TWI768723B - Core-shell compound, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and cmos image sensor - Google Patents

Abstract

Disclosed are a core-shell compound, a photosensitive resin composition including the same, a photosensitive resin layer produced using the photosensitive resin composition, a color filter including the photosensitive resin layer, and a CMOS image sensor including the color filter. The core-shell compound consisting of a core represented by Chemical Formula 1 and a shell surrounding the core and represented by Chemical Formula 2. The definition of Chemical Formula 1 and Chemical Formula 2 are the same as in the specification.

Description

Core-shell compound, photosensitive resin composition including the same, photosensitive resin layer, color filter and CMOS image sensor

The present disclosure relates to a core-shell compound, a photosensitive resin composition including the same, a photosensitive resin layer produced using the photosensitive resin composition, a color filter including the photosensitive resin layer, and a CMOS image sensor including the color filter .

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0022394 filed in the Korea Intellectual Property Office on February 24, 2020, the entire contents of which are incorporated herein by reference.

With the recent development of the computer industry and the communication industry, image sensors with improved performance (such as digital cameras, camcorders, personal communication systems (PCS), game devices, security cameras) are being introduced in various fields and medical micro-cameras) increased demand. Image sensors can be classified into charge coupled devices (CCDs) and CMOS image sensors, in which CMOS image sensors (hereinafter, CIS) can adopt a simple driving method and The number processing circuitry is integrated on a single chip and thus contributes to product reduction. In addition, CIS consumes very little power and thus can be properly applied to products with limited battery capacity. The use of CIS is rapidly increasing as technology develops to achieve high resolution.

The technical trend related to CIS achieves high definition and device downsizing by increasing the number of pixels but reducing the size of the pixels, and thus, development of photosensitive resin compositions of high transmission type CIS is underway. In general, in a photosensitive resin composition for CIS having green, red, and blue color filters, a green pixel has transmittance satisfying a specific wavelength or a specific wavelength range.

However, the currently developed green photosensitive resin composition for CIS does not satisfy the transmittance at 540 nm and the transmittance in the range of 600 nm to 640 nm, and does not improve the crosstalk problem. And especially, a high transmission type CIS cannot be provided.

Embodiments provide a core-shell compound that constitutes a green pixel in a color filter for CIS.

Another embodiment provides a photosensitive resin composition including a compound.

Another embodiment provides a photosensitive resin layer produced using the photosensitive resin composition.

Another embodiment provides a color filter including a photosensitive resin layer.

Another embodiment provides a CIS that includes a color filter.

Embodiments of the present invention provide a core-shell compound consisting of a core represented by Chemical Formula 1 and a shell surrounding the core and represented by Chemical Formula 2.

[Chemical formula 1]

In Chemical Formula 1 and Chemical Formula 2, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkane base, substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, ^R2 and R4 ^exist independently or are fused to each other to form a fused ring, ^R3 and R ⁵ exist independently or are fused to each other to form a fused ring, and L ^a and L ^b are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene.

The core represented by Chemical Formula 1 may be represented by Chemical Formula 1-1.

In Chemical Formula 1-1, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group , substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, R ² and R ⁴ exist independently or are condensed with each other to form a fused ring, R ³ and R ⁵ Exist independently or fused with each other to form fused rings.

The core represented by Chemical Formula 1-1 may be represented by Chemical Formula 1-1-1 or Chemical Formula 1-1-2.

In Chemical Formula 1-1-1 and Chemical Formula 1-1-2, R ¹ to R ³ and R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy, or substituted or unsubstituted C6 to C20 aryl.

R ¹ may be a substituted or unsubstituted C1 to C20 alkoxy group.

R ² can be a substituted or unsubstituted C3 to C20 cycloalkyl, such as an alkoxy substituted C3 to C20 cycloalkyl.

R ³ can be a substituted or unsubstituted C6 to C20 aryl group, eg, a C6 to C20 aryl group substituted with at least one alkyl group.

R ⁶ may be a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkoxy group.

The core represented by Chemical Formula 1 may have a maximum absorption wavelength at 610 nm to 640 nm.

The shell represented by Chemical Formula 2 may be represented by Chemical Formula 2-1.

The core-shell compound may be represented by one of Formula A to Formula I.

[Chemical formula A]

[chemical formula D]

[chemical formula G]

The core-shell compound can be a green dye.

Another embodiment provides a photosensitive resin composition including a core-shell compound.

The transmittance of the photosensitive resin composition at 540 nm can be 90% or more 90% and the transmittance may be 10% or less at 600 nm to 640 nm.

The photosensitive resin composition may have a transmittance of 5% or less at 450 nm.

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

Another embodiment provides a photosensitive resin layer produced by using the photosensitive resin composition.

Another embodiment provides a color filter including a photosensitive resin layer.

Another embodiment provides a CMOS image sensor including a color filter.

Other embodiments of the invention are included in the following detailed description.

The photosensitive resin composition including the core-shell compound according to the embodiment can form a green pixel to provide a color filter for a CMOS image sensor with high transmittance.

1 is a graph of absorbance according to wavelength of green dyes used in Example 1 and Comparative Example 2 (Synthesis Example 1 and Comparative Synthesis Example 1).

2 is a graph of transmittance according to wavelength of the photosensitive resin composition according to Example 1, Comparative Example 1, and Comparative Example 2. FIG.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto and the invention is defined by the scope of the claimed scope.

In this specification, when a specific definition is not otherwise provided, "substituted" means that one is substituted with a substituent selected from the group consisting of halogen (F, Br, Cl or I), hydroxy, nitro, cyano , amine group (NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different, and each independently is a C1 to C10 alkyl group), methyl amidino, hydrazino, hydrazone, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alicyclic Organic, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclyl.

In this specification, when a specific definition is not otherwise provided, "alkyl" refers to C1 to C20 alkyl, and specifically C1 to C15 alkyl, "cycloalkyl" refers to C3 to C20 cycloalkyl, and C3 to C18 cycloalkyl in particular, "alkoxy" refers to C1 to C20 alkoxy, and C1 to C18 alkoxy in particular, "aryl" refers to C6 to C20 aryl, and in particular C6 to C18 aryl, "alkenyl" refers to C2 to C20 alkenyl, and specifically C2 to C18 alkenyl, "alkylene" refers to C1 to C20 alkylene, and specifically C1 to C18 alkylene Alkyl, and "arylene" refers to C6 to C20 aryl, and specifically C6 to C16 aryl.

In this specification, when a specific definition is not otherwise provided, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic acid" and "methacrylic acid".

In this specification, when no definition is otherwise provided, the term "combination" refers to mixing or copolymerization.

In the chemical formulas of the present specification, unless a specific definition is provided otherwise, when a chemical bond is not drawn at a position where it should be given, the hydrogen at the position is removed.

In this specification, when a specific definition is not otherwise provided, "*" indicates where Connect dots of the same or different atoms or chemical formulas.

Embodiments provide a core-shell compound consisting of a core represented by Chemical Formula 1 and a shell surrounding the core and represented by Chemical Formula 2.

In Chemical Formula 1 and Chemical Formula 2, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkane base, substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, ^R2 and R4 ^exist independently or are fused to each other to form a fused ring, ^R3 and R ⁵ exist independently or are fused to each other to form a fused ring, and L ^a and L ^b are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene.

When a light transmittance of less than or equal to 10% is satisfied at random wavelengths in the range of 600 nm to 640 nm in the transmission spectrum of the green pixel, the crosstalk problem can be improved to realize the photosensitive resin composition for high transmission type CIS , and thus achieve high quality image.

Therefore, by using aryl cyanine dyes that do not absorb light in the short wavelength region but selectively absorb light in the desired wavelength region by minimizing the reference absorption full width at half maximum (FWHM) Efforts have been made to realize a photosensitive resin composition for a high transmission type CIS, but a satisfactory composition has still not been obtained. The inventors of the present invention have used an asymmetric aryl cyanine dye with a specific structure to prepare a photosensitive resin composition for CIS, and then measured its transmission spectrum and confirmed that the composition satisfies the transmission of a high-transmission green photosensitive resin composition transmittance conditions (greater than or equal to 90% transmittance at any wavelength in the wavelength range from 500 nm to 600 nm (eg, at 540 nm), and in the wavelength range from 600 nm to 640 nm less than or equal to 10% transmittance at any wavelength).

In addition, when the asymmetric aryl cyanine compounds with a specific structure have a maximum absorption wavelength in the range of 610 nm to 640 nm, the transmittance in the long wavelength region (600 nm to 640 nm) is greatly improved ( less than or equal to 10%).

For example, the core represented by Chemical Formula 1 may be represented by Chemical Formula 1-1.

In Chemical Formula 1-1, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group , substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, R ² and R ⁴ exist independently or are condensed with each other to form a fused ring, and R ³ and R ⁵ exist independently or are fused to each other to form a fused ring.

For example, the core represented by Chemical Formula 1-1 may be represented by Chemical Formula 1-1-1 or Chemical Formula 1-1-2.

In Chemical Formula 1-1-1 and Chemical Formula 1-1-2, R ¹ to R ³ and R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy, or substituted or unsubstituted C6 to C20 aryl.

For example, R ¹ can be substituted or unsubstituted C1 to C20 alkoxy.

For example, R ² can be a substituted or unsubstituted C3 to C20 cycloalkyl, such as an alkoxy substituted C3 to C20 cycloalkyl.

For example, ^R3 can be a substituted or unsubstituted C6-C20 aryl group, such as a C6-C20 aryl group substituted with at least one alkyl group.

For example, R ⁶ may be a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkoxy group.

For example, the core represented by Chemical Formula 1 may have a maximum absorption wavelength at 610 nm to 640 nm. If even a dye compound having an excellent solubility of 10% or more in an organic solvent has a maximum absorption wavelength at 610 nm to 640 nm, it may not be suitable for use as a green photosensitive resin composition for high transmission type CIS .

The shell represented by Chemical Formula 2 may be represented by Chemical Formula 2-1.

For example, the core-shell compound may be represented by one of Chemical Formula A to Chemical Formula I, but is not limited thereto.

[Chemical formula A]

[chemical formula D]

[chemical formula G]

For example, the core-shell compound can be a green dye.

According to another embodiment, there is provided a photosensitive resin composition including the core-shell compound according to the embodiment.

For example, the transmittance of the photosensitive resin composition can be 90% at 540 nm or greater than 90%, the transmittance may be 10% or less at 600 nm to 640 nm, and the transmittance may be 5% or less at 450 nm, and thus may be suitable for implementing Green filter for high transmission type CIS. That is, the photosensitive resin composition can be used in a high transmission type CMOS image sensor.

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

The core-shell compound according to the embodiment may be included in an amount of 1 wt % to 10 wt %, for example, 3 wt % to 7 wt %, based on the total amount of the photosensitive resin composition. When the core-shell compound according to the embodiment is included in the above range, the color reproducibility and the contrast ratio are improved.

The photosensitive resin composition may further contain pigments such as yellow pigments, green pigments, or a combination thereof.

In the color index, the yellow pigments may be C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and the like, and these may be used alone or in a mixture of two or more.

In the color index, the green pigments may be C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, and the like, and these may be used alone or in a mixture of two or more.

The pigment may be contained in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may contain a solid pigment, a solvent, and a dispersant that uniformly disperses the pigment in the solvent.

The solid pigment may be included in an amount of 1 wt% to 20 wt%, such as 8 wt% to 20 wt%, such as 8 wt% to 15 wt%, such as 10 wt% to 20 wt%, based on the total amount of the pigment dispersion %, for example from 10% to 15% by weight.

The dispersing agent may be a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent, and the like. Specific examples of dispersants may be polyalkylene glycols and their esters, polyalkylene oxides, polyol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonates, sulfonates, carboxylates , carboxylates, alkylamide alkylene oxide addition products, alkylamines, and the like, and these may be used alone or in mixtures of two or more.

Commercially available examples of the dispersing agent may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-140, manufactured by BYK Co., Ltd., Germany Disc-160, Disc-161, Disc-162, Disc-163, Disc-164, Disc-165, Disc-166, Disc-1 G-170, DESP-171, DESP-182, DESP-2000, DESP-2001 and the like; manufactured by EFKA Chemicals Co. Efka-47, Efka-47EA, Efka-48, Efka-49, Efka-100, Efka-400, Efka-450 and similar; by Zeneca Corporation Solsperse 5000, Sosperse 12000, Sosperse 13240, Sosperse 13940, Sosperse 17000, Sosperse 20000, Sosperse 24000GR, Sosperse 27000, manufactured by (Zeneka Co.) Sospos 28000 and the like; or PB711, PB821 and the like manufactured by Ajinomoto Inc.

The dispersant may be included in an amount of 1% to 20% by weight based on the total amount of the pigment dispersion. When the dispersant is included in the range, the dispersion of the photosensitive resin composition is improved due to an appropriate viscosity, and thus, when the photosensitive resin composition is applied to a product, optical, physical, and chemical qualities can be maintained.

The solvent used to form the pigment dispersion can be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol Methyl ether and the like.

The pigment dispersion may be included in an amount of 10% by weight to 20% by weight, for example, 12% by weight to 18% by weight, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included in the above range, it is advantageous to ensure a process margin, and it is possible to have improved color reproducibility and contrast ratio.

The binder resin may be an acrylic binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one acryl-based repeating unit.

The first ethylenically unsaturated monomer may be an ethylenically unsaturated monomer containing at least one carboxyl group and examples of the monomer may include acrylic acid, methacrylic acid, maleic acid, itonic acid, fumaric acid acid or a combination thereof.

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

The second ethylenically unsaturated monomer may be: an aromatic vinyl compound such as styrene, alpha-methylstyrene, vinyltoluene, vinylbenzyl methyl ether and the like; an unsaturated carboxylate compound, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate ) Benzyl acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate and the like; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate and the like; vinyl carboxylate compounds such as vinyl acetate, vinyl benzoate and the like; unsaturated glycidyl carboxylate compounds such as (methyl) Glycidyl acrylate and the like; cyanogen ethylene compounds such as (meth)acrylonitrile and the like; unsaturated amide compounds such as (meth)acrylamide and the like; and the like, and may be used alone or in combination of two or more used in the form of a mixture.

Specific examples of the acrylic binder resin may be (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate copolymer Methyl ester/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/methyl 2-hydroxyethyl acrylate copolymer and the like, but are not limited thereto and these may be used alone or in a mixture of two or more.

The weight average molecular weight of the binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the binder resin has a weight average molecular weight within the range, the photosensitive resin composition has good physical and chemical properties, appropriate viscosity, and close contact properties with the substrate during the manufacture of color filters.

The acid value of the binder resin may be 15 mg KOH/gram to 60 mg KOH/gram, eg, 20 mg KOH/gram to 50 mg KOH/gram. When the acid value of the binder resin is within the range, the resolution of the pixel pattern is improved.

The binder resin may be included in an amount of 1 wt % to 30 wt %, for example, 1 wt % to 20 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included in the range, the composition can have excellent developability and improved crosslinking, and thus have excellent surface flatness when manufactured into a color filter.

The photopolymerizable compound may be a (meth)acrylic monofunctional or polyfunctional ester containing at least one ethylenically unsaturated double bond.

The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization and form a pattern having excellent heat resistance, light resistance, and chemical resistance during exposure in a patterning process.

Specific examples of the photopolymerizable compound may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Acrylates, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate Meth)acrylate, neotaerythritol di(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, neotaerythritol hexa(meth)acrylate ) Acrylates, Dipiveaerythritol di(meth)acrylate, Dipiveaerythritol tri(meth)acrylate, Dipiveaerythritol penta(meth)acrylate, Dipiotaerythritol hexa(meth)acrylate Meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(methyl)phosphate Acrylooxyethyl ester, novolac epoxy (meth)acrylate and the like.

Commercial examples of the photopolymerizable compound are as follows. Monofunctional (meth)acrylates may include: Aronix M-101 ^® , Aronix M-111 ^® , Aronix M-114 ^® (Toagosei Chemistry Industry Co. , Ltd.)); KAYARAD TC-110S ^® , KAYARAD TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V- 2311 ^® (Osaka Organic Chemical Ind., Ltd.) and the like. Examples of bifunctional (meth)acrylates may include: Anix M-210 ^® , Anix M-240 ^® , Anix M-6200 ^® (Toa Gosei Chemical Co., Ltd.); Kayarad HDDA ^® , Kayarad HX-220 ^® , Kayarad R-604 ^® (Nihon Kayaku Co., Ltd.); V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Industry Co., Ltd.) and the like. Examples of trifunctional (meth)acrylates may include Anix M-309 ^® , Anix M-400 ^® , Anix M-405 ^® , Anix M-450 ^® from Toagosei Chemicals Co., Ltd. , Anix M-710 ^® , Anix M-8030 ^® , Anix M-8060 ^® and the like; Kaylar TMPTA ^® , Kaylar DPCA-20 ^® , Nippon Kayaku Co., Ltd. Kayarad DPCA-30 ^® , Kayarad DPCA-60 ^® , Kayarad DPCA-120 ^® , V-295 ^® , V-295 of Osaka Yuki Kayaku Kogyo Co. Ltd. ^-300® , V- ^360® , V- ^GPT® , V- ^3PA® , V- ^400® and the like. These can be used alone or in a mixture of two or more.

The photopolymerizable compound may be treated with an acid anhydride to improve developability.

The photopolymerizable compound may be included in an amount of 1 wt % to 15 wt %, for example, 5 wt % to 10 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included in the range, the photopolymerizable monomer is sufficiently cured during exposure in the pattern formation process with excellent reliability, and developability to an alkaline developing solution can be improved.

The photopolymerization initiator can be a general initiator for photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds or its combination.

Examples of acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tertiary Butyltrichloroacetophenone, p-tertiary butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1 -(4-(Methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl -1-keto and the like.

Examples of benzophenone compounds may be benzophenone, benzyl benzoate Esters, 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 and the like.

Examples of thioxanthones may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of benzoin compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of triazine compounds may be 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) base)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine , 2-(naphtholyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtholyl)-4,6-bis(trichloromethyl) -s-triazine, 2-4-bis(trichloromethyl)-6-sunenyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyrene) base)-s-triazine and the like.

Examples of the oxime compound may be o-acyl oxime, 2-(o-benzyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-( o-Acetyl oxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone, o-ethoxycarbonyl-α-oxyamino -1-Phenylpropan-1-one and the like. Specific examples of the ortho-acyl oxime compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-phthalate, 1-(4-phenylthiophenyl) phenyl)-octane-1,2-dione-2-oxime-phthalate, 1-(4-phenylthiophenyl)-oct-1-one oxime-o-acetate, and 1 -(4-Phenylthiophenyl)-butan-1-one oxime-o-acetate and the like.

In addition to the above-mentioned compounds, the photopolymerization initiator may further comprise carbazole compounds, diketone compounds, pericynium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, benzoindene compounds and the like By.

The photopolymerization initiator can be used together with a photosensitizer that can cause a chemical reaction by absorbing light and become excited and then transfer its energy.

Examples of photosensitizers can be tetraethylene glycol bis-3-mercaptopropionate, tetra-3-mercaptopropionate neotaerythritol, tetra-3-mercaptopropionate of dipeotaerythritol, and the like.

The photopolymerization initiator may be included in an amount of 0.01 wt % to 10 wt %, for example, 0.1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the range, sufficient photopolymerization occurs during exposure in the pattern forming process, excellent reliability can be achieved, heat resistance, light resistance, and chemical resistance of the pattern can be improved, analysis and close contact properties, and can prevent the reduction of transmittance due to unreacted initiators.

The solvent is a material compatible with but not reactive with the core-shell compound, the pigment according to the embodiment, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

Examples of the solvent may include: alcohols such as methanol, ethanol and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran and the like; glycol ethers such as ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, and the like; ethylene glycol ethyl acetate, such as methyl glycol ethyl acetate, ethyl glycol ethyl acetate, diethyl glycol ethyl acetate, and the like; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like ; aromatic hydrocarbons such as toluene, xylene and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl- n-Butanone, methyl-n-pentyl ketone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactic acid Esters such as methyl lactate, ethyl lactate and the like; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate and the like; alkyl alkoxyacetates , such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxypropionate, such as methyl 3-oxypropionate, ethyl 3-oxypropionate and the like; alkyl 3-alkoxypropanoates such as methyl 3-methoxypropionate, 3-methoxypropionate acid ethyl esters, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like; alkyl 2-oxypropionates such as methyl 2-oxypropionate, 2-oxo ethyl propionate, propyl 2-oxypropionate, and the like; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate and the like; 2-oxy-2-methylpropionate, such as methyl 2-oxy-2-methylpropionate , ethyl 2-oxy-2-methylpropanoate and the like; monooxymonocarboxylates of alkyl 2-alkoxy-2-methylpropanoates, such as 2-methoxy- Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate and the like; ketoesters such as ethyl pyruvate and the like; and also high boiling solvents such as N-methyl methyl Carboxamide, N,N-Dimethylcarboxamide, N-Methylcarboxanilide, N-Methylacetamide, N,N-Dimethylacetamide, N-Methylpyrrolidone, Dimethylacetamide Methyl sulfite, benzyl ether, Dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, cis-butyl Diethyl enedioate, γ-butyrolactone, ethylidene carbonate, propylidene carbonate, phenylglycol ethyl acetate and the like.

In view of mutual solubility and reactivity, glycol ethers such as ethylene glycol monoethyl ether and the like; glycol alkyl ether acetates such as ethyl glycol ethyl acetate and the like; esters, such as ethyl 2-hydroxypropionate and the like; carbitol such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate Esters and the like; and/or ketones such as cyclohexanone and the like.

The solvent may be included in the balance of, for example, 30% by weight to 80% by weight based on the total amount of the photosensitive resin composition. When the solvent is included in the range, the photosensitive resin composition can have an appropriate viscosity, thereby causing improvement in coating characteristics of the color filter.

The photosensitive resin composition according to another embodiment may further include an epoxy compound in order to improve the close contact property with the substrate.

Examples of epoxy compounds may include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

The epoxy compound may be included in an amount of 0.01 parts by weight to 20 parts by weight, for example, 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the range, close contact properties, storage properties, and the like can be improved.

In addition, the photosensitive resin composition may further include a silane coupling agent having reactive substituents such as carboxyl group, methacryloyl group, isocyanate group, epoxy group and the like to improve its adhesion to the substrate.

Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ- Isocyanatepropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane and the like, and these may be used alone or in combination or more than a mixture of the two.

The silane coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the range, close contact properties, storage properties, and the like can be excellent.

In addition, as necessary, the photosensitive resin composition may further contain a surfactant in order to improve coating properties and prevent defects.

Examples of surfactants may be commercially available fluorine-based surfactants, such as BM- ^1000® , BM- ^1100® and the like from BM Chemie Inc.; Dainippon Ink F142D ^® , F172 ^® , F173 ^® , F183 ^® and the like from Kagaku Kogyo Co., Ltd.; FULORAD FC-135 ^® , FULORAD ® from Sumitomo 3M Co., Ltd. Rollard FC-170C ^® , Florard FC-430 ^® , Flourard FC-431 ^® and the like; SURFLON S-112 ^® from ASAHI Glass Co., Ltd. , Schaefflon S-113 ^® , Schaefflon S-131 ^® , Schaefflon S-141 ^® , Schaefflon S-145 ^® and similar; SH-28PA ^® , SH190 ^® , SH-193 ^® , SZ -6032 ^® , SF-8428 ^® and similar.

The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the range, coating uniformity is ensured, no stain is found, and the wetting property to the glass substrate is improved.

In addition, the photosensitive resin composition may further contain predetermined amounts of other additives, such as oxidation inhibitors, stabilizers, and the like, unless the properties are deteriorated.

According to another embodiment, there is provided a color filter produced using the photosensitive resin composition according to the embodiment.

The pattern forming process in the photosensitive resin layer is as follows.

The process includes coating the photosensitive resin composition according to the embodiment on a support substrate by spin coating, slot coating, ink jet printing, and the like; drying the coated positive photosensitive resin composition to form a photosensitive resin composition resin composition film; exposing the positive-type photosensitive resin composition film to light; developing the exposed positive-type photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin film; and heat-treating the photosensitive resin film. The conditions for the patterning process are well known in the prior art and will not be shown in detail in this specification.

Another embodiment provides a CMOS image sensor including a color filter.

In the following, the present invention is shown in more detail with reference to examples, however, these examples are not to be construed as limiting the scope of the present invention in any sense.

(synthetic compound)

Synthesis Example 1: Synthesis of Compound Represented by Chemical Formula A

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene- 1,2-Dione (60 mmol) and 1-[4-(2-ethyl-hexyloxy)-phenyl]-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then the resulting water was removed by refluxing using a Dean-stark still. After stirring for 12 hours, the green reaction was distilled under reduced pressure and purified via column chromatography to obtain asymmetric arylcyanine compound. This compound (5 mmol) was dissolved in 600 mL of chloroform solvent, and isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and The obtained solution was then added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated via column chromatography to obtain the compound represented by Chemical Formula A.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (Maldi-tof MS): 1243.5 mass-to-charge ratio

Synthesis Example 2: Synthesis of Compound Represented by Chemical Formula B

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene- 1,2-Dione (60 mmol) and 1-[4-(2-ethyl-hexyloxy)-phenyl]-6-methoxy-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then the resulting water was removed by refluxing using a Dean-Stark still. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. within 12 hours After that, the obtained mixture was distilled under reduced pressure and separated via column chromatography to obtain the compound represented by Chemical Formula B.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1273.58 mass-to-charge ratio

Synthesis Example 3: Synthesis of Compound Represented by Chemical Formula C

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene- 1,2-Dione (60 mmol) and 1-[4-(2-ethyl-hexyloxy)-phenyl]-1H-indole-6-carbonitrile (60 mmol) were added to Toluene (200 mL) and butanol (200 mL), and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated via column chromatography to obtain the compound represented by Chemical Formula C.

[Chemical formula C]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1268.73 mass-to-charge ratio

Synthesis Example 4: Synthesis of Compound Represented by Chemical Formula D

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene- 1,2-Dione (60 mmol) and 1-[4-(2-ethyl-hexyloxy)-phenyl]-6-fluoro-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and purified via column chromatography to obtain the compound represented by Chemical Formula D.

[chemical formula D]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1261.73 mass-to-charge ratio

Synthesis Example 5: Synthesis of Compound Represented by Chemical Formula E

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino) -Phenyl]-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol) and 6-fluoro-1-(4-methoxy-phenyl)-1H-indone Toluene (60 mmol) was added to toluene (200 mL) and butanol (200 mL), and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and then purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and purified via column chromatography to obtain the compound represented by Chemical Formula E.

[chemical formula E]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1251.75 mass-to-charge ratio

Synthesis Example 6: Synthesis of Compound Represented by Chemical Formula F

3-Hydroxy-4-(2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)-cyclobut-3-ene-1 , 2-dione (60 mmol) and 6-fluoro-1-(4-methoxy-phenyl)-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL) and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated via column chromatography to obtain the compound represented by Chemical Formula F.

[chemical formula F]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1027.49 mass-to-charge ratio

Synthesis Example 7: Synthesis of Compound Represented by Chemical Formula G

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino) -Phenyl]-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol) and 4-indol-1-yl-benzonitrile (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The resulting solution was simultaneously added for 5 hours at room temperature. After 12 hours, the obtained mixture was distilled under reduced pressure and purified via column chromatography to obtain the compound represented by Chemical Formula G.

[chemical formula G]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1242.54 mass-to-charge ratio

Synthesis Example 8: Synthesis of Compound Represented by Chemical Formula H

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino) -Phenyl]-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol) and 1-(4-fluoro-phenyl)-1H-indole (60 mmol) Toluene (200 mL) and butanol (200 mL) were added and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure distillation and separated via column chromatography to obtain the compound represented by Chemical Formula H.

[chemical formula H]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1221.67 mass-to-charge ratio

Synthesis Example 9: Synthesis of Compounds Represented by Chemical Formula I

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino) -Phenyl]-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol) and 1-[4-(2-ethyl-hexyloxy)-phenyl]-1H - Indole (60 mmol) was added to toluene (200 mL) and butanol (200 mL) and then refluxed using a Dean-Stark still to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and purified via column chromatography to obtain the compound represented by Chemical Formula I.

[Chemical formula I]

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1331.81 mass-to-charge ratio

Comparative Synthesis Example 1: Synthesis of Compound Represented by Chemical Formula C-1

Propionic acid 2-{(2-cyano-ethyl)-[4-(2-hydroxy-3,4-dioxy-cyclobut-1-enyl)-phenyl]-amino}- Ethyl ester (60 mmol) and 1-(2-ethyl-hexyl)-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL), and then using Di The En-Stark still was refluxed to remove the resulting water. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified via column chromatography to obtain the asymmetric aryl cyanine compound. This compound (5 mmol) was dissolved in 600 ml of chloroform solvent, isophthalide chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 ml of chloroform, and then The obtained solution was added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and purified via column chromatography to obtain the compound represented by Chemical Formula C-1.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: 1088.48 mass-to-charge ratio

Evaluation 1: Measure the wavelength of maximum absorption

The core-shell compounds according to Synthesis Example 1 and Synthesis Example 9 and Comparative Synthesis Example 1 were used with a diluting solvent (ANONE) at a concentration of 0.001 wt % to obtain each absorption spectrum thereof, and the results are shown in Table 1 and Fig. 1 (UV-1800, Shimazu Corp.).

Assessment 2: Measuring Solubility

By adding a dilution solvent (PGMEA) to 0.5 g of each compound, a mixing rotor (Mixrotar) VMR-5 (Iuchi Seieido Co., Ltd.) was used at 25°C at 100 rpm/ The solution was stirred for 1 hour for 1 hour to evaluate the solubility of the compounds according to Synthesis Example 1 to Synthesis Example 9 and Comparative Synthesis Example 1, and the results are shown in Table 2.

Solubility Evaluation Reference

Dissolve 10% by weight or more of compounds (solutes) based on the total amount of the dilution solvent: ○

Dissolve less than 10% by weight of compound (solute) based on the total amount of dilution solvent: X

Referring to Table 2, the compounds of Synthesis Example 1 to Synthesis Example 9 and Comparative Synthesis Example 1 all exhibited excellent solubility.

(Synthetic photosensitive resin composition)

Example 1

The following components were mixed in each of the compositions shown in Table 3 to prepare the photosensitive resin composition according to Example 1.

Specifically, the photopolymerization initiator was dissolved in the solvent, the solution was stirred at room temperature for 2 hours, the binder resin and the photopolymerizable compound were added thereto, and the obtained mixture was stirred at room temperature 2 hours. Subsequently, the compound according to Synthesis Example 1 (represented by Chemical Formula A) was added thereto as a colorant and a pigment (in the form of a dispersion) and then stirred at room temperature for 1 hour. Next, the product was filtered three times to remove impurities and prepare a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared according to the same method as 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).

Example 3

A photosensitive resin composition was prepared according to the same method as 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 (represented by Chemical Formula A).

Example 4

A photosensitive resin composition was prepared according to the same method as 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 (represented by Chemical Formula A).

Example 5

A photosensitive resin composition was prepared according to the same method as 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 (represented by Chemical Formula A).

Example 6

Except using the compound according to Synthesis Example 6 (represented by Chemical Formula F) instead of A photosensitive resin composition was prepared according to the same method as in Example 1 except for the compound according to Synthesis Example 1 (represented by Chemical Formula A).

Example 7

A photosensitive resin composition was prepared according to the same method as 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).

Example 8

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 (represented by Chemical Formula A).

Example 9

A photosensitive resin composition was prepared according to the same method as 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 (represented by Chemical Formula A).

Comparative Example 1

A photosensitive resin composition was prepared according to the same method as Example 1, except that the compound (represented by Chemical Formula A) according to Synthesis Example 1 was not used as a colorant.

Comparative Example 2

A photosensitive resin composition was prepared according to the same method as 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).

Evaluation 3: Color Coordinates, Brightness, and Contrast Ratios

The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 and 2 were respectively coated on a 1 mm thick degreased glass substrate to have a thickness of 1 μm. to a thickness of 3 micrometers, and then dried on a 90°C hot plate for 2 minutes to obtain a film. Subsequently, the film was exposed to light by using a high pressure mercury lamp with a dominant wavelength of 365 nm. Next, the film was dried in a forced convection drying oven at 200° C. for 5 minutes to obtain a sample. The transmittances of the samples were measured at 450 nm, 540 nm, and 620 nm by using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 4 and in Figure 2.

Referring to Table 4, compared with the photosensitive resin compositions of Comparative Example 1 and Comparative Example 2 that do not contain the compound, the photosensitive resin compositions of Examples 1 to 9 containing the core-shell compounds according to the Examples as dyes satisfy the requirements at 450 nanometers. The transmittance is less than or equal to 5% at meters, greater than or equal to 90% at 540 nm, and less than or equal to 10% at 620 nm, and thus can be used to manufacture high transmission type CIS. (Comparative Example 2 exhibits a transmittance of less than or equal to 90% at 540 nm, which is not suitable for a green photosensitive resin composition for CIS. In addition, when a transmittance of less than or equal to 5% at 450 nm is satisfied improved transmission rate and at the same time greater than or equal to 90% transmittance at 540 nm and less than or equal to 10% transmittance at 620 nm Crosstalk problem, and the final photosensitive resin composition can be used to manufacture high transmission type CIS green filter. )

While this invention has been described in connection with what are presently considered to be practical example embodiments, it is to be understood that this invention is not limited to the disclosed embodiments, but on the contrary, this invention is intended to be encompassed within the spirit and scope of the appended claims various modifications and equivalent configurations.

Claims (20)

A core-shell compound consisting of: a core represented by Chemical Formula 1; and a shell surrounding the core and represented by Chemical Formula 2: [Chemical Formula 1]

[Chemical formula 2]

wherein, in Chemical Formula 1 and Chemical Formula 2, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 Cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, R ² and R ⁴ exist independently or are fused to each other to form a fused ring, R ³ and R ⁵ are independently present or fused to each other to form a fused ring, and L ^a and L ^b are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene. The core-shell compound of claim 1, wherein the core represented by Chemical Formula 1 is represented by Chemical Formula 1-1: [Chemical Formula 1-1]

wherein, in Chemical Formula 1-1, R ¹ to R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 ring alkyl, substituted or unsubstituted C1 to C20 alkoxy or substituted or unsubstituted C6 to C20 aryl, R ² and R ⁴ exist independently or are fused to each other to form a fused ring, and R ³ and R ⁵ exist independently or are fused to each other to form a fused ring. The core-shell compound of claim 2, wherein the core represented by Chemical Formula 1-1 is represented by Chemical Formula 1-1-1 or Chemical Formula 1-1-2: [Chemical Formula 1-1-1]

[Chemical formula 1-1-2]

Wherein, in Chemical Formula 1-1-1 and Chemical Formula 1-1-2, R ¹ to R ³ and R ⁶ are independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group , substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy, or substituted or unsubstituted C6 to C20 aryl. The core-shell compound of claim 1, wherein R ¹ is a substituted or unsubstituted C1 to C20 alkoxy group. The core-shell compound of claim 4, wherein R ² is a substituted or unsubstituted C3 to C20 cycloalkyl. The core-shell compound of claim 5, wherein R ² is an alkoxy-substituted C3 to C20 cycloalkyl group. The core-shell compound of claim 4, wherein R ³ is a substituted or unsubstituted C6 to C20 aryl group. The core-shell compound of claim 7, wherein R ³ is a C6 to C20 aryl group substituted with at least one alkyl group. The core-shell compound of claim 1, wherein R ⁶ is a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkoxy group. The core-shell compound of claim 1, wherein the core represented by Chemical Formula 1 has a maximum absorption wavelength at 610 nm to 640 nm. The core-shell compound as claimed in claim 1, wherein the shell represented by the chemical formula 2 is represented by the chemical formula 2-1 [chemical formula 2-1]

. The core-shell compound of claim 1, wherein the core-shell compound is represented by one of Chemical Formula A to Chemical Formula I: [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]

. The core-shell compound of claim 1, wherein the core-shell compound is a green dye. A photosensitive resin composition, comprising the core-shell compound according to any one of claim 1 to claim 13. The photosensitive resin composition of claim 14, wherein the photosensitive resin composition has a transmittance of 90% or more at 540 nm and a transmittance of 10% or less at 600 nm to 640 nm 10%. The photosensitive resin composition of claim 15, wherein the photosensitive resin composition has a transmittance of 5% or less at 450 nm. The photosensitive resin composition according to claim 15, wherein the photosensitive resin composition is used in a CMOS image sensor. A photosensitive resin layer produced by using the photosensitive resin composition as claimed in claim 14. A color filter comprising the photosensitive resin layer as claimed in claim 18. A CMOS image sensor, comprising the color filter of claim 19.

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