KR102575019B1 - Core-shell compound, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and cmos image sensor - Google Patents

Abstract

A core-shell compound, a photosensitive resin composition including the same, a photosensitive resin film prepared using the photosensitive resin composition, a color filter including the photosensitive resin film, and a CMOS image sensor including the color filter are provided.

Description

Core-shell compound, photosensitive resin composition containing the same, photosensitive resin film, 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 film prepared using the photosensitive resin composition, a color filter including the photosensitive resin film, and a CMOS image sensor including the color filter.

Recently, with the development of the computer industry and the communication industry, demand for image sensors with improved performance is increasing in various fields such as digital cameras, camcorders, personal communication systems (PCS), game devices, security cameras, and medical micro cameras. Image sensors include charge coupled devices (CCD) and CMOS image sensors. Here, CMOS image sensors (hereinafter referred to as CIS) are easy to drive and can integrate signal processing circuits into a single chip, miniaturizing the product. is possible In addition, it has the advantage of being easily applied to products with limited battery capacity due to very low power consumption. The use of CIS is rapidly increasing as high resolution can be realized along with technology development.

As a CIS-related technology trend, the number of pixels and the size of pixels are increasing and decreasing in order to implement high-definition and miniaturized devices. Accordingly, development of photosensitive resin compositions for high-permeability CIS is in progress. Among the photosensitive resin compositions for CIS having green, red, and blue color filters, green pixels generally have transmittance that must be satisfied at a specific wavelength or a specific wavelength range.

However, in the case of the green photosensitive resin composition for CIS developed so far, the transmittance at 540 nm and the transmittance at 600 nm to 640 nm have not been satisfied at the same time, so the color mixing problem has not been improved, and above all, it has been impossible to provide a high transmittance type CIS. .

One embodiment is to provide a core-shell compound constituting a green pixel in a color filter for CIS.

Another embodiment is to provide a photosensitive resin composition containing the compound.

Another embodiment is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment is to provide a color filter including the photosensitive resin film.

Another embodiment is to provide a CIS including the color filter.

One embodiment of the present invention provides a core-shell compound consisting of a core represented by Formula 1 below and a shell surrounding the core and represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ to R ⁶ are each 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, a substituted or unsubstituted C1 to C20 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ² and R ⁴ may each independently exist or may be fused with each other to form a fused ring;

R ³ and R ⁵ may each independently exist or may be fused with each other to form a fused ring;

L ^a and L ^b are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

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

[Formula 1-1]

In Formula 1-1,

R ¹ to R ⁶ are each 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, a substituted or unsubstituted C1 to C20 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ² and R ⁴ may each independently exist or may be fused with each other to form a fused ring;

R ³ and R ⁵ may each independently exist or may be fused with each other to form a fused ring.

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

[Formula 1-1-1]

[Formula 1-1-2]

In Formula 1-1-1 and Formula 1-1-2,

R ¹ to R ³ and R ⁶ are each 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, a substituted or unsubstituted C1 to C20 An alkoxy group or a substituted or unsubstituted C6 to C20 aryl group.

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

R ² may be a substituted or unsubstituted C3 to C20 cycloalkyl group, for example, a C3 to C20 cycloalkyl group substituted with an alkoxy group.

R ³ may be a substituted or unsubstituted C6 to C20 aryl group, for example, a C6 to C20 aryl group substituted with one or more alkyl groups.

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 below.

[Formula 2-1]

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

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

[Formula F]

[Formula G]

[Formula H]

[Formula I]

The core-shell compound may be a green dye.

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

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

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

The photosensitive resin composition may be used for a CMOS image sensor.

Another embodiment provides a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

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

The specific details of other aspects of the present invention are included in the detailed description below.

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

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

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "substituted" to "substituted" means that one or more hydrogen atoms in the functional group of the present invention is a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino 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 from each other, and are each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and It means substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heterocyclic groups.

In this specification, unless otherwise specified, "alkyl group" means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and "cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically C3 to C18 cycloalkyl group, "alkoxy group" means a C1 to C20 alkoxy group, specifically means a C1 to C18 alkoxy group, "aryl group" means a C6 to C20 aryl group, and specifically means a C6 to C20 alkoxy group. Means a C18 aryl group, "alkenyl group" means a C2 to C20 alkenyl group, specifically means a C2 to C18 alkenyl group, "alkylene group" means a C1 to C20 alkylene group, specifically C1 to C18 alkylene group, and "arylene group" means a C6 to C20 arylene group, specifically a C6 to C16 arylene group.

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

Unless otherwise defined herein, "combination" means mixing or copolymerization. Further, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formula within this specification, if a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

In addition, unless otherwise defined in this specification, "*" means a part connected to the same or different atom or chemical formula.

One embodiment provides a core-shell compound consisting of a core represented by Formula 1 below and a shell surrounding the core and represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ to R ⁶ are each 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, a substituted or unsubstituted C1 to C20 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ² and R ⁴ may each independently exist or may be fused with each other to form a fused ring;

R ³ and R ⁵ may each independently exist or may be fused with each other to form a fused ring;

L ^a and L ^b are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

When the light transmittance of 10% or less is satisfied at any wavelength within the range of 600 nm to 640 nm in the transmission spectrum of the green pixel, crosstalk can be improved to implement a photosensitive resin composition for high transmission type CIS, thereby providing high quality images. can be implemented

Accordingly, efforts are being made to realize a photosensitive resin composition for high transmission CIS using a squarylium-based dye that does not have other light absorption in the short wavelength region and can selectively absorb a desired wavelength region by minimizing the absorption reference half-width, but still A satisfactory level of composition implementation has not been achieved. Accordingly, the inventors of the present invention prepared a photosensitive resin composition for CIS using the asymmetrical squarylium-based dye having a specific structure as described above and measured the transmission spectrum. It was confirmed that the condition that the light transmittance is 90% or more at any wavelength within the range, for example, the condition that the light transmittance is 10% or less at any wavelength within the wavelength range of 600 nm to 640 nm) was satisfied.

Furthermore, it was confirmed that the transmittance in the long wavelength region (600 nm to 640 nm) was further improved (less than 10%) when the asymmetric squarylium-based compound having a specific structure as described above had a maximum absorption wavelength at 610 nm to 640 nm.

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

[Formula 1-1]

In Formula 1-1,

R ¹ to R ⁶ are each 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, a substituted or unsubstituted C1 to C20 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ² and R ⁴ may each independently exist or may be fused with each other to form a fused ring;

R ³ and R ⁵ may each independently exist or may be fused with 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.

[Formula 1-1-1]

[Formula 1-1-2]

In Formula 1-1-1 and Formula 1-1-2,

R ¹ to R ³ and R ⁶ are each 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, a substituted or unsubstituted C1 to C20 An alkoxy group or a substituted or unsubstituted C6 to C20 aryl group.

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

For example, R ² may be a substituted or unsubstituted C3 to C20 cycloalkyl group, for example, a C3 to C20 cycloalkyl group substituted with an alkoxy group.

For example, R ³ may be a substituted or unsubstituted C6 to C20 aryl group, for example, a C6 to C20 aryl group substituted with one or more alkyl groups.

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. Even if a dye compound having an excellent solubility in an organic solvent of 10% or more does not have a maximum absorption wavelength at 610 nm to 640 nm, it may be unsuitable for use as a high transmission type CIS green photosensitive resin composition.

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

[Formula 2-1]

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

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

[Formula F]

[Formula G]

[Formula H]

[Formula I]

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

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

For example, the photosensitive resin composition may have a transmittance of 90% or more at 540 nm, a transmittance of 10% or less between 600 nm and 640 nm, and a transmittance of 5% or less at 450 nm, which is a green color for high transmission type CIS. May be suitable for filter implementation. That is, the photosensitive resin composition may be used for a high transmission type CMOS image sensor.

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

The core-shell compound according to one 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 one embodiment is included in the above range, the color gamut and contrast ratio are excellent .

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

The yellow pigment is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The green pigment is C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59 etc. are mentioned, These can be used individually or in mixture of 2 or more types.

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

The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment in the solvent.

The solid content of the pigment is 1% to 20% by weight, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% to 20% by weight, based on the total amount of the pigment dispersion. 15% by weight.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent, and the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol esters, alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

For example, commercially available products of the dispersant include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK from BYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 and the like from EFKA Chemical; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711, PB821, etc.

The dispersing agent 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 within the above range, an appropriate viscosity can be maintained, and thus the photosensitive resin composition has excellent dispersibility, thereby maintaining optical, physical and chemical qualities during product application.

Ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like may be used as the solvent forming the pigment dispersion.

The pigment dispersion may be included in an amount of 10 wt % to 20 wt %, for example, 12 wt % to 18 wt %, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included within the above range, it is advantageous to secure a process margin, and the color reproduction rate and contrast ratio are excellent.

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 includes one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric 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, α-methylstyrene, vinyltoluene, or vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds, such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate. acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc., but are not limited thereto, and may be used alone or in combination of two or more thereof. there is.

The weight average molecular weight of the binder resin may be 3,000 g/mol to 150,000 g/mol, eg 5,000 g/mol to 50,000 g/mol, eg 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to a substrate when manufacturing a color filter.

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

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 within the above range, it is possible to obtain excellent surface smoothness due to excellent developability and improved crosslinking property during manufacture of the color filter.

The photopolymerizable compound may be a monofunctional or multifunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

Since the photopolymerizable compound has the ethylenically unsaturated double bond, it can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Acrylates, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri( meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

Examples of commercially available products of the photopolymerizable compound are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S ^® of Nippon Kayaku Co., Ltd., the same TC-120S ^® , etc.; Osaka Yuki Kagaku Kogyo Co., Ltd.'s V- ^158® , V- ^2311® , etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M- ^210® , M- ^240® , and M- ^6200® of Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA ^® from Nippon Kayaku Co., Ltd., HX-220 ^® , R-604 ^® , etc.; Examples include V- ^260® , V- ^312® , and V-335 ^HP® of Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronix M- ^309® , M- ^400® , M- ^405® , M- ^450® , and M from Toagosei Chemical Industry Co., Ltd. -710 ^® , copper M-8030 ^® , copper M-8060 ^® , etc.; KAYARAD TMPTA ^® from Nippon Kayaku Co., Ltd., Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® , etc.; V-295 ^® , Dong-300 ^® , Dong-360 ® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® and ^the like of Osaka Yuki Kayaku Kogyo Co., Ltd. These products may be used alone or in combination of two or more.

The photopolymerizable compound may be used after being treated with an acid anhydride to impart better 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 within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability and excellent developability with an alkaline developer.

The photopolymerization initiator is an initiator generally used in photosensitive resin compositions, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, 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 the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

Examples of the triazine-based compound 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, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime) )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O- Acetate etc. are mentioned.

As the photopolymerization initiator, a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, a fluorene-based compound, and the like may be used in addition to the above compounds.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy thereto.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like. can be heard

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 within the above range, excellent reliability can be obtained due to sufficient curing during exposure in the pattern forming process, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to the unreacted initiator A decrease in transmittance can be prevented.

As the solvent, materials that have compatibility with the core-shell compound, pigment, binder resin, photopolymerizable compound, and photopolymerization initiator according to one embodiment but do not react may be used.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons, such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetic acid alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters such as 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as methyl ethyl propionate; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; ketonic acid esters such as ethyl pyruvate, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, considering compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxy ethyl propionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and/or ketones such as cyclohexanone may be used.

The solvent may be included in a balance amount, for example, 30 wt % to 80 wt %, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and therefore, processability in manufacturing the color filter is excellent.

The photosensitive resin composition according to another embodiment may further include an epoxy compound to improve adhesion to a substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 part by weight to 20 parts by weight, for example, 0.1 part by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, adhesion, storability, and the like are excellent.

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

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidox cypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 part 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 within the above range, adhesion, storability, and the like are excellent.

In addition, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defect formation, if necessary.

Examples of the surfactant, BM Chemie's BM-1000 ^® , BM-1100 ^® and the like; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® and the like of Dainippon Inki Kagaku Kogyo Co., Ltd.; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® and the like of Sumitomo 3M Co., Ltd.; Saffron S-112 ^® , S-113 ^® , S-131 ® , S-141 ^® , S-145 ^® and the like of Asahi ^Grass Co., Ltd.; Fluorine-based surfactants commercially available under names such as SH-28PA ^® , Copper-190 ^® , Copper-193 ^® , SZ-6032 ^® , SF-8428 ^® from Toray Silicone Co., Ltd. can be used.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is secured, stains are not generated, and wettability to a glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair physical properties.

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

A process of forming a pattern in the color filter is as follows.

applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied photosensitive resin composition to form a film of the photosensitive resin composition; exposing the film of the photosensitive resin composition to light; preparing a photosensitive resin film by developing the exposed photosensitive resin composition film with an aqueous alkali solution; and a step of heat-treating the photosensitive resin film. Since the process conditions and the like are widely known in the art, a detailed description thereof will be omitted in the present specification.

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

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

(Synthesis of compounds)

Synthesis Example 1: Synthesis of Compound Represented by Formula A

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol), 1-[4-(2-Ethyl-hexyloxy)-phenyl]-1H-indole (60 mmol) was added to toluene (200 mL) and butanol (200 mL) and refluxed, and the resulting water was removed with a Dean-stark distillation device. do. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula A below.

[Formula A]

Maldi-tof MS: 1243.5 m/z

Synthesis Example 2: Synthesis of Compound Represented by Formula B

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol), 1-[4-(2-Ethyl-hexyloxy)-phenyl]-6-methoxy-1H-indole (60 mmol) was added to toluene (200 mL) and butanol (200 mL) and refluxed, and the resulting water was prepared by Dean-stark removed by distillation. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula B below.

[Formula B]

Maldi-tof MS : 1273.58 m/z

Synthesis Example 3: Synthesis of Compound Represented by Formula C

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol), 1-[4-(2-Ethyl-hexyloxy)-phenyl]-1H-indole-6-carbonitrile (60 mmol) was added to toluene (200 mL) and butanol (200 mL) and refluxed, and the resulting water was dean-stark removed by distillation. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula C below.

[Formula C]

Maldi-tof MS : 1268.73 m/z

Synthesis Example 4: Synthesis of Compound Represented by Formula D

3-{4-[(2,4-Dimethyl-phenyl)-(2-methoxy-cyclohexyl)-amino]-phenyl}-4-hydroxy-cyclobut-3-ene-1,2-dione (60 mmol), 1-[4-(2-Ethyl-hexyloxy)-phenyl]-6-fluoro-1H-indole (60 mmol) was added to toluene (200 mL) and butanol (200 mL) and refluxed. removed by distillation. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula D below.

[Formula D]

Maldi-tof MS : 1261.73 m/z

Synthesis Example 5: Synthesis of Compound Represented by Formula E

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino)-phenyl]-4-hydroxy-cyclobut-3- Produced by refluxing ene-1,2-dione (60 mmol) and 6-Fluoro-1-(4-methoxy-phenyl)-1H-indole (60 mmol) in toluene (200 mL) and butanol (200 mL) The water is removed with a Dean-stark distillation device. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula E below.

[Formula E]

Maldi-tof MS : 1251.75 m/z

Synthesis Example 6: Synthesis of Compound Represented by 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), 6-Fluoro-1-(4-methoxy-phenyl)-1H-indole (60 mmol) in toluene (200 mL) and butanol (200 mL) and reflux the resulting water into a Dean-stark distillation device remove with After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula F below.

[Formula F]

Maldi-tof MS: 1027.49 m/z

Synthesis Example 7: Synthesis of Compound Represented by Formula G

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino)-phenyl]-4-hydroxy-cyclobut-3- After putting ene-1,2-dione (60 mmol) and 4-indol-1-yl-benzonitrile (60 mmol) in toluene (200 mL) and butanol (200 mL) and refluxing it, the water produced is a Dean-stark distillation device remove with After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula G below.

[Formula G]

Maldi-tof MS : 1242.54 m/z

Synthesis Example 8: Synthesis of Compound Represented by Formula H

3-[4-((2,4-Dimethyl-phenyl)-{2-[2-(2-methoxy-ethoxy)-ethoxy]-cyclohexyl}-amino)-phenyl]-4-hydroxy-cyclobut-3- After adding ene-1,2-dione (60 mmol) and 1-(4-Fluoro-phenyl)-1H-indole (60 mmol) to toluene (200 mL) and butanol (200 mL) and refluxing, the resulting water was deaned. Remove with -stark distillation equipment. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula H below.

[Formula H]

Maldi-tof MS : 1221.67 m/z

Synthesis Example 9: Synthesis of Compound Represented by 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), 1-[4-(2-Ethyl-hexyloxy)-phenyl]-1H-indole (60 mmol) were added to toluene (200 mL) and butanol (200 mL) and refluxed. The resulting water is removed with a Dean-stark distillation device. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by the following formula (I).

[Formula I]

Maldi-tof MS: 1331.81 m/z

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

Propionic acid 2-{(2-cyano-ethyl)-[4-(2-hydroxy-3,4-dioxo-cyclobut-1-enyl)-phenyl]-amino}-ethyl ester (60 mmol), 1-( 2-Ethyl-hexyl)-1H-indole (60 mmol) is added to toluene (200 mL) and butanol (200 mL) and refluxed, and the resulting water is removed using a Dean-stark distillation apparatus. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an asymmetric squailium-based compound. After dissolving this compound (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and added dropwise at room temperature for 5 hours at the same time. After 12 hours, it was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by the following formula C-1.

[Formula C-1]

Maldi-tof MS: 1088.48 m/z

Evaluation 1: Maximum absorption wavelength measurement

Compounds according to Synthesis Example 1 and Synthesis Example 9 to Comparative Synthesis Example 1 were prepared at a concentration of 0.001 wt% using a diluting solvent (ANONE), and according to Synthesis Example 1 and Synthesis Example 9 to Comparative Synthesis Example 1 Absorption spectra were obtained for each of the core-shell compounds, and the results are shown in Table 1 and FIG. 1. (UV-1800, SHIMADZU)

Maximum absorption wavelength (nm) Synthesis Example 1 620 Synthesis Example 2 625 Synthesis Example 3 618 Synthesis Example 4 619 Synthesis Example 5 620 Synthesis Example 6 625 Synthesis Example 7 621 Synthesis Example 8 617 Synthesis Example 9 620 Comparative Synthesis Example 1 596

Evaluation 2: Solubility measurement

A diluting solvent (PGMEA) was added to 0.5 g of the compound according to Synthesis Examples 1 to 9 and Comparative Synthesis Example 1, respectively, and the solution was stirred at 25°C and 100 rpm with a mix rotor (Iuchi Co., Ltd., MIXROTAR VMR-5). After stirring for 1 hour, the results of checking the solubility of each compound are shown in Table 2 below.

Solubility Evaluation Criteria

10% by weight or more of the compound (solute) dissolved in the total amount of the diluent: ○

Dissolves less than 10% by weight of the compound (solute) relative to the total amount of diluent: X

solubility Synthesis Example 1 ○ Synthesis Example 2 ○ Synthesis Example 3 ○ Synthesis Example 4 ○ Synthesis Example 5 ○ Synthesis Example 6 ○ Synthesis Example 7 ○ Synthesis Example 8 ○ Synthesis Example 9 ○ Comparative Synthesis Example 1 ○

From Table 2, it can be confirmed that both the compounds of Synthesis Examples 1 to 9 and the compound of Comparative Synthesis Example 1 have excellent solubility.

(Synthesis of photosensitive resin composition)

Example 1

The photosensitive resin composition according to Example 1 was prepared by mixing the components mentioned below in the composition shown in Table 3 below.

Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 2 hours, and then a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 2 hours. Subsequently, the compound prepared in Synthesis Example 1 (compound represented by Formula A) and a pigment (in the form of a pigment dispersion) as a coloring agent were added to the obtained reactant and stirred at room temperature for 1 hour. Subsequently, a photosensitive resin composition was prepared by filtering the product three times to remove impurities.

(Unit: % by weight) Mixed raw materials content coloring agent dyes Compound of Synthesis Example 1 5.0 pigment dispersion C.I. green pigment58 15.0 binder resin (A)/(B)=15/85(w/w),
Molecular Weight (Mw)=22,000g/mol
(A): methacrylic acid
(B): benzyl methacrylate 3.5 photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA) 8.0 photopolymerization initiator 1,2-Octanedione 1.0 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one 0.5 menstruum cyclohexanone 37.0 Propylene Glycol Monomethyl Ether Acetate (PGMEA) 30.0 Total 100.00

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except for using the compound of Synthesis Example 2 (compound represented by Formula B) instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 3 (compound represented by Formula C) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Example 4

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

Example 5

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

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 6 (compound represented by Formula F) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 7 (compound represented by Formula G) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Example 8

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 8 (compound represented by Formula H) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Example 9

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 9 (compound represented by Formula I) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A).

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 1 (compound represented by Formula A) was not used as a coloring agent.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 1 (compound represented by Formula C-1) was used instead of the compound of Synthesis Example 1 (compound represented by Formula A). .

Evaluation 3: Measurement of color coordinates, luminance and contrast ratio

The photosensitive resin composition prepared in Examples 1 to 9, Comparative Example 1 and Comparative Example 2 was applied to a thickness of 1 μm to 3 μm on a glass substrate having a thickness of 1 mm washed and degreased, and a hot plate at 90 ° C. dried for 2 minutes on top to obtain a coating film. Subsequently, the coating film was exposed to light using a high-pressure mercury lamp having a dominant wavelength of 365 nm. Thereafter, a sample was obtained by drying for 5 minutes in a hot air circulation drying furnace at 200 ° C. The transmittance of the sample was measured at wavelengths of 450 nm, 540 nm and 620 nm using a spectrophotometer (MCPD3000, Otsuka electronic Co.), and the results are shown in Table 4 and FIG. 2 below.

(unit: %) Transmittance at 450 nm Transmittance at 540 nm Transmittance at 620 nm Example 1 4.1 91.6 5.7 Example 2 4.1 93.8 4.3 Example 3 4.1 90.7 6.2 Example 4 4.1 91.2 6.0 Example 5 4.1 91.6 5.7 Example 6 4.1 93.8 4.3 Example 7 4.1 92.1 5.4 Example 8 4.1 90.3 6.5 Example 9 4.1 91.6 5.7 Comparative Example 1 4.1 95.3 34.5 Comparative Example 2 4.1 81.0 12.4

From Table 4, the photosensitive resin compositions of Examples 1 to 9 containing the core-shell compound according to one embodiment as a dye were compared with the photosensitive resin compositions of Comparative Examples 1 and 2 not containing the compound. Thus, the transmittance at 450 nm is 5% or less, the transmittance at 540 nm is 90% or more, and the transmittance at 620 nm is 10% or less. By using this as a green photosensitive resin composition, high transmittance type CIS can be manufactured. You can check if it is possible. (In the case of Comparative Example 2, the transmittance at 540 nm is 90% or less, which is a transmittance that is not applicable to a general CIS green photosensitive resin composition. In addition, the transmittance at 450 nm is 5% or less, and the transmittance at 540 nm is 90% or more When the condition is satisfied and the transmittance at 620 nm is as low as 10% or less, color mixing can be improved, ultimately enabling the manufacture of a high transmission type CIS green color filter.)

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and the detailed description of the invention and the accompanying drawings, and this is also the present invention. It goes without saying that it falls within the scope of the invention.

Claims (20)

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

[Formula 1-1-2]

[Formula 2]

In Formula 1-1-1,
R ¹ to R ³ and R ⁶ are each 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, a substituted or unsubstituted C1 to C20 An alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,
In Formula 1-1-2,
R ¹ is 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, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group,
R ⁶ is a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group Gigo,
In Formula 2,
L ^a and L ^b are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
delete delete According to claim 1,
Wherein R ¹ is a substituted or unsubstituted C1 to C20 alkoxy group.
According to claim 4,
Wherein R ² is a substituted or unsubstituted C3 to C20 cycloalkyl group.
According to claim 5,
Wherein R ² is a C3 to C20 cycloalkyl group substituted with an alkoxy group.
According to claim 4,
Wherein R ³ is a substituted or unsubstituted C6 to C20 aryl group.
According to claim 7,
Wherein R ³ is a C6 to C20 aryl group substituted with one or more alkyl groups.
According to claim 1,
In Formula 1-1-1, R ⁶ is a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkoxy group;
In Formula 1-1-2, R ⁶ is a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkoxy group.
According to claim 1,
The core represented by Formula 1 is a compound having a maximum absorption wavelength at 610 nm to 640 nm.
According to claim 1,
The shell represented by Formula 2 is a compound represented by Formula 2-1.
[Formula 2-1]

According to claim 1,
The core-shell compound is a compound represented by any one of Formulas A to Formula I.
[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

[Formula F]

[Formula G]

[Formula H]

[Formula I]

According to claim 1,
The compound is a green dye compound.
A photosensitive resin composition comprising the compound of any one of claims 1 and 4 to 13.
According to claim 14,
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.
According to claim 15,
The photosensitive resin composition has a transmittance of 5% or less at 450 nm.
According to claim 15,
The photosensitive resin composition is a photosensitive resin composition for a CMOS image sensor.
A photosensitive resin film prepared using the photosensitive resin composition of claim 14.
A color filter comprising the photosensitive resin film of claim 18.
A CMOS image sensor comprising the color filter of claim 19 .

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