Nuclear-shell compound, resin composition and layer thereof, optical filter, and image sensor

Abstract

Disclosed are a core-shell compound including a squarylium inner ylidic core including three or more (meth)acrylate groups and a shell surrounding the squarylium inner ylidic core, a photosensitive resin composition including 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 (CMOS) image sensor including the color filter.

Description

[0001] [Cross-reference to related applications]

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2020-0186683, filed on December 29, 2020, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates 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 comprising the photosensitive resin layer, and a complementary metal-oxide-semiconductor (CMOS) image sensor comprising 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, there is a demand for next-generation detectors capable of rapidly transmitting and receiving large amounts of information, necessitating the development of novel concept devices and systems. Specifically, 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] An image sensor, which is a semiconductor that converts photons into electrons and displays them on a display or stores them in a storage device, consists of a light-receiving element that converts light signals into electrical signals, a pixel circuit section that amplifies and compresses the converted electrical signals, and an application-specific integrated circuit (ASIC) section that converts these pre-processed analog signals into digital signals to process image signals. Examples of such sensors include CCD, CMOS, and contact image sensors (CIS).

[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. More specifically, a CCD image sensor moves electrons generated by light to the output unit exactly as they are generated using a gate pulse, while a CMOS image sensor converts the electrons generated by light into a voltage in each pixel and then outputs it through several CMOS switches. These image sensors have a wide range of applications, from consumer products such as digital cameras and mobile phones to endoscopes used in hospitals and telescopes used in satellites orbiting the Earth.

[0007] CMOS image sensors have evolved along the technological trend of increasing pixel count and reducing size to achieve high resolution and miniaturize devices. However, as pixels become smaller, the creation of intricate patterns using pigments becomes limited, necessitating the development of dyes to compensate for this need. However, dyes present challenges in processability during pattern creation compared to pigments. Specifically, dyes suffer from chemical resistance issues because pigments are fine-particle and crystalline, resulting in insufficient solubility and thus not eluting in solvents such as propylene glycol methyl ether acetate (PGMEA) after baking. Dyes, on the other hand, are amorphous solids and therefore dissolve in solvents after baking. In particular, the chemical resistance of dyes is difficult to improve due to the high content of colorants used in CMOS image sensors and the relatively low ratio of binder resins or monomers. Summary of the Invention

[0008] One embodiment provides a core-shell compound that forms a green pixel in a color filter for a CMOS image sensor.

[0009] Another embodiment provides a photosensitive resin composition comprising the compound.

[0010] Another embodiment provides a photosensitive resin layer manufactured using the aforementioned photosensitive resin composition.

[0011] Another embodiment provides a color filter including the photosensitive resin layer.

[0012] Another embodiment provides a CMOS image sensor including the color filter.

[0013] One embodiment provides a core-shell compound comprising a squaric acid inneronium core containing three or more (meth)acrylate groups and a shell surrounding the squaric acid inneronium core.

[0014] The squaric acid endomonium system core may include four or more (meth)acrylate groups.

[0015] The owner of the three or more (meth)acrylate groups may be present as a substituent for an alkyl group constituting a squaric acid endomonium core, or as a substituent for an alkoxy group constituting a squaric acid endomonium core.

[0016] At least one of the three or more (meth)acrylate groups may be present as a substituent for the aryl group constituting the squaric acid mesonoside core, and at least one of the three or more (meth)acrylate groups may be present as a substituent for the alkyl or alkoxy group constituting the squaric acid mesonoside core.

[0017] The squaric acid inneronium system core can be represented by chemical formula 1.

[0018] [Chemical Formula 1]

[0019]

[0020] In chemical formula 1,

[0021] R 1 To R 8 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, provided that R 1 To R 8 They are not both hydrogen atoms.

[0022] R 1 R 2 R 5 and R 6 At least one of them contains a (meth)acrylate group at the end.

[0023] R 3 R 4 R 7 and R 8 At least two or more of them contain (meth)acrylate groups at the end, and

[0024] n1, n2, n3, and n4 are each independent integers from 0 to 2, where n1 + n2 ≠ 0 and n3 + n4 ≠ 0.

[0025] R 1R 2 R 5 and R 6 Any two of them and R 3 R 4 R 7 and R 8 Either of the two groups may independently contain a (meth)acrylate group at its end.

[0026] R 1 R 2 R 5 and R 6 Any three of them and R 3 R 4 R 7 and R 8 Any three of them may independently contain a (meth)acrylate group at their end.

[0027] Chemical formula 1 can be represented by chemical formula 1-1.

[0028] [Chemical Formula 1-1]

[0029]

[0030] In chemical formula 1-1,

[0031] R 2 R 4 R 6 and R 8 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, provided that R 1 To R 4 R 6 and R 8 They are not both hydrogen atoms.

[0032] R 2 R 4 R 6 and R 8 The owner of the product does not contain (meth)acrylate groups.

[0033] R 1 R 3 R 5 and R 7 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0034] n5 and n6 are each an independent integer from 0 to 2.

[0035] Chemical formula 1 can be represented by chemical formula 1-2.

[0036] [Chemical Formula 1-2]

[0037]

[0038] In chemical formulas 1-2,

[0039] R 6 and R 8 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, R 6 With R 8 They are not both hydrogen atoms.

[0040] R 6 With R 8 Neither of them contains (meth)acrylate groups.

[0041] R 1 To R 4 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0042] n5 and n6 are each an independent integer from 0 to 2.

[0043] Chemical formula 1 can be represented by chemical formulas 1-3.

[0044] [Chemical Formulas 1-3]

[0045]

[0046] In chemical formulas 1-3,

[0047] R 6 and R 8 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, provided that R 6 With R 8 They are not both hydrogen atoms.

[0048] R 6 and R 8 It does not contain siloxane.

[0049] R 1 To R 5 and R 7 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0050] n5 and n6 are each an independent integer from 0 to 2.

[0051] The nucleus represented by chemical formula 1 has a maximum absorption wavelength in the range of approximately 610 nm to approximately 640 nm.

[0052] The shell can be represented by chemical formula 2.

[0053] [Chemical Formula 2]

[0054]

[0055] In chemical formula 2,

[0056] L a and L b Each is independently a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and

[0057] n is an integer greater than or equal to 2.

[0058] The shell represented by chemical formula 2 can also be represented by chemical formula 2-1.

[0059] [Chemical Formula 2-1]

[0060]

[0061] The core-shell compound may be represented by any of the chemical formulas A to N.

[0062] [Chemical Formula A]

[0063]

[0064] [Chemical Formula B]

[0065]

[0066] [Chemical formula C]

[0067]

[0068] [Chemical formula D]

[0069]

[0070] [Chemical Formula E]

[0071]

[0072] [Chemical formula F]

[0073]

[0074] [Chemical formula G]

[0075]

[0076] [Chemical formula H]

[0077]

[0078] [Chemical Formula I]

[0079]

[0080] [Chemical Formula J]

[0081]

[0082] [Chemical formula K]

[0083]

[0084] [Chemical formula L]

[0085]

[0086] [Chemical Formula M]

[0087]

[0088] [Chemical formula N]

[0089]

[0090] In chemical formulas A to N

[0091] R 9 It is a hydrogen atom, or a substituted or unsubstituted C1 to C10 alkyl group.

[0092] The compound may be a green dye.

[0093] Another embodiment provides a photosensitive resin composition comprising the compound.

[0094] The compound may be contained in an amount from about 15% by weight (wt%) to about 30% by weight, based on the total amount of the photosensitive resin composition.

[0095] The photosensitive resin composition may further comprise an adhesive resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

[0096] The photosensitive resin composition can be used in CMOS image sensors.

[0097] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0098] Another embodiment provides a color filter including the photosensitive resin layer.

[0099] Another embodiment provides a CMOS image sensor including the color filter.

[0100] Other embodiments of this disclosure are included in the following detailed description.

[0101] According to one embodiment, the core-shell compound itself has excellent chemical resistance, and therefore maintains improved chemical resistance even after curing and heat treatment. Thus, the photosensitive resin composition containing the core-shell compound as a dye can form fine patterns, thereby providing a green filter for CMOS image sensors. Detailed Implementation

[0102] Embodiments of this disclosure will be described in detail below. However, these embodiments are exemplary, and this disclosure is not limited thereto, and is defined by the scope of the claims.

[0103] 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.

[0104] 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. The term “or” as used herein is not an exclusive term; for example, “A or B” includes A, B, or A and B.

[0105] Unless otherwise defined, “(meth)acrylate” as used herein refers to “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylic acid”.

[0106] Unless otherwise defined, the term “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.

[0107] In the chemical formulas of this specification, unless otherwise specifically defined, hydrogen is bonded at the positions where chemical bonds should be given but are not shown.

[0108] In this specification, unless otherwise specifically defined, " "Points that indicate the connection between the same or different atoms or chemical formulas."

[0109] One embodiment provides a core-shell compound comprising a squaric acid inneronium core containing three or more (e.g., four or more) (meth)acrylate groups and a shell surrounding the squaric acid inneronium core.

[0110] Color filters formed from pigment-based photosensitive resin compositions suffer from color mixing problems due to limitations in pigment particle size and film-thinning. Furthermore, color imaging devices used in image sensors require small particle sizes to form intricate patterns. To meet this requirement, efforts have long been focused on improving resolution by introducing non-particulate dyes to replace pigments in the preparation of dye-compatible photosensitive resin compositions.

[0111] This disclosure relates to a green dye in a color filter for use in a CMOS image sensor. Due to the small size of pixels, the fabrication of fine patterns using pigments is limited, and therefore, there is a need to develop a dye to compensate for this limitation. However, due to problems with the processability of dyes during pattern fabrication, and specifically exhibiting significantly deteriorated chemical resistance, it is very difficult to form fine patterns after curing and heat treatment. Furthermore, when a small amount of dye as a colorant is contained in the total composition, the chemical resistance of the dye itself is slightly insufficient but not a major problem. However, when the photosensitive resin composition for a CMOS image sensor contains an excessive amount (approximately 15% to 30% by weight, for example, approximately 16% to 27% by weight) of dye, there is a strong need to develop dyes with excellent chemical resistance.

[0112] After numerous trials and errors, the inventors have synthesized a core-shell compound by introducing three or more (e.g., four or more) (meth)acrylate groups into a squaric acid intraonium compound forming a core under specific control and surrounding the core with a shell. Since the core-shell compound according to the embodiments has excellent chemical resistance, the photosensitive resin composition containing an excess of such compound as a green dye does not show a significant deterioration in chemical resistance even after curing and heat treatment, and is therefore very suitable for use as a green filter for CMOS image sensors.

[0113] (Meth)acrylate groups can be represented by the chemical formula S.

[0114] [Chemical formula S]

[0115]

[0116] In the chemical formula S,

[0117] R 9 It is a hydrogen atom, or a substituted or unsubstituted C1 to C10 alkyl group.

[0118] For example, the owner of the three or more (meth)acrylate groups may be present as a substituent for an alkyl group constituting a squaric acid endomonium core, or as a substituent for an alkoxy group constituting a squaric acid endomonium core.

[0119] For example, at least one of the three or more (meth)acrylate groups may be present as a substituent for an aryl group constituting a squaric acid endomonium core, and at least one of the three or more (meth)acrylate groups may be present as a substituent for an alkyl or alkoxy group constituting a squaric acid endomonium core.

[0120] When the three or more (e.g., four or more) (meth)acrylate groups are controlled under the positional conditions described above, the durability of the core-shell dye itself according to the embodiments can be further improved.

[0121] For example, the squaric acid endothelial nucleus can be represented by chemical formula 1.

[0122] [Chemical Formula 1]

[0123]

[0124] In chemical formula 1,

[0125] R 1 To R 8 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, provided that R1 To R 8 They are not both hydrogen atoms.

[0126] R 1 R 2 R 5 and R 6 At least one of them contains a (meth)acrylate group at the end.

[0127] R 3 R 4 R 7 and R 8 At least two or more of them contain (meth)acrylate groups at the end, and

[0128] n1, n2, n3, and n4 are each independent integers from 0 to 2, where n1 + n2 ≠ 0 and n3 + n4 ≠ 0.

[0129] For example, in chemical formula 1, R 1 R 2 R 5 and R 6 Any two of them and R 3 R 4 R 7 and R 8 Either of the two can independently contain a (meth)acrylate group at its end. More specifically, Formula 1 can be represented by Formula 1-1 or Formula 1-2.

[0130] [Chemical Formula 1-1]

[0131]

[0132] In chemical formula 1-1,

[0133] R 2 R 4 R 6 and R 8 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, provided that R 1 To R 4 R 6 and R 8 They are not both hydrogen atoms.

[0134] R 2 R 4 R 6 and R 8 The owner of the product does not contain (meth)acrylate groups.

[0135] R 1R 3 R 5 and R 7 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0136] n5 and n6 are each an independent integer from 0 to 2.

[0137] [Chemical Formula 1-2]

[0138]

[0139] In chemical formulas 1-2,

[0140] R 6 and R 8 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, provided that R 6 With R 8 They are not both hydrogen atoms.

[0141] R 6 and R 8 The owner of the product does not contain (meth)acrylate groups.

[0142] R 1 To R 4 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0143] n5 and n6 are each an independent integer from 0 to 2.

[0144] For example, in chemical formula 1, R 1 R 2 R 5 and R 6 Any three of them and R 3 R 4 R 7 and R 8 Any three of them may independently contain a (meth)acrylate group at their end. More specifically, Formula 1 may be represented by Formulas 1-3.

[0145] [Chemical Formulas 1-3]

[0146]

[0147] In chemical formulas 1-3,

[0148] R 6 and R8 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, provided that R 6 With R 8 They are not both hydrogen atoms.

[0149] R 6 and R 8 It does not contain siloxane.

[0150] R 1 To R 5 and R 7 Each is independently a C1 to C20 alkyl group containing a (meth)acrylate group at the end or a C1 to C20 alkoxy group containing a (meth)acrylate group at the end, and

[0151] n5 and n6 are each an independent integer from 0 to 2.

[0152] The core represented by Formula 1 may include three or more (e.g., three, four, five, or six) (meth)acrylate groups. For example, the core represented by Formula 1 may include four or six (meth)acrylate groups. Compared to structures having two or fewer (meth)acrylate groups, the core represented by Formula 1, which includes three or five (meth)acrylate groups, exhibits excellent compound durability, but is difficult to synthesize due to its structure (low yield). Even if actual synthesis is successful, it may be undesirable in terms of economic efficiency when applied to actual production lines due to high costs.

[0153] Furthermore, the more (meth)acrylate groups contained in the core represented by Formula 1, the better the chemical resistance. In other words, when considering only the chemical resistance of the compound, the core represented by Formula 1 may contain four (meth)acrylate groups instead of three, five (meth)acrylate groups instead of the four (meth)acrylate groups, and six (meth)acrylate groups instead of the five (meth)acrylate groups.

[0154] On the other hand, when one or two (meth)acrylate groups are included in the core represented by Formula 1, the chemical resistance may be greatly degraded, and in addition, when one (meth)acrylate group is included, it is difficult to synthesize as described above, so the core represented by Formula 1 contains three or more (meth)acrylate groups.

[0155] In other words, in terms of the chemical resistance and ease of synthesis of the compound, the core represented by Formula 1 may contain four or more (meth)acrylate groups, for example, four or six (meth)acrylate groups.

[0156] For example, the nucleus represented by Formula 1 may have a maximum absorption wavelength at about 610 nm to about 640 nm. When a dye compound that has excellent solubility in organic solvents, even at a rate of more than or equal to about 10%, does not have a maximum absorption wavelength at about 610 nm to about 640 nm, it may be unsuitable for use in green photosensitive resin compositions for CMOS image sensors due to its low transmittance.

[0157] The shell can be represented by chemical formula 2.

[0158] [Chemical Formula 2]

[0159]

[0160] In chemical formula 2,

[0161] L a and L b Each is independently a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and

[0162] n is an integer greater than or equal to 2.

[0163] The shell represented by chemical formula 2 can also be represented by chemical formula 2-1.

[0164] [Chemical Formula 2-1]

[0165]

[0166] For example, core-shell compounds can be represented by any of the chemical formulas A to N, but are not necessarily limited to these.

[0167] [Chemical Formula A]

[0168]

[0169] [Chemical Formula B]

[0170]

[0171] [Chemical formula C]

[0172]

[0173] [Chemical formula D]

[0174]

[0175] [Chemical Formula E]

[0176]

[0177] [Chemical formula F]

[0178]

[0179] [Chemical formula G]

[0180]

[0181] [Chemical formula H]

[0182]

[0183] [Chemical Formula I]

[0184]

[0185] [Chemical Formula J]

[0186]

[0187] [Chemical formula K]

[0188]

[0189] [Chemical formula L]

[0190]

[0191] [Chemical Formula M]

[0192]

[0193] [Chemical formula N]

[0194]

[0195] In chemical formulas A to N

[0196] R 9 It is a hydrogen atom, or a substituted or unsubstituted C1 to C10 alkyl group.

[0197] For example, core-shell compounds can be green dyes.

[0198] According to another embodiment, a photosensitive resin composition comprising a core-shell compound according to the embodiment is provided.

[0199] For example, the photosensitive resin composition may have a transmittance of greater than or equal to about 90% at 540 nm, a transmittance of less than or equal to about 10% at 600 nm to 640 nm, and a transmittance of less than or equal to about 5% at 450 nm, and therefore is suitable for realizing a green filter for high-transmittance CIS. That is, the photosensitive resin composition can be used in high-transmittance CMOS image sensors.

[0200] The photosensitive resin composition may further comprise a core-shell compound, an adhesive resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

[0201] The core-shell compound according to the embodiments may be included in an amount from about 15% to about 30% by weight, for example, from about 16% to about 27% by weight, based on the total amount of the photosensitive resin composition. When the core-shell compound according to the embodiments is included within the above range, color reproducibility and contrast ratio are improved, and it may be possible to apply it to CMOS image sensors.

[0202] The photosensitive resin composition may further comprise pigments, such as yellow pigments, green pigments, or combinations thereof.

[0203] Yellow pigments can be classified 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.

[0204] 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.

[0205] Pigments can be contained in the photosensitive resin composition in the form of pigment dispersions.

[0206] Pigment dispersions may include solid pigments, solvents, and dispersants for uniformly dispersing pigments in the solvent.

[0207] The total amount of the pigment dispersion may include solid pigments in amounts ranging from about 1% to about 20% by weight, for example, from about 8% to about 20% by weight, for example, from about 8% to about 15% by weight, for example, from about 10% to about 20% by weight, for example, from about 10% to about 15% by weight.

[0208] Dispersants can be nonionic, anionic, cationic, etc. Specific examples of dispersants include polyalkylene glycols and their esters, polyoxyalkylene glycols, polyol ester epoxy alkyl addition products, alcohol epoxy alkyl addition products, sulfonates, sulfonates, carboxylic esters, carboxylates, alkylamide epoxy alkyl addition products, alkylamines, etc., and these dispersants can be used alone or as a mixture of two or more of them.

[0209] Commercially available examples of dispersants may include 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.

[0210] The dispersant may be included in an amount from about 1% to about 20% by weight, based on the total amount of the pigment dispersion. When a dispersant is included within this range, the dispersion of the photosensitive resin composition is improved due to the suitable viscosity, and therefore the optical, physical, and chemical qualities can be maintained when the photosensitive resin composition is applied to a product.

[0211] Solvents used to form pigment dispersions may include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc.

[0212] The pigment dispersion may be included in an amount from about 10% to about 20% by weight, for example, from about 12% to about 18% by weight, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included within the above range, it is advantageous to ensure a process margin and can result in improved color reproduction and contrast.

[0213] The adhesive resin may be an acrylic adhesive resin.

[0214] The acrylic adhesive resin is a copolymer of a first ethylene-based unsaturated monomer and a second olefin-based unsaturated monomer that can copolymerize therewith, and is a resin containing at least one repeating acrylic unit.

[0215] The first vinyl unsaturated monomer may be an vinyl unsaturated monomer containing at least one carboxyl group, and examples of said monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

[0216] The first ethylene-based unsaturated monomer may be contained in an amount from about 5% to about 50% by weight, for example from about 10% to about 40% by weight, based on the total amount of the acrylic adhesive resin.

[0217] The second vinyl unsaturated monomer may be: aromatic vinyl compounds, such as styrene, α-methylstyrene, vinyltoluene, vinylbenzene methyl ether, etc.; unsaturated carboxylic acid ester compounds, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, etc.; unsaturated aminoalkyl carboxylic acid ester compounds, such as 2-aminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, etc.; vinyl carboxylic acid ester compounds, such as vinyl acetate, vinyl benzoate, etc.; unsaturated glycidyl carboxylic acid ester compounds, such as glycidyl methacrylate, etc.; acrylonitrile compounds, such as methacrylonitrile, etc.; unsaturated amide compounds, such as methacrylamide, etc.; etc., and the second vinyl unsaturated monomer may be used alone or as a mixture of two or more thereof.

[0218] Specific examples of acrylic adhesive resins may be (meth)acrylic acid / benzyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene copolymers, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymers, etc., but are not limited thereto, and these materials may be used alone or as a mixture of two or more of them.

[0219] 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, for example from about 20,000 g / mol to about 30,000 g / mol. When the adhesive resin has a weight-average molecular weight within the said range, the photosensitive resin composition has good physical and chemical properties, suitable viscosity, and good adhesion to the substrate during the manufacture of color filters.

[0220] The acid value of the adhesive resin can be from about 15 mgKOH / g to about 60 mgKOH / g, for example from about 20 mgKOH / g to about 50 mgKOH / g. When the acid value of the adhesive resin is within the range described above, the resolution of the pixel pattern is improved.

[0221] 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 amount of the photosensitive resin composition. When the binder resin is included in the range described above, the composition may have excellent developability and improved crosslinking properties, and therefore excellent surface flatness when manufactured into a color filter.

[0222] Photopolymerizable monomers can be monofunctional or polyfunctional esters of (meth)acrylic acid containing at least one ethylene-based unsaturated double bond.

[0223] Photopolymerizable monomers have vinyl-based unsaturated double bonds, and therefore can induce sufficient polymerization during exposure in the patterning process to form patterns with excellent heat resistance, light resistance and chemical resistance.

[0224] 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, 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.

[0225] Examples of commercially available photopolymerizable monomers are as follows. Monofunctional (meth)acrylates may include Aronix M-101. ® M-111 ® M-114 ® (Toagosei Chemistry Industry Co., Ltd.); KAYARAD TC-110S ® TC-120S ®(Nippon Kayaku Co., Ltd.); V-158 ® V-2311 ® (Osaka Organic Chemical Industry, Ltd.) etc. Examples of difunctional (meth)acrylates may include Yronis M-210. ® M-240 ® M-6200 ® (Dong-A Synthetic Chemical Co., Ltd.), Kayalade HDDA ® HX-220 ® R-604 ® (Nippon Kayaku Co., Ltd.), V-260 ® V-312 ® V-335 HP ® (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Arones M-309 from Toa Synthetic Chemical Co., Ltd. ® M-400 ® M-405 ® M-450 ® M-710 ® M-8030 ® M-8060 ® etc.; Kayarad TMPTA from Nippon Kayaku Co., Ltd. ® DPCA-20 ® DPCA-30 ® DPCA-60 ® DPCA-120 ® V-295 from Osaka Yuki Kayaku Kogyo Co. Ltd. ® V-300 ® V-360 ® V-GPT ® V-3PA ® V-400 ® These photopolymerizable monomers can be used alone or as a mixture of two or more.

[0226] Photopolymerizable monomers can be treated with acid anhydrides to improve their developability.

[0227] 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 amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the range described above, the photopolymerizable monomer is fully cured during exposure in the patterning process and exhibits excellent reliability, and improves the developability of alkaline developing solutions.

[0228] Photopolymerization initiators can be commonly used in photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0229] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropinophenone, 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.

[0230] Examples of benzophenone compounds include benzoyl benzoate, benzoyl benzoate, benzoyl 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.

[0231] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0232] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0233] 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.

[0234] Examples of oxime compounds include O-acyloxime compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone, 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-phenylthiophenyl)-but-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, and 1-(4-phenylthiophenyl)-but-1-one oxime-O-acetate, etc.

[0235] In addition to the compounds mentioned above, photopolymerization initiators may further include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc.

[0236] Photopolymerization initiators can be used with photosensitizers that can induce a chemical reaction by absorbing light, being excited, and subsequently transferring their energy.

[0237] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0238] 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 amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range described above, sufficient photopolymerization occurs 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.

[0239] The solvent is a material that is compatible with the core-shell compound, the pigment according to the embodiment, the adhesive resin, the photopolymerizable monomer, and the photopolymerization initiator but does not react with them.

[0240] 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.; cellolytic acetates, such as methyl cellolytic acetate, ethyl cellolytic acetate, diethyl cellolytic acetate, 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, etc. 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, 3... -Ethyl methoxypropionate, 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 cellosolve acetate, etc.

[0241] 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 cellosolve 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.

[0242] The solvent may be included in a balanced amount (e.g., from about 30% to about 80% by weight) based on the total amount of the photosensitive resin composition. When the solvent is included within the range described above, the photosensitive resin composition may have a suitable viscosity, thereby improving the coating characteristics of the color filter.

[0243] According to another embodiment, the photosensitive resin composition may further include an epoxy compound to improve its close contact properties with the substrate.

[0244] Examples of epoxy compounds may include phenolic aldehyde epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0245] 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. When an epoxy compound is included within the range described above, the contact properties, storage properties, etc., can be improved.

[0246] In addition, the photosensitive resin composition may further include a silane coupling agent having reactive substituents (such as carboxyl, methacryloyl, isocyanate, epoxy, etc.) to improve its adhesion to the substrate.

[0247] Examples of silane-based 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.

[0248] Based on 100 parts by weight of the photosensitive resin composition, a silane coupling agent may be included in an amount from about 0.01 parts by weight to about 10 parts by weight. When a silane coupling agent is included within the range described above, it can improve contact properties, storage properties, etc.

[0249] In addition, the photosensitive resin composition may further contain surfactants to improve coating properties and prevent defects when necessary.

[0250] Examples of surfactants include commercially available fluorinated surfactants, such as BM-1000 from BM Chemie Inc. ® BM-1100 ® etc.; F 142D of Dainippon Ink Kagaku Kogyo Co., Ltd. ® F 172 ® F 173 ® F 183 ® etc.; FULORAD FC-135 from Sumitomo 3M Co., Ltd. ® FC-170C ® FC-430 ® FC-431 ® etc.; SURFLON S-112 from Asahi Glass Co., Ltd. ® S-113 ® S-131 ® S-141 ® S-145 ® etc.; SH-28PA ® SH-190 ® SH-193 ® SZ-6032 ® SF-8428 ® wait.

[0251] The surfactant may be included in an amount from about 0.001 parts by weight to about 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the range described above, coating uniformity is ensured, no stains are found, and the wetting properties of the glass substrate are improved.

[0252] In addition, unless the properties deteriorate, the photosensitive resin composition may further contain other additives, such as oxidation inhibitors, stabilizers, etc., in a predetermined amount.

[0253] According to another embodiment, a photosensitive resin layer manufactured using the photosensitive resin composition according to the embodiment is provided.

[0254] According to another embodiment, a color filter including the photosensitive resin layer is provided.

[0255] The pattern formation process in color filters is as follows.

[0256] The process includes: coating a photosensitive resin composition according to the embodiment onto a support substrate using methods such as spin coating, slot coating, or 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. The conditions for the patterning process are well known in the relevant art and will not be described in detail in this specification.

[0257] Another embodiment provides a CMOS image sensor including a color filter.

[0258] The present disclosure is illustrated in more detail below with reference to examples, but these examples are not to be construed in any way as limiting the scope of the disclosure.

[0259] (Compound Synthesis)

[0260] Synthesis Example 1: Synthesis of a compound represented by chemical formula A

[0261]

[0262] 0.1 mol of 4-hydroxydiphenylamine, 0.15 mol of hydroxyacetone, 0.02 mol of SnCl₂2H₂O, and 0.2 mol of poly(methyl)hydrosiloxane were added to methanol, and the mixture was then heated and stirred at 60 °C for 10 hours. The resulting polymer was removed by filtration, and the residue was extracted with ethyl acetate after distillation of a portion of the methanol under reduced pressure, followed by washing with 10% HCl and water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate 1.

[0263] Intermediate 1 (0.05 mol) and Et3N (0.11 mol) were added to dichloromethane. After correcting the temperature to 0 °C, methacryloyl chloride (1.05 mol) was slowly added dropwise while stirring for 2 hours. The resulting product was extracted with dichloromethane and washed with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate 2.

[0264]

[0265] Intermediate 2 (0.01 mol), squaric acid (0.05 mol), and triethylorthoformate (TEOF) (0.15 mol) were added to pentanol, and the mixture was then heated and stirred at 90 °C for 7 hours. After distilling off pentanol under reduced pressure, the residue was purified by column chromatography to obtain intermediate 3.

[0266]

[0267] (Encapsulation method) Intermediate 3 (5 mmol) was dissolved in 600 mL of chloroform, and a solution prepared by dissolving 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) in 60 mL of chloroform was added dropwise to it at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and then columnarized to synthesize the compound represented by chemical formula A.

[0268] [Chemical Formula A]

[0269]

[0270] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (Maldi-Tof MS): R 9 = Methyl (1370.53) m / z

[0271] Maldi-Tof MS:R 9 =H(1314.47)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0272] Synthesis Example 2: Synthesis of a compound represented by chemical formula B

[0273] Except for the use of 5-hydroxy-2-pentanone, the compound represented by chemical formula B was synthesized in the same manner as in Synthesis Example 1.

[0274] [Chemical Formula B]

[0275]

[0276] Maldi-Tof MS:R 9 =Methyl (1426.59) m / z

[0277] Maldi-Tof MS:R 9 =H(1370.52)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0278] Synthesis Example 3: Synthesis of compounds represented by chemical formula C

[0279] Except for the use of 2,3-dimethyl-4-hydroxydiphenylamine, compounds represented by chemical formula C were synthesized in the same manner as in Synthesis Example 1.

[0280] [Chemical formula C]

[0281]

[0282] Maldi-Tof MS:R 9 =Methyl (1426.59) m / z

[0283] Maldi-Tof MS:R 9 =H(1370.53)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0284] Synthesis Example 4: Synthesis of a compound represented by chemical formula D

[0285] Except for the use of 2,3-dimethyl-4-hydroxydiphenylamine and 5-hydroxy-2-pentanone, the compound represented by chemical formula D was synthesized in the same manner as in Synthesis Example 1.

[0286] [Chemical formula D]

[0287]

[0288] Maldi-Tof MS:R 9 =Methyl (1482.65) m / z

[0289] Maldi-Tof MS:R 9 =H(1426.59)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0290] Synthesis Example 5: Synthesis of a compound represented by chemical formula E

[0291] Except for the use of 4-methyl-3-hydroxydiphenylamine and hydroxyacetone, the compound represented by chemical formula E was synthesized in the same manner as in Synthesis Example 1.

[0292] [Chemical Formula E]

[0293]

[0294] Maldi-Tof MS:R 9 =Methyl (1398.56) m / z

[0295] Maldi-Tof MS:R 9 =H(1342.50)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0296] Synthesis Example 6: Synthesis of a compound represented by chemical formula F

[0297] Except for the use of 4-methyl-3-hydroxydiphenylamine and 5-hydroxy-2-pentanone, compounds represented by chemical formula F were synthesized in the same manner as in Synthesis Example 1.

[0298] [Chemical formula F]

[0299]

[0300] Maldi-Tof MS:R 9 =Methyl (1454.62) m / z

[0301] Maldi-Tof MS:R 9 =H(1398.56)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0302] Synthesis Example 7: Synthesis of a compound represented by the chemical formula G

[0303]

[0304] 4-Hydroxydiphenylamine (0.1 mol), 2-iodoethanol (0.12 mol), and K₂CO₃ (0.15 mol) were added to acetone, and the mixture was then heated and stirred at 50 °C for 12 hours. The resulting mixture was extracted with ethyl acetate and washed with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate 1.

[0305] Other processes (such as intermediate synthesis) were performed using the same method as in Synthesis Example 1 to synthesize the compound represented by chemical formula G.

[0306] [Chemical formula G]

[0307]

[0308] Maldi-Tof MS:R 9 =Methyl (1486.61) m / z

[0309] Maldi-Tof MS:R 9 =H(1430.55)m / z (In this case, acryloyl chloride can be used instead of methacryloyl chloride.)

[0310] Synthesis Example 8: Synthesis of a compound represented by the chemical formula H

[0311] Except for the use of 5-hydroxy-2-pentanone, compounds represented by chemical formula H were synthesized in the same manner as in Synthesis Example 7.

[0312] [Chemical formula H]

[0313]

[0314] Maldi-Tof MS:R 9 =Methyl (1514.67) m / z

[0315] Maldi-Tof MS:R 9 =H(1456.60)m / z (In this case, acryloyl chloride can be used instead of methacryloyl chloride.)

[0316] Synthesis Example 9: Synthesis of a compound represented by chemical formula I

[0317] Except for the use of 1-bromobutane and 1,3-dihydroxyacetone, the compound represented by chemical formula I was synthesized in the same manner as in Synthesis Example 1.

[0318] [Chemical Formula I]

[0319]

[0320] Maldi-Tof MS:R 9 =Methyl (1514.64) m / z

[0321] Maldi-Tof MS:R 9 =H(1458.58)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0322] Synthesis Example 10: Synthesis of a compound represented by the chemical formula K

[0323] Except for the use of 1,3-dihydroxyacetone and 4-methyldiphenylamine, a compound represented by chemical formula K was synthesized in the same manner as in Synthesis Example 1.

[0324] [Chemical formula K]

[0325]

[0326] Maldi-Tof MS:R 9 =Methyl (1398.56) m / z

[0327] Maldi-Tof MS:R 9 =H(1342.50)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0328] Synthesis Example 11: Synthesis of a compound represented by chemical formula M

[0329] Except for the use of 4-hydroxydiphenylamine and 1,3-dihydroxyacetone, compounds represented by chemical formula M were synthesized in the same manner as in Synthesis Example 1.

[0330] [Chemical Formula M]

[0331]

[0332] Maldi-Tof MS:R 9 =Methyl (1538.57) m / z

[0333] Maldi-Tof MS:R 9 =H(1454.48)m / z (In this case, when synthesizing intermediate 2, acryloyl chloride can be used instead of methacryloyl chloride.)

[0334] Synthesis Example 12: Synthesis of compounds represented by the chemical formula O

[0335]

[0336] (Synthesis of Compound 1)

[0337] After adding 0.025 mol of thionyl chloride to squaric acid (0.01 mol), a small amount of dimethylformamide (DMF) was added, and the mixture was heated at 75 °C for 3 hours. After removing excess thionyl chloride by distillation, the residue was stirred at 80 °C in a methacrylic acid intermediate and toluene solvent for 16 hours. The result was extracted with ethyl acetate and washed with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain compound 1.

[0338] (Synthesis of compound 2)

[0339] Subsequently, acetic acid (8 times), distilled water (8 times), and hydrochloric acid (0.1 times) were added to intermediate 1 (0.01 mol), and the mixture was stirred at 130 °C for 16 hours. The result was extracted with ethyl acetate and washed with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain compound 2. "Times" refers to mass multiples; therefore, the mass of acetic acid is 8 times the mass of intermediate 1. The weight-average molecular weight of intermediate 1 is 243.3 g, therefore the mass of intermediate 1 (0.01 mol) is 2.433 g. In this case, the mass of acetic acid (8 times) is 19.464 g (2.433 g x 8).

[0340] Other processes (such as the synthesis of squaric acid endothelial dyes and encapsulation methods) are performed using the same method as in Example 1 to synthesize compounds represented by the chemical formula O.

[0341] [Chemical formula O]

[0342]

[0343] Maldi-Tof MS: 1342.57 m / z

[0344] Comparative Synthesis Example 1: Synthesis of Compounds Represented by Chemical Formula C-1

[0345] (1-Methylhexyl)-phenyl-p-tolyl-amine (100 mmol) and 3,4-dihydroxy-cyclobutane-3-ene-1,2-dione (50 mmol) were added to toluene (300 mL) and butanol (300 mL), and then refluxed. The resulting water was distilled off using a Dean-Stark distillation apparatus. The reaction mixture was stirred for 12 hours, distilled off under reduced pressure, and purified by column chromatography to obtain a squaric acid endothelioid compound. This compound (5 mmol) was dissolved in 600 mL of chloroform, and a solution prepared by dissolving pyridine-2,6-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) in 60 mL of chloroform was added dropwise to it at room temperature for 5 hours. After 12 hours, the mixture was distilled off under reduced pressure and then separated by column chromatography to obtain the compound represented by the chemical formula C-1.

[0346] [Chemical formula C-1]

[0347]

[0348] Maldi-tof MS: 1175.5 m / z

[0349] Comparative Synthesis Example 2: Synthesis of a compound represented by chemical formula C-2

[0350] 2-{(2-cyanoethyl)-[4-(2-hydroxy-3,4-dioxane-1-enyl)-phenyl]-amino}-ethyl propionate (60 mmol) and 1-(2-ethylhexyl)-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then refluxed. The water produced was removed using a Dean-Stark distillation apparatus. The resulting green reaction mixture was stirred for 12 hours, distilled under reduced pressure, and purified by column chromatography to obtain an asymmetric squaric acid endothelial compound. This compound (5 mmol) was dissolved in 600 mL of chloroform, and then pyridine-2,6-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform and added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the mixture obtained by distillation under reduced pressure was separated by column chromatography to obtain the compound represented by the chemical formula C-2.

[0351] [Chemical formula C-2]

[0352]

[0353] Maldi-tof MS: 1088.48 m / z

[0354] Comparative Synthesis Example 3: Synthesis of Compounds Represented by Chemical Formula C-3

[0355] Synthesis of starting materials

[0356]

[0357] 2,4-Dimethyldiphenylamine (0.1 mol), NaH (0.2 mol), and ethylene carbonate (0.2 mol) were heated in DMF solvent at 140 °C for 16 hours. The result was extracted with ethyl acetate and washed with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to synthesize the intermediate. Methacrylic acid was also synthesized using conventional methods. Furthermore, the same squaric acid-internium dye and encapsulation method as in Synthesis Example 1 were used to obtain the compound represented by chemical formula C-3.

[0358] [Chemical formula C-3]

[0359]

[0360] Maldi-tof MS: 1230.52 m / z

[0361] (Synthesis of photosensitive resin composition)

[0362] Example 1

[0363] The following components were mixed in each of the compositions shown in Table 1 to prepare the photosensitive resin composition according to Example 1.

[0364] Specifically, a photopolymerization initiator was dissolved in a solvent, and the solution was stirred at room temperature for 2 hours. An adhesive resin and a photopolymerizable monomer were then added, and the resulting mixture was stirred at room 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 then stirred at room temperature for 1 hour. The product was then filtered three times to remove impurities and a photosensitive resin composition was prepared.

[0365] (Table 1)

[0366] (Unit: weight %)

[0367]

[0368] Example 2

[0369] A photosensitive resin composition was prepared according to the same method as in Example 1, 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).

[0370] Example 3

[0371] A photosensitive resin composition was prepared according to the same method as in Example 1, 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.

[0372] Example 4

[0373] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 4 (represented by chemical formula D) was used instead of the compound according to Synthesis Example 1.

[0374] Example 5

[0375] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 5 (represented by chemical formula E) was used instead of the compound according to Synthesis Example 1.

[0376] Example 6

[0377] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 6 (represented by chemical formula F) was used instead of the compound according to Synthesis Example 1.

[0378] Example 7

[0379] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 7 (represented by chemical formula G) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0380] Example 8

[0381] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 8 (represented by chemical formula H) was used instead of the compound according to Synthesis Example 1.

[0382] Example 9

[0383] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 9 (represented by chemical formula I) was used instead of the compound according to Synthesis Example 1.

[0384] Example 10

[0385] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 10 (represented by chemical formula K) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0386] Example 11

[0387] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 11 (represented by chemical formula M) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0388] Example 12

[0389] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Synthesis Example 12 (represented by chemical formula O) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0390] Comparative Example 1

[0391] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Comparative Synthesis Example 1 (represented by chemical formula C-1) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0392] Comparative Example 2

[0393] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Comparative Synthesis Example 2 (represented by chemical formula C-2) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0394] Comparative Example 3

[0395] A photosensitive resin composition was prepared according to the same method as in Example 1, except that the compound according to Comparative Synthesis Example 3 (represented by chemical formula C-3) was used instead of the compound according to Synthesis Example 1 (represented by chemical formula A).

[0396] Evaluation: Measurement of the chemical resistance of the composition

[0397] Each color filter sample prepared using the photosensitive resin compositions according to Examples 1 to 12 and Comparative Examples 1 to 3 was immersed in a PGMEA solution for 10 minutes at room temperature, and the chemical resistance was evaluated by referring to the rate of change of absorption intensity at λmax before and after immersion in the solution. The results are shown in Table 2.

[0398] (Table 2)

[0399] (unit:%)

[0400]

[0401] Referring to Table 2, the photosensitive resin compositions comprising Examples 1 to 12 of the core-shell compounds according to the embodiments exhibit excellent chemical resistance and have proven to be highly suitable for use in CMOS image sensors.

[0402] Although this disclosure has been set forth in conjunction with exemplary embodiments which are now considered practical, it should be understood that this disclosure is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent configurations contained within the spirit and scope of the appended claims.

Claims

1. A core-shell compound comprising: a squarylium core represented by Chemical Formula 1; and a shell surrounding the squarylium core, [Chemical Formula 1] wherein, in Chemical Formula 1, R 1 to R 8 each independently is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, provided that R 1 to R 8 is not a hydrogen atom at the same time, R 1 , R 2 , R 5 , and R 6 comprises a (meth)acrylate group at the terminal end, R 3 , R 4 , R 7 , and R 8 comprise at least two or more (meth)acrylate groups at the terminal ends, and n1, n2, n3, and n4 are each independently an integer of 0 to 2, wherein n1+n2≠0 and n3+n4≠0, wherein the shell is represented by Chemical Formula 2: [Chemical Formula 2] wherein, in Chemical Formula 2, L a and L b each independently is a single bond, or substituted or unsubstituted C1to C10alkylene, and n is an integer greater than or equal to 2.

2. The core-shell compound according to claim 1, wherein the squarylium core comprises four or more (meth)acrylate groups.

3. The core-shell compound according to claim 1, wherein all of the (meth)acrylate groups are present as substituents of an alkyl group constituting the squarylium core, or as substituents of an alkoxy group constituting the squarylium core.

4. The core-shell compound according to claim 1, wherein at least one (meth)acrylate group is present as a substituent of an aryl group constituting the squarylium core, and at least one (meth)acrylate group is present as a substituent of an alkyl group or an alkoxy group constituting the squarylium core.

7. The core-shell compound according to claim 5, wherein Chemical Formula 1 is represented by Chemical Formula 1-1: [Chemical Formula 1-1] 5. The core-shell compound of claim 1, wherein any two of R 1 , R 2 , R 5 , and R 6 , and any two of R 3 , R 4 , R 7 , and R 8 each independently comprise a (meth)acrylate group at its terminus.

6. The core-shell compound of claim 1, wherein any three of R 1 , R 2 , R 5 , and R 6 and any three of R 3 , R 4 , R 7 , and R 8 each independently comprise a (meth)acrylate group at its terminus. in Chemical Formula 1-1, n5 and n6 are each independently an integer of 0 to 2. wherein, 8. The core-shell compound according to claim 5, wherein Chemical Formula 1 is represented by Chemical Formula 1-2: R 2 , R 4 , R 6 , and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, provided that R 2 , R 4 , R 6 , and R 8 are not simultaneously hydrogen atoms, R 2 , R 4 , R 6 and R 8 do not contain a (meth)acrylate group, R 1 , R 3 , R 5 and R 7 each independently is C1to C20alkyl comprising a (meth)acrylate group at the end or C1to C20alkoxy comprising a (meth)acrylate group at the end, and [Chemical Formula 1-2] in Chemical Formula 1-2, n5 and n6 are each independently an integer of 0 to 2. wherein 9. The core-shell compound according to claim 6, wherein Chemical Formula 1 is represented by Chemical Formula 1-3: R 6 and R 8 each independently is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, provided that R 6 and R 8 are not simultaneously a hydrogen atom, R 6 and all of the owners in R 8 do not contain a (meth)acrylate group, R 1 to R 4 each independently C1to C20alkyl comprising a (meth)acrylate group at the terminal or C1to C20alkoxy comprising a (meth)acrylate group at the terminal, and [Chemical Formula 1-3] in Chemical Formula 1-3, n5 and n6 are each independently an integer of 0 to 2. wherein, 10. The core-shell compound according to claim 1, wherein the squarylium core represented by Chemical Formula 1 has a maximum absorption wavelength at 610 nm to 640 nm. R 6 and R 8 each independently is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, provided that R 6 and R 8 are not simultaneously a hydrogen atom, R 6 and R 8 does not contain a siloxane group, R 1 to R 5 and R 7 each independently is C1to C20alkyl comprising a (meth)acrylate group at the terminal or C1to C20alkoxy comprising a (meth)acrylate group at the terminal, and 11. 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] 12. The core-shell compound according to claim 1, wherein the core-shell compound is represented by any one of Chemical Formula A to Chemical Formula N: [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] [Chemical Formula D] [Chemical Formula E] [Chemical Formula F] [Chemical Formula G] [Chemical Formula H] [Chemical Formula I] [Chemical Formula J] [Chemical Formula K] [Chemical Formula L] [Chemical Formula M] [Chemical Formula N] in Chemical Formula A to Chemical Formula N, 13. The core-shell compound according to claim 1, wherein the core-shell compound is a green dye. wherein 14. A photosensitive resin composition comprising the core-shell compound of claim 1. R 9 is a hydrogen atom, or a substituted or unsubstituted C1to C10alkyl group.

15. The photosensitive resin composition according to claim 14, wherein the core-shell compound is contained in an amount of 15 to 30% by weight based on the total amount of the photosensitive resin composition. ​ ​ 16. The photosensitive resin composition according to claim 14, wherein the photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

17. The photosensitive resin composition according to claim 14, wherein the photosensitive resin composition is used for a complementary metal-oxide semiconductor image sensor.

18. A photosensitive resin layer produced by using the photosensitive resin composition according to claim 14.

19. A color filter comprising the photosensitive resin layer according to claim 18.

20. A complementary metal-oxide semiconductor image sensor comprising the color filter according to claim 19.

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