 20 mg KOH / g to about 50 mg KOH / g. When the acid value of the adhesive resin is within these ranges, the resolution of the pixel pattern can be improved.

[0109] The binder resin may be included in an amount from about 1% to about 30% by weight, for example from about 1% to about 20% by weight, based on the total weight of the photosensitive resin composition. If the binder resin is included within these ranges, the composition may have excellent developability and improved crosslinking, and therefore may have excellent surface smoothness when manufactured into a color filter.

[0110] Photopolymerizable monomers may be, for example, monofunctional or polyfunctional (meth)acrylic acid esters comprising at least one olefinic unsaturated double bond.

[0111] Photopolymerizable monomers can have olefinic unsaturated double bonds, and therefore can fully polymerize during exposure in the patterning process, forming patterns with excellent heat resistance, light resistance and chemical resistance.

[0112] Examples of photopolymerizable monomers may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyl phosphate, phenolic epoxy(meth)acrylate, etc.

[0113] Commercially available examples of photopolymerizable monomers are as follows. Monofunctional (meth)acrylates may include, for example, Aronix. (Toagosei Chemistry Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.) (Osaka Organic Chemical Ind., Ltd.) etc. Examples of difunctional (meth)acrylates may include, for example, Yarrow's. (Dong-A Synthetic Chemical Co., Ltd.), Kayara (Nippon Kayaku Co., Ltd.) V-335 (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth)acrylates may include, for example, Aronis from Toa Synthetic Chemical Co., Ltd. etc.; Kayarad from Nippon Kayaku Co., Ltd. Osaka Yuki Kayaku Kogyo Co., Ltd. These photopolymerizable monomers can be used alone or as a mixture of two or more.

[0114] Acid anhydrides can be used to treat photopolymerizable monomers to improve their developability.

[0115] The photopolymerizable monomer may be included in an amount from about 1% to about 15% by weight, for example from about 5% to about 10% by weight, based on the total weight of the photosensitive resin composition. If the photopolymerizable monomer is included within the range described above, the photopolymerizable monomer can be fully cured during exposure in the patterning process and can have excellent reliability, and the developability of the alkaline developing solution can be improved.

[0116] Photopolymerization initiators can be common initiators in photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0117] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-but-1-one, etc.

[0118] Examples of benzophenone compounds include benzoyl benzoate, benzoyl benzoate, methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0119] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0120] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0121] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)- s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthyl-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0122] Examples of oxime compounds may 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]acetone, O-ethoxycarbonyl-α-oxoamino-1-phenylprop-1-one, etc. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylhydrothiophenyl)-but-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-oct-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-oct-1-one oxime-O-acetate, 1-(4-phenylhydrothiophenyl)-but-1-one oxime-O-acetate, etc.

[0123] In addition to the compounds mentioned above, photopolymerization initiators may also include, for example, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc.

[0124] Photopolymerization initiators can be used with photosensitizers that can induce a chemical reaction by absorbing light, being excited, and then transferring their energy.

[0125] Examples of photosensitizers may include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, etc.

[0126] The photopolymerization initiator may be included in an amount from about 0.01% to about 10% by weight, for example from about 0.1% to about 5% by weight, based on the total weight of the photosensitive resin composition. If a photopolymerization initiator within these ranges is included, sufficient photopolymerization can occur during exposure in the patterning process, resulting in excellent reliability, improved heat resistance, light resistance, chemical resistance, resolution, and close contact properties of the pattern, and prevention of transmittance reduction due to non-reactive initiators.

[0127] The solvent may be a material that is compatible with, but does not react with, the core-shell compound, adhesive resin, photopolymerizable monomer, photopolymerization initiator, and pigment according to some exemplary embodiments.

[0128] Examples of solvents may include: alcohols, such as methanol and ethanol; ethers, such as dichloroethyl ether, n-butyl ether, diisopentyl ether, methyl phenyl ether, tetrahydrofuran, etc.; ethylene glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, etc.; selenoacetic acid, such as methyl selenoacetic acid, ethyl selenoacetic acid, diethyl selenoacetic acid, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene and xylene; ketones, such as methyl ethyl ketone and cyclohexanone. 4-Hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters, such as methyl lactate, ethyl lactate, etc.; oxyacetic acid alkyl esters, such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetic acid alkyl esters, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxypropionic acid alkyl esters, such as methyl 3-oxypropionic acid, ethyl 3-oxypropionic acid, etc.; 3-alkoxypropionic acid alkyl esters, such as methyl 3-methoxypropionic acid, methyl 3-methylpropionic acid, etc. Ethyl oxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxypropionates, such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionates, such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, etc.; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylalkylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, for example... Examples of suitable solvents include ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, etc.; keto esters, such as ethyl pyruvate, etc. Additionally, high-boiling-point solvents can also be used, such as N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celecoxalate, etc.

[0129] Considering compatibility and reactivity, the following are desirable to use: alcohol ethers, such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates, such as ethyl celusyl acetate; esters, such as ethyl 2-hydroxypropionate; carbitol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate; and / or ketones, such as cyclohexanone.

[0130] The solvent may be included in the balance (e.g., from about 30% to about 80% by weight) based on the total weight of the photosensitive resin composition. If the solvent is included within these ranges, the photosensitive resin composition may have a suitable viscosity, thereby improving the coating characteristics of the color filter.

[0131] The photosensitive resin composition according to some exemplary embodiments may also contain an epoxy compound to improve its close contact properties with the substrate.

[0132] Examples of epoxy compounds may include phenolic aldehyde epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0133] Based on 100 parts by weight of the photosensitive resin composition, an epoxy compound may be included in an amount from about 0.01 parts by weight to about 20 parts by weight, for example from about 0.1 parts by weight to about 10 parts by weight. If an epoxy compound is included within the above range, the contact properties, storage properties, etc., can be improved.

[0134] In one embodiment, the photosensitive resin composition may further comprise a silane coupling agent having reactive substituents (e.g., carboxyl, methacryloyl, isocyanate, epoxy, etc.) to help improve its adhesion to the substrate.

[0135] Examples of silane coupling agents may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, etc., and these materials may be used alone or as a mixture of two or more.

[0136] Based on 100 parts by weight of the photosensitive resin composition, a silane coupling agent may be included, for example, in an amount from about 0.01 parts by weight to about 10 parts by weight. The inclusion of a silane coupling agent within this range can improve contact properties, storage properties, etc.

[0137] In one embodiment, the photosensitive resin composition may further contain a surfactant to improve coating properties and prevent defects where necessary.

[0138] Examples of surfactants include commercially available fluorosurfactants such as those from BM Chemie Inc. etc.; F of Dainippon Ink Kagaku Kogyo Co., Ltd. F F F etc.; Florad of Sumitomo 3M Co., Ltd. etc.; SURFLON from ASAHI Glass Co., Ltd. wait; wait.

[0139] Based on 100 parts by weight of the photosensitive resin composition, a surfactant may be included, for example, in an amount from about 0.001 parts by weight to about 5 parts by weight. If a surfactant is included within this range, coating uniformity is guaranteed, no stains are found, and the wetting properties of the glass substrate are improved.

[0140] In one embodiment, unless the properties deteriorate, the photosensitive resin composition may also contain other additives, such as oxidation inhibitors, stabilizers, etc., in predetermined amounts.

[0141] According to some exemplary embodiments, a photosensitive resin layer manufactured using a photosensitive resin composition according to some exemplary embodiments may be provided.

[0142] According to some exemplary embodiments, a color filter including the photosensitive resin layer may be provided.

[0143] The pattern formation process in the color filter can be as follows.

[0144] The process may include: coating a photosensitive resin composition according to some exemplary embodiments onto a support substrate by methods such as spin coating, slot coating, inkjet printing; drying the coated positive photosensitive resin composition to form a photosensitive resin composition film; exposing the positive photosensitive resin composition film; developing the exposed positive photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin layer; and heat-treating the photosensitive resin layer.

[0145] Some exemplary embodiments may provide a CMOS image sensor or OLED OS (on-silicon display) including the color filter.

[0146] OLED devices.

[0147] The following examples and comparative examples are provided to highlight the features of one or more embodiments. However, it should be understood that these examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should they be construed as exceeding the scope of the embodiments. Furthermore, it should be understood that the embodiments are not limited to the specific details set forth in the examples and comparative examples.

[0148] (Compound Synthesis)

[0149] (Synthesis Example 1: Synthesis of a compound represented by chemical formula A)

[0150] (Reaction Scheme 1)

[0151]

[0152] Compounds 1a (12 mmol) and 1b (10 mmol) were dissolved in 2-propanol with CuCl (0.5 mmol) and NaOH (20 mmol) and then reacted by heating to 90 °C for 12 hours. After cooling to ambient temperature, distilled water was added, and extraction was performed using dichloromethane (DCM). The resulting organic layer was passed through MgSO4, concentrated under reduced pressure, and treated by column chromatography (eluent: n-Hex / EtOAc) to obtain compound 1c.

[0153] (Reaction Scheme 2)

[0154]

[0155] At 0 °C, 15 mmol of NaH (60% in mineral oil) was added dropwise to a tetrahydrofuran (THF) solution of compound 1c (10 mmol) over 30 minutes. After the addition of compound 1d (10.5 mmol), the reaction temperature was raised to ambient temperature and the reaction was carried out overnight. The aqueous layer was extracted with 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 / EtOAc).

[0156] (Reaction Scheme 3)

[0157]

[0158] Compounds 1e (10 mmol) and 1f (11 mmol) were added to a mixed solution of 1,4-dioxane / H2O (v / v = 4 / 1) with K2CO3 (15 mmol) and Pd(PPh3)4 (1.0 mmol) and then reacted under reflux. After cooling to ambient temperature, the organic layer was separated. The organic layer was passed through MgSO4, concentrated under reduced pressure, and treated by column chromatography (eluent: n-Hex / EtOAc) to obtain 1 g of compound.

[0159] (Reaction Scheme 4)

[0160]

[0161] At ambient temperature, 1 g (10 mmol) of compound 1 h (7 mmol) was dissolved in n-butanol, and triethyl orthoformate (30 mmol) was added. The reaction mixture was then heated to 90 °C and reacted for 4 hours. After removing the solvent under reduced pressure, n-hexane was added to the remaining reaction mixture, and the mixture was stirred at 0 °C for 15 minutes. The solid obtained by filtration under reduced pressure was washed and dried to obtain compound 1i.

[0162] (Reaction Scheme 5)

[0163]

[0164] After dissolving compound 1i (10 mmol) in chloroform and then cooling the solution to 0°C, two additional solutions were prepared: (solution A), in which compound 1k (30 mmol) and triethylamine (60 mmol) were dissolved in chloroform; and (solution B), in which compound 1j (30 mmol) was dissolved in chloroform. These two solutions were slowly added to the solution of compound 1i in the order of solution A followed by solution B, and then stirred at ambient temperature for 2 hours. After removing the solvent under reduced pressure, the residue was redissolved in EtOAC to precipitate polymer byproducts. After removing the byproducts by filtration under reduced pressure, the solvent was removed under reduced pressure. The above process was repeated twice after dissolving the residue in chloroform. The material corresponding to compound 1l was obtained by purification using column chromatography (eluent: DCM-EtOAc).

[0165] (Reaction Scheme 6)

[0166]

[0167] Compound 1L (10 mmol) was dissolved in THF to obtain a solution, to which 1M tetrabutylammonium fluoride (TBAF, 22 mmol) was added, and the mixture was stirred at ambient temperature for 2 hours. After checking by thin-layer chromatography to see if compound 1L was completely consumed, 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. The resulting solid was separated by filtration under reduced pressure.

[0168] The solid was washed with distilled water and dried in a vacuum oven at 40°C to obtain compound 1m.

[0169] (Reaction Scheme 7)

[0170]

[0171] Compound 1m (10 mmol) was dissolved in dimethyl sulfoxide (DMSO) to obtain a solution, to which KOH (50 mmol) and epichlorohydrin (ECH, 100 mmol) were added, and the mixture was stirred at 60 °C for 2 hours. Subsequently, distilled water was added, and extraction was performed using DCM. The resulting organic layer was washed with brine, then dried and concentrated. Purification using column chromatography (eluent: DCM-EtOAc) yielded the material corresponding to chemical formula A.

[0172] The HRMS analysis results for chemical formula A are as follows.

[0173] For C 80 H 87 N8O 14 ([M+H)) + The calculated m / z is 1383.6336; the measured value is 1383.6336.

[0174] (Synthesis Example 2: Synthesis of a compound represented by chemical formula B)

[0175] (Reaction Scheme 8)

[0176]

[0177] Compound 2b was synthesized in the same manner as compound 1c, except that compound 2a was used instead of compound 1b.

[0178] (Reaction Scheme 9)

[0179]

[0180] Compound 2c was synthesized in the same manner as compound 1g, except that compound 2b was used instead of compound 1e.

[0181] (Reaction Scheme 10)

[0182]

[0183] Compound 2d was synthesized in the same manner as compound 1i, except that compound 2c was used instead of compound 1g.

[0184] (Reaction Scheme 11)

[0185]

[0186] Compound 2e was synthesized in the same manner as compound 1l, except that compound 2d was used instead of compound 1i.

[0187] (Reaction Scheme 12)

[0188]

[0189] NaI (50 mmol) was added to an acetone solution of compound 2f (10 mmol), and the mixture was stirred overnight at 50 °C. The solvent was removed under reduced pressure, distilled water was added, and extraction was performed using DCM. The organic layer was washed with brine, dried, and concentrated to obtain 2 g of compound.

[0190] (Reaction Scheme 13)

[0191]

[0192] Compound 2h was synthesized in the same manner as compound 1m, except that compound 2e was used instead of compound 1l.

[0193] (Reaction Scheme 14)

[0194]

[0195] Compound 2 g (43.6 mmol) was added to a solution of compound 2 h (4.36 mmol) dissolved in DMSO and K₂CO₃ (43.6 mmol), and the temperature was raised to 80 °C. After stirring overnight, the temperature was slowly cooled to ambient temperature. Diethyl ether was added to the reaction mixture to produce a solid, which was separated by vacuum filtration. The solid was washed with a 10% sodium chloride aqueous solution and dried overnight in a vacuum oven at 40 °C to obtain compound 2i.

[0196] (Reaction Scheme 15)

[0197]

[0199] A 1N NaOH aqueous solution (20 mmol) was added to a THF solution of compound 2i (2.1 mmol), and the mixture was stirred overnight at ambient temperature. A 1N HCl aqueous solution was slowly added to the reaction mixture, followed by extraction with DCM. The organic layer was passed through MgSO4, and the solvent was removed under reduced pressure to obtain compound 2j, which was used in subsequent reactions without further purification. KOH (5.0 mmol) and epichlorohydrin (ECH, 10 mmol) were added to a DMSO solution of compound 2j (1.0 mmol), and the mixture was stirred at 60 °C for 2 hours. After adding distilled water, extraction with DCM was performed. The organic layer was washed with brine, then dried and concentrated. The material corresponding to formula B was obtained by purification using column chromatography (eluent: DCM-EtOAc).

[0200] The HRMS analysis results for chemical formula B are as follows.

[0201] For C 82 H 87 N8O 16 ([M+H)) + The calculated m / z is 1439.6235; the measured value is 1439.6236.

[0202] (Synthesis Example 3: Synthesis of a compound represented by chemical formula C)

[0203] (Reaction Scheme 16)

[0204]

[0205] Compound 3b was synthesized in the same manner as compound 1c, except that compound 3a was used instead of compound 1b.

[0206] (Reaction Scheme 17)

[0207]

[0208] Compound 3c was synthesized in the same manner as compound 1e, except that compound 3b was used instead of compound 1c.

[0209] (Reaction Scheme 18)

[0210]

[0211] Compound 3d was synthesized in the same manner as compound 1g, except that compound 3c was used instead of compound 1e.

[0212] (Reaction Scheme 19)

[0213]

[0214] Compound 3e was synthesized in the same manner as compound 1i, except that compound 3d was used instead of compound 1g.

[0215] (Reaction Scheme 20)

[0216]

[0217] Compound 3f was synthesized in the same manner as compound 1l, except that compound 3e was used instead of compound 1i.

[0218] (Reaction Scheme 21)

[0219]

[0220] Compound 3g was synthesized in the same manner as compound 1m, except that compound 3f was used instead of compound 1l.

[0221] (Reaction Scheme 22)

[0222]

[0223] Compound 3h was synthesized in the same manner as compound 2i, except that compound 3g was used instead of compound 2h.

[0224] (Reaction Scheme 23)

[0225]

[0226] Except for replacing compound 2i with compound 3h, the material corresponding to chemical formula C was synthesized in the same manner as the material corresponding to chemical formula B.

[0227] The HRMS analysis results for chemical formula C are as follows.

[0228] For C 90 H 103 N8O 20 ([M+H)) + The calculated m / z is 1615.7283; the measured value is 1615.7283.

[0229] (Comparative Synthesis Example 1: Synthesis of a compound represented by chemical formula D)

[0230] (Reaction Scheme 24)

[0231]

[0232] Compound 4b was synthesized in the same manner as compound 1c, except that compound 4a was used instead of compound 1b.

[0233] (Reaction Scheme 25)

[0234]

[0235] Compound 4c was synthesized in the same manner as compound 1g, except that compound 4b was used instead of compound 1e.

[0236] (Reaction Scheme 26)

[0237]

[0238] Compound 4d was synthesized in the same manner as compound 1i, except that compound 4c was used instead of compound 1g.

[0239] (Reaction Scheme 27)

[0240]

[0241] Compound 4e was synthesized in the same manner as compound 1l, except that compound 4d was used instead of compound 1i.

[0242] (Reaction Scheme 28)

[0243]

[0244] Compound 4f was synthesized in the same manner as compound 1m, except that compound 4e was used instead of compound 1l.

[0245] (Reaction Scheme 29)

[0246]

[0247] Except for replacing compound 1m with compound 4f, the material corresponding to chemical formula D was synthesized in the same manner as the substance corresponding to chemical formula A.

[0248] The HRMS analysis results for chemical formula D are as follows.

[0249] For C 78 H 83 N8O 10 ([M+H)) + The calculated m / z is 1291.6227; the measured value is 1291.6228.

[0250] (Comparative Synthesis Example 2: Synthesis of a compound represented by chemical formula E)

[0251] (Reaction Scheme 30)

[0252]

[0253] Compound 5b was synthesized in the same manner as compound 1c, except that compound 5a was used instead of compound 1b.

[0254] (Reaction Scheme 31)

[0255]

[0256] Compound 5d was synthesized in the same manner as compound 1e, except that compound 5b was used instead of compound 1c and compound 5c was used instead of compound 1d.

[0257] (Reaction Scheme 32)

[0258]

[0259] Compound 5e was synthesized in the same manner as compound 1g, except that compound 5d was used instead of compound 1e.

[0260] (Reaction Scheme 33)

[0261]

[0262] Compound 5f was synthesized in the same manner as compound 1i, except that compound 5e was used instead of compound 1g.

[0263] (Reaction Scheme 34)

[0264]

[0265] Compound 5g was synthesized in the same manner as compound 1l, except that compound 5f was used instead of compound 1i.

[0266] (Reaction Scheme 35)

[0267]

[0268] Compound 5h was synthesized in the same manner as compound 1m, except that compound 5g was used instead of compound 1l.

[0269] (Reaction Scheme 36)

[0270]

[0271] Except that compound 5h was used instead of compound 1m, the material corresponding to chemical formula E was synthesized in the same manner as the material corresponding to chemical formula A.

[0272] The HRMS analysis results for chemical formula E are as follows.

[0273] For C 74 H 75 N8O 12 ([M+H)) + The calculated m / z is 1267.5499; the measured value is 1267.5499.

[0274] (Comparative Synthesis Example 3: Synthesis of a compound represented by chemical formula F)

[0275] (Reaction Scheme 37)

[0276]

[0277] At ambient temperature, NaH (60%, 15 mmol in mineral oil) was added dropwise to a DMF (N,N-dimethylformamide) solution of compound 6a (10 mmol) over 30 minutes. After the addition of compound 6b (10.5 mmol), the reaction temperature was increased 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 (eluent: n-Hex / EtOAc).

[0278] (Reaction Scheme 38)

[0279]

[0280] 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.

[0281] (Reaction Scheme 39)

[0282]

[0283] Compound 6f was synthesized in the same manner as compound 1i, except that compound 6e was used instead of compound 1g.

[0284] (Reaction Scheme 40)

[0285]

[0286] Except that compound 6f was used instead of compound 1i, the material corresponding to chemical formula F was synthesized in the same manner as compound 1l.

[0287] The HRMS analysis results for chemical formula F are as follows.

[0288] For C 84 H 95 N8O 12 ([M+H)) + The calculated m / z is 1407.7064; the measured value is 1407.7065.

[0289] (Comparative Synthesis Example 4: Synthesis of a compound represented by the chemical formula G)

[0290] (Reaction Scheme 41)

[0291]

[0292] Compound 7b was synthesized in the same manner as compound 1e, except that compound 6c was used instead of compound 1c and compound 7a was used instead of compound 1d.

[0293] (Reaction Scheme 42)

[0294]

[0295] Compound 7c was synthesized in the same manner as compound 1i, except that compound 7b was used instead of compound 1g.

[0296] (Reaction Scheme 43)

[0297]

[0298] Except that compound 7c was used instead of compound 1i, the material corresponding to chemical formula G was synthesized in the same manner as compound 1l.

[0299] The HRMS analysis results for chemical formula G are as follows.

[0300] For C 88 H 103 N8O 14 ([M+H)) + The calculated m / z is 1495.7588; the measured value is 1495.7588.

[0301] (Synthesis of photosensitive resin composition)

[0302] Example 1

[0303] The following components were mixed with each of the components shown in Table 1 to prepare the photosensitive resin composition according to Example 1.

[0304] Specifically, a photopolymerization initiator was dissolved in a solvent, and the solution was stirred at ambient temperature for 2 hours. A binder resin and a photopolymerizable monomer were then added, and the resulting mixture was stirred at ambient temperature for 2 hours. Subsequently, the compound according to Synthesis Example 1 (represented by chemical formula A) was added as a colorant, and the mixture was stirred at ambient temperature for 1 hour. The product was then filtered three times to remove impurities and a photosensitive resin composition was prepared.

[0305] (Table 1)

[0306] (Unit: % by weight)

[0307]

[0308] Example 2

[0309] Except that the compound according to Synthesis Example 2 (represented by chemical formula B) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0310] Example 3

[0311] Except that the compound according to Synthesis Example 3 (represented by chemical formula C) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0312] Comparative Example 1

[0313] Except that the compound according to Comparative Synthesis Example 1 (represented by chemical formula D) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0314] Comparative Example 2

[0315] Except that the compound according to Comparative Synthesis Example 2 (represented by chemical formula E) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0316] Comparative Example 3

[0317] Except that the compound according to Comparative Synthesis Example 3 (represented by chemical formula F) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0318] Comparative Example 4

[0319] Except that the compound according to Comparative Synthesis Example 4 (represented by chemical formula G) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A), the photosensitive resin composition was prepared according to the same method as in Example 1.

[0320] Evaluation: Measurement of the developability of the composition

[0321] The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were spin-coated onto a silicon wafer to a thickness of 0.6 μm and then pre-baked on a hot plate at 100°C for 3 minutes. Exposure was performed using a KrF scanner (248 nm) at 200 mJ / cm². 2 The formed film was exposed. Then, 0.2% tetramethylammonium hydroxide (TMAH) was used in a developer (SVS, SSP-200) to remove unexposed areas to form a colored pattern. It was then post-baked on a hot plate at 230°C for 5 minutes.

[0322] The developability of the obtained colored patterns was evaluated by examining the formation of patterns and surrounding residues using a Hitachi critical dimension-scanning electron microscopy (CD-SEM), and the results are shown in Table 2.

[0323] (Table 2)

[0324] radioactivity Example 1 ◎ Example 2 ○ Example 3 ◎ Comparative Example 1 X Comparative Example 2 X Comparative Example 3 △ Comparative Example 4 △

[0325] (standard)

[0326] ◎: No residue;

[0327] ○: Only slight residue remains around the pattern;

[0328] △: Residue was found throughout the area;

[0329] X: Not developed.

[0330] As can be seen from Table 2, the photosensitive resin compositions of Examples 1 to 3, which contain high amounts of the core-shell compounds according to the above embodiments, have excellent developability, making the photosensitive resin compositions very suitable for CMOS image sensors or OLED devices.

[0331] In summary, CMOS image sensors are trending towards increasing pixel count and decreasing size to achieve high resolution and smaller device size. As pixels become smaller, there may be limitations in using pigments to create intricate patterns, and therefore, dyes can be considered to compensate for this. However, dyes may present problems with processability during pattern creation compared to pigments. For example, dyes may have issues with chemical resistance because pigments are fine-particle and crystalline, resulting in insufficient solubility and thus not eluting in solvents such as PGMEA after baking, while dyes are amorphous solids and therefore dissolve in solvents after baking. CMOS image sensors can use high concentrations of colorants and therefore use binder resins or monomers at relatively low ratios, and the chemical resistance of dyes can be difficult to improve. Some exemplary embodiments provide a core-shell compound constituting a green pixel in a color filter for a CMOS image sensor.

[0332] Some exemplary embodiments may provide a photosensitive resin composition comprising the compound.

[0333] Some exemplary embodiments may provide a photosensitive resin layer made using a photosensitive resin composition.

[0334] Some exemplary embodiments may provide a color filter that includes a photosensitive resin layer.

[0335] Some exemplary embodiments may provide a CMOS image sensor including a color filter.

[0336] The core-shell compound according to some exemplary embodiments can itself have excellent developability and retain excellent developability even after curing and heat treatment, and the photosensitive resin composition containing the core-shell compound as a dye can form fine patterns and provide a green filter for CMOS image sensors.

[0337] Exemplary embodiments have been disclosed herein, and although specific terminology has been used, it is used in a general and illustrative sense only and should be interpreted in that general and illustrative sense, and is not intended to be limiting. In some instances, it will be apparent to those skilled in the art at the time of filing this application that, unless otherwise specifically stated, features, characteristics, and / or elements set forth in connection with particular embodiments may be used alone or in combination with features, characteristics, and / or elements set forth in connection with other embodiments. Therefore, those skilled in the art will understand that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the foregoing claims.

Claims

1. A core-shell compound comprising a core represented by chemical formula 1 and a shell surrounding said core, said shell being represented by chemical formula 2: [Chemical Formula 1] [Chemical Formula 2] Among them, in chemical formula 1 and chemical formula 2, R 1 It is a thermosetting group. R 2 and R 3 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group. L 1 and L 6 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, or a group represented by the chemical formula L, with the restriction that L is... 1 and L 6 At least one of them is a group represented by the chemical formula L. L 2 L 4 L a and L b Each is independently a single bond, or a substituted or unsubstituted C1 to C10 alkylene group. L 3 It is a single bond, or an ester group represented by *-C(=O)O-* or *-OC(=O)-*. L 5 It is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and n is an integer greater than or equal to 2. [Chemical formula L] In the chemical formula L, L 7 It is a substituted or unsubstituted C1 to C10 alkylene group, and m is an integer from 2 to 10.

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

3. The core-shell compound according to claim 1, wherein: R 1 It is a thermosetting group. R 2 and R 3 Each is independently a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group. L 1 and L 5 Each is independently a substituted or unsubstituted C1 to C10 alkylene group. L 2 To L 4 Each is an independent single bond, and L 6 It is a group represented by the chemical formula L.

4. The core-shell compound according to claim 1, wherein: R 1 It is a thermosetting group. R 2 and R 3 Each is independently a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group. L 1 It is a group represented by the chemical formula L. L 2 L 4 and L 6 Each is independently a substituted or unsubstituted C1 to C10 alkylene group. L 3 For ester groups represented by *-C(=O)O-* or *-OC(=O)-*, and L 5 It is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.

5. The core-shell compound according to claim 1, wherein: R 1 It is a thermosetting group. R 2 and R 3 Each is independently a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group. L 1 and L 6 Each is an independent group represented by the chemical formula L. L 2 and L 4 Each is independently a substituted or unsubstituted C1 to C10 alkylene group. L 3 For ester groups represented by *-C(=O)O-* or *-OC(=O)-*, and L 5 It is a substituted or unsubstituted C1 to C10 alkylene group.

6. The core-shell compound according to claim 1, wherein the core represented by chemical formula 1 has a maximum absorption wavelength 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 chemical formula 2-1: [Chemical Formula 2-1] 8. The core-shell compound according to claim 1, wherein the core-shell compound is represented by one of chemical formulas A to C: [Chemical Formula A] [Chemical Formula B] [Chemical formula C] 9. The core-shell compound according to claim 1, wherein the core-shell compound is a green dye.

10. A photosensitive resin composition comprising the core-shell compound as described in claim 1.

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

12. The photosensitive resin composition of claim 10, wherein the photosensitive resin composition is used in a complementary metal-oxide-semiconductor image sensor.

13. A photosensitive resin layer, manufactured using the photosensitive resin composition as described in claim 10.

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

15. A complementary metal-oxide-semiconductor image sensor, comprising the color filter as claimed in claim 14.

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