KR20230149596A - Photosensitive resin composition, photosensitive resin layer using the same, color filter comprising the photosensitive resin layer, cmos image sensor comprising the photosensitive resin layer, display device comprising the color filter and camera comprising the cmos image sensor - Google Patents

Abstract

Provided are a photosensitive resin composition which includes (A) binder resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, (D) colorant, and (E) solvent, wherein the colorant includes an organic pigment coated with dyes and the dyes includes at least one of the following chemical formulae 1 to 5 as a functional group; a photosensitive resin film manufactured using the same; a color filter and a CMOS image sensor including the photosensitive resin film, a display device including the color filter, and a camera including the CMOS image sensor. In the chemical formulae 1 to 5, each substituent is defined in the specification.

Description

Photosensitive resin composition, photosensitive resin film manufactured using the same, color filter and CMOS image sensor including the photosensitive resin film, display device and camera {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME, COLOR FILTER COMPRISING THE PHOTOSENSITIVE RESIN LAYER, CMOS IMAGE SENSOR COMPRISING THE PHOTOSENSITIVE RESIN LAYER, DISPLAY DEVICE COMPRISING THE COLOR FILTER AND CAMERA COMPRISING THE CMOS IMAGE SENSOR}

This description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, a color filter and a CMOS image sensor including the photosensitive resin film, a display device including the color filter, and a camera including the color filter.

An image sensor is a device that reads information about a subject and converts it into electrical image signals, and is used in various electronic devices such as smartphones, cars, laptops, and cameras. Image quality is greatly influenced by the amount of light collected in the pixels that make up the sensor, and with the trend toward miniaturization of image sensors, technology to increase light reception rate (the degree to which the image sensor receives light) is required. In this way, technology is needed to improve the patterning (regularity/straightness) of the color filter pattern to prevent electrical & optical crosstalk and deterioration of quantum efficiency.

As image sensors become smaller, the thickness of the color filter is becoming thinner. Accordingly, each RGB color must be separated, so the pigment content is increased or dye is added to realize spectral RGB, but the problem is the dye input. As a result, the content of the pigment is relatively reduced, which reduces durability, which ultimately affects the transmittance of the composition and also reduces the patterning of the color filter, which is a problem.

In one embodiment, a dye having maximum absorbance in a specific wavelength range is coated with an organic pigment so that the pigment contains a specific auxochromophore, so that the photosensitive resin composition containing the pigment has the lowest transmittance within a specific wavelength range. The purpose is to provide a photosensitive resin composition that can control and improve the pattern properties of patterns in a color filter.

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

Another embodiment is to provide a color filter and a CMOS image sensor including the photosensitive resin film.

Another embodiment is to provide a display device including the color filter.

Another implementation example is to provide a camera including the CMOS image sensor.

One embodiment includes (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, wherein the colorant includes an organic pigment coated with a dye, The dye provides a photosensitive resin composition including at least one of the following Chemical Formulas 1 to 5 as a functional group.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 1 to 5,

R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, provided that R ¹ and R ² are not hydrogen atoms at the same time,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

The dye may have a moiety represented by the following formula M-1.

[Formula M-1]

R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁵ and R ⁶ may each independently be fused with a nitrogen atom to form a nitrogen-containing fused ring.

The formula M-1 may be represented by the following formula M-1-1 or formula M-1-2.

[Formula M-1-1]

[Formula M-1-2]

In the above formulas M-1-1 and M-1-2,

R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

_and ^_

[Formula X-1]

The dye may have a moiety represented by the formula M-2 below.

[Formula M-2]

The dye may be represented by any one of the following formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8,

R ⁵ to R ⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁹ is a functional group represented by at least one of Formulas 1 to 5 above.

The dye may be represented by any one of the following formulas 6-1 to 8-1.

[Formula 6-1]

[Formula 7-1]

[Formula 8-1]

The dye may have a maximum absorbance within a wavelength range of 500 nm to 540 nm.

The organic pigment may include red pigment, green pigment, yellow pigment, or a combination thereof.

The colorant includes an organic pigment coated with the dye and an organic pigment not coated with the dye, and the organic pigment coated with the dye may be included in a smaller amount than the organic pigment not coated with the dye.

The binder resin may include a cardo-based binder resin and an acrylic-based binder resin.

The photosensitive resin composition includes 0.1% to 10% by weight of the (A) binder resin, 0.5% to 5% by weight of the (B) photopolymerizable monomer, and 0.1% by weight of the (C) photopolymerization initiator, based on the total amount of the photosensitive resin composition. It may include weight% to 5% by weight, 20% to 70% by weight of the colorant (D), and the remaining amount of the solvent (E).

The photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, or a combination thereof.

Another embodiment provides a photosensitive resin film manufactured 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 photosensitive resin film.

Another embodiment provides a display device including the color filter.

Another implementation provides a camera including the CMOS image sensor.

Details of other aspects of the invention are included in the detailed description below.

The photosensitive resin composition according to one embodiment includes an organic pigment coated with a dye containing a specific functional group as a colorant, and has the lowest transmittance within the wavelength range of 500 nm to 540 nm, making it suitable for application to a CMOS image sensor. Furthermore, it can have a positive effect on the pattern properties of the color filter.

Figure 1 is a graph of absorbance according to wavelength of the compound represented by Chemical Formula 6-1.
Figure 2 is a graph of transmittance according to wavelength of the photosensitive resin compositions according to Examples 1 to 3, Comparative Examples 1, and Comparative Examples 2.
Figure 3 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using the photosensitive resin composition according to Example 1.
Figure 4 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using the photosensitive resin composition according to Example 2.
Figure 5 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using the photosensitive resin composition according to Example 3.
Figure 6 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using the photosensitive resin composition according to Comparative Example 1.
Figure 7 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using the photosensitive resin composition according to 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, “alkyl group” refers to a C1 to C20 alkyl group, “alkenyl group” refers to a C2 to C20 alkenyl group, and “cycloalkenyl group” refers to a C3 to C20 cycloalkenyl group. , “Heterocycloalkenyl group” refers to a C3 to C20 heterocycloalkenyl group, “aryl group” refers to a C6 to C20 aryl group, “arylalkyl group” refers to a C6 to C20 arylalkyl group, and “alkylene group” means a C1 to C20 alkylene group, “arylene group” means a C6 to C20 arylene group, “alkylarylene group” means a C6 to C20 alkylarylene group, and “heteroarylene group” means a C3 to C20 heteroarylene group. It means an arylene group, and “alkoxylene group” means a C1 to C20 alkoxylene group.

Unless otherwise specified herein, “substitution” means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, “hetero” means that at least one hetero atom of N, O, S, and P is included in the chemical formula.

Also, unless otherwise specified in the specification, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid.” "It means that both are possible.

Unless otherwise defined herein, “combination” means mixing or copolymerization. Additionally, “copolymerization” refers to block copolymerization to random copolymerization, and “copolymer” refers to block copolymerization to random copolymerization.

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

As used herein, cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of the following formulas 9-1 to 9-11 is included in the backbone of the resin.

Unless otherwise defined herein, “*” means a part connected to the same or different atoms (including hydrogen atoms) or a chemical formula.

The photosensitive resin composition according to one embodiment includes (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, and the colorant is an organic pigment coated with a dye. Since the dye includes at least one of the following Chemical Formulas 1 to 5 as a functional group, the photosensitive resin film (cured film) manufactured using the photosensitive resin composition according to one embodiment is a color filter and a CMOS image. It can be applied to all sensors to provide excellent performance.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 1 to 5,

R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, provided that R ¹ and R ² are not hydrogen atoms at the same time,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

Specifically, in the case of a CMOS image sensor, it is advantageous in terms of light reception rate when the absorbance is high within a specific wavelength range, such as 400 nm to 700 nm, such as 500 nm to 580 nm, and such as 500 nm to 540 nm. The photosensitive resin composition according to one embodiment has By modifying the colorant to have maximum absorbance within the wavelength range of 500 nm to 540 nm, it can be excellent for application to CMOS image sensors.

In addition, photosensitive resin compositions go through coating, exposure, development, and curing processes. In some cases, the dye melts during development, and when dye is added instead of the binder resin, the relative content of the binder resin decreases, resulting in poor patterning. According to one embodiment, by covering the dye with an organic pigment, the problem of the dye melting away during development can be solved, and since the part that does not form a pattern is replaced with a dye, it also has a positive effect on the patternability. .

Below, each component is described in detail.

(D) Colorant

For example, the dye may have a moiety represented by the following formula M-1, and the moiety may be substituted with a functional group represented by any one of formulas 1 to 5.

[Formula M-1]

R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁵ and R ⁶ may each independently be fused with a nitrogen atom (of Formula M-1) to form a nitrogen-containing fused ring.

For example, the formula M-1 may be represented by the following formula M-1-1 or the formula M-1-2, but is not necessarily limited thereto.

[Formula M-1-1]

[Formula M-1-2]

In the above formulas M-1-1 and M-1-2,

R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

X is chloride ions ( ^CL- ), fluorine ions ( ^F- ), Iodinization ions ( ^I- ), brominated ions ( ^br- ), nitrate ions (NO _3- ⁾ , hydroxide ions ( ^oh- ) (ClO ₄ ^- ) or is represented by the formula X-1 below.

[Formula X-1]

For example, the dye may have a moiety represented by the following formula M-2, and the moiety may be substituted with a functional group represented by any one of formulas 1 to 5.

[Formula M-2]

For example, the dye may be represented by any one of the following formulas 6 to 8, but is not necessarily limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8,

R ⁵ to R ⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁹ is a functional group represented by at least one of Formulas 1 to 5 above.

For example, the dye may be represented by any one of the following formulas 6-1 to 8-1, but is not necessarily limited thereto.

[Formula 6-1]

[Formula 7-1]

[Formula 8-1]

For example, the dye may have a maximum absorbance within a wavelength range of 500 nm to 540 nm.

For example, the dye may be a salt form dye and/or a nonionic dye. If the dye is a cationic dye or an anionic dye, it is difficult to control the maximum absorbance within a specific wavelength range, and it may have a negative effect on the patterning within the color filter, which may be undesirable.

Meanwhile, the dye is coated on the surface of an organic pigment and not on the surface of an inorganic pigment such as carbon black. In the case of photosensitive resin compositions containing inorganic pigments such as carbon black as a colorant, they are mainly used for the purpose of achieving black color, and therefore cannot achieve the intended effect of the present invention at all. For example, the organic pigment may be a non-black organic pigment.

For example, the organic pigment may include red pigment, green pigment, yellow pigment, blue pigment, or a combination thereof.

Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89, etc. can be mentioned. Examples of the green pigment include C.I. Green Pigment 36, C.I. Green Pigment 7, C.I. Green Pigment 58, C.I. Green Pigment 59, C.I. Green pigment 62, etc. can be mentioned. Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Copper phthalocyanine pigments such as blue pigment 16 and the like can be mentioned. Examples of the yellow pigment include C.I. Isoindoline pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. and nickel complex pigments such as yellow pigment 150. The above pigments can be used alone or in a mixture of two or more, and are not limited to these examples.

For example, the colorant may include an organic pigment coated with the dye and an organic pigment not coated with the dye. In this case, the organic pigment coated with the dye may be included in a smaller amount than the organic pigment not coated with the dye.

Both the organic pigment coated with the dye and the organic pigment not coated with the dye may be included in the photosensitive resin composition in the form of a dispersion. This pigment dispersion may be composed of the pigment, solvent, dispersant, dispersion resin, etc.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, and carboxylic acid salt. , alkyl amide, alkylene oxide adduct, alkyl amine, etc., and these can be used alone or in a mixture of two or more.

Examples of commercially available dispersants include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -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, etc. from EFKA Chemicals; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the composition has excellent dispersibility, resulting in excellent stability, developability, and patternability when manufacturing a partition for light blocking.

The dispersion resin may be an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patterning of the pixel.

Meanwhile, the organic pigment may be used after pretreatment using a water-soluble inorganic salt and a wetting agent. When the organic pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed through the steps of kneading the organic pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be performed at a temperature of 40°C to 100°C, and the filtration and washing may be performed by washing the inorganic salt with water or the like and then filtering.

Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed and the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. alkylene glycol monoalkyl ether; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyethylene glycol, etc. can be used alone or in a mixture of two or more.

The organic pigment that has gone through the kneading step may have an average particle diameter of 5 nm to 200 nm, for example, 5 nm to 150 nm. When the average particle diameter of the organic pigment is within the above range, stability in the pigment dispersion is excellent, and there is no concern about deterioration of pixel resolution.

The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. Among these, propylene glycol methyl ether acetate is preferred. You can.

Based on the total amount of the photosensitive resin composition, the colorant may be included in an amount of 20% by weight to 70% by weight. When the colorant is included in the above weight ratio range, it can have excellent heat resistance while maintaining color characteristics.

(A) Binder resin

The binder resin may be a cardo-based binder resin, an acrylic binder resin, a polyimide-based binder resin, a polyurethane-based binder resin, or a combination thereof.

The binder resin may be a mixture of the cardo-based binder resin and the acrylic-based binder resin. In this case, the heat resistance and chemical resistance of the photosensitive resin composition can be improved, and above all, it can be very advantageous in securing low-reflection characteristics.

The weight average molecular weight of the cardo-based binder resin may be 1,000 g/mol to 50,000 g/mol, specifically 3,000 g/mol to 35,000 g/mol. If the weight average molecular weight of the cardo-based binder resin is within the above range, excellent patternability and developability can be obtained when manufacturing a black matrix or a partition for light blocking.

The cardo-based binder resin may be a compound containing a repeating unit represented by the following formula (9).

[Formula 9]

In Formula 9 above,

R ₂₄ to R ₂₇ may each independently be a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ and R ₂₉ may each independently be a hydrogen atom, or CH ₂ OR _a (R _a is a vinyl group, an acrylic group, or a methacryl group),

R ₃₀ may be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylic group, or a methacryl group,

Z ₁ is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (where R _b to R _e are the same or different from each other and represent a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group ), or any one selected from the group consisting of compounds represented by the following formulas 9-1 to 9-11,

Z ₂ may be an acid anhydride residue or an acid dianhydride residue.

[Formula 9-1]

[Formula 9-2]

[Formula 9-3]

[Formula 9-4]

[Formula 9-5]

In Formula 9-5,

R _f is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ , or a phenyl group.

[Formula 9-6]

[Formula 9-7]

[Formula 9-8]

[Formula 9-9]

[Formula 9-10]

[Formula 9-11]

The cardo-based binder resin can be specifically obtained by reacting a compound represented by the following formula (10) with tetracarboxylic dianhydride.

[Formula 10]

The tetracarboxylic dianhydride may be aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromelliic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4-biphenyltetracarboxylic acid dianhydride, 2, 2',3,3'-Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3 ,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc. may be mentioned, but are not limited thereto.

The acrylic binder resin is a first ethylenically unsaturated monomer　and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing 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 to 50% by weight, specifically, 10 to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and 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; These can be mentioned, and these can be used alone or in a mixture of two or more.

Specific examples of the acrylic binder resin include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, and methacrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer. Polymers, methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, etc. may be mentioned, but are not limited thereto, and may be used alone or in combination of two or more types.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, specifically 5,000 g/mol to 50,000 g/mol, and more specifically 20,000 g/mol to 30,000 g/mol. It can be mol.　When the weight average molecular weight of the acrylic binder resin is within the above range, the black photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate when manufacturing the light blocking layer.

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

When the cardo-based binder resin and the acrylic binder resin are mixed and used, the acrylic binder resin may be included in the same amount as the cardo-based binder resin. In this case, it is possible to improve developability and process margin.

The binder resin may be included in an amount of 0.1 wt% to 10 wt%, for example, 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, the viscosity is appropriately maintained, and patternability, processability, and developability are excellent when manufacturing a photosensitive resin film.

(B) Photopolymerizable monomer

The photopolymerizable monomer may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

Since the acrylic photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization occurs during exposure to light in the pattern formation process, thereby forming a pattern with excellent heat resistance, light resistance, and chemical resistance.

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

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

The photopolymerizable monomer may be used after being treated with an acid anhydride to provide better developability.

The photopolymerizable monomer may be included in an amount of 0.5% to 5% by weight, for example, 1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.

(C) Photopolymerization initiator

The photopolymerization initiator may be 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.

Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

Examples of the benzophenone-based compounds 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, etc.

Examples of the thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso Propyl thioxanthone, etc. can be mentioned.

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

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-Biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichlor Romethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. can be mentioned.

Examples of the oxime-based compounds 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, 1-(3-Cyclopentyl-1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)propylideneaminooxy)ethanone, 2-(benzoyloxyimino)-3 -Cyclopentyl-1-(4-(phenylthio)phenyl)propan-1-one, etc. can be used. Specific examples of the O-acyloxime compounds 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)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime- O-acetate, etc. can be used.

In addition to the above compounds, the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and fluorene-based compounds.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 0.1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization sufficiently occurs during exposure in the pattern formation process, and the sensitivity of the manufactured photosensitive resin film becomes excellent.

(E) Solvent

The solvent may be a material that is compatible with but does not react with the colorant, binder resin, photopolymerizable monomer, photopolymerization initiator, and other additives described later.

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, ethylene glycol monoethyl ether, and ethylene glycol dimethyl 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 ethyl methyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl 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; Alkyl oxyacetic acid esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetic acid alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionate esters such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2- Monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate; Keto acid esters such as ethyl pyruvate, etc. Also include N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, 3-methylbenzoic acid, 3-methoxybutyl acetate, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, considering compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol ethylmethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, 3-methylbenzoic acid, 3-methoxybutyl acetate, etc. may be used.

The solvent may be included in a residual amount, for example, 10% to 70% by weight, for example, 20% to 60% by weight, or for example, 25% to 60% by weight, relative to the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity and thus the processability in manufacturing the photosensitive resin film is excellent.

(F) Other additives

Meanwhile, the photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, silane-based coupling agent, leveling agent, surfactant, or a combination thereof.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, carboxyl group, methacryloxy group, isocyanate group, or epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-gly. Sidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be used alone or in combination of two or more.

The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion, storage, etc. are excellent.

In addition, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant and/or a silicone-based surfactant, if necessary, to improve coating properties and prevent defects.

Examples of the fluorine-based surfactants include BM-1000 ^® and BM-1100 ^® from BM Chemie; Mechapack F 142D ^® , Mechapack F 172 ^® , Mechapack F 173 ^® , Mechapack F 183 ^® , Mechapack F 554 ^® , etc. from Dainippon Inki Chemicals Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , Prorad FC-170C ^® , Prorad FC-430 ^® , Prorad FC-431 ^® , etc.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , Saffron S-113 ^® , Saffron S-131 ^® , Saffron S-141 ^® , Saffron S-145 ^® , etc.; Those commercially available under names such as SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , and SF-8428 ^® from Toray Silicone Co., Ltd. can be used.

The silicone-based surfactants include BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, manufactured by BYK Chem. You can use one that is commercially available under names such as BYK-325.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on the total amount of the photosensitive resin composition. When the surfactant is contained within the above range, coating uniformity is ensured, stains do not occur, and wetting on an IZO substrate or glass substrate is excellent.

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

The photosensitive resin composition according to one embodiment may be a positive type or a negative type, but in order to more completely remove residues in the area where the pattern is exposed after exposure and development of the composition having light blocking properties, it is better to use the negative type. desirable.

Another embodiment provides a photosensitive resin film manufactured by exposing, developing, and curing the photosensitive resin composition described above.

The photosensitive resin film manufacturing method is as follows.

(1) Application and film formation stage

The photosensitive resin composition is applied to a desired thickness using a spin or slit coat method, roll coat method, screen printing method, or applicator method on a substrate such as a glass substrate or ITO substrate that has been pretreated, and then cooled at 70°C. A coating film is formed by removing the solvent by heating (prebaking) at 110°C for 1 to 10 minutes.

(2) exposure step

In order to form the necessary pattern on the obtained coating film, a mask is interposed, and then exposure is performed by irradiating active rays of 200 nm to 500 nm. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

The exposure amount varies depending on the type, mixing amount, and dry film thickness of each component of the composition, but when using a high-pressure mercury lamp, it is 500 mJ/cm ² (based on a 365 nm sensor) or less.

(3) Development stage

An alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed parts remaining to form a pattern.

(4) Post-processing step

There is a post-heating process to obtain an image pattern obtained through development that is excellent in terms of heat resistance, adhesion, chemical resistance, etc. For example, after development, the image pattern obtained by development can be placed in a convection oven at 250°C and then heated (post-baking) for 1 hour.

Another embodiment provides a color filter and/or a CMOS image sensor including the photosensitive resin film.

Another embodiment provides a display device including the color filter.

Another implementation provides a camera including the CMOS image sensor.

Hereinafter, preferred embodiments of the present invention will be described. However, the following example is only a preferred example of the present invention, and the present invention is not limited by the following example.

(Dye synthesis)

Synthesis Example 1

Manufacturer: Merck

Product Name: Rhodamine 6G

[Formula 6-1]

Synthesis Example 2

Manufacturer: TCI

Product Name: Acid Red 289

[Formula 7-1]

Synthesis Example 3

Manufacturer: Merck

Product Name: Acid Blue 25

[Formula 8-1]

(Manufacturing of organic pigment dispersion coated with dye)

Manufacturing Example 1

1000 g of yellow pigment (BJ1144; SANYO) was mixed with water to prepare 10 L of slurry, stirred at 95°C for 1 hour, allowed to cool, and then washed with water. This was again mixed with water to prepare 10 L of slurry, 42.9 g of 70% nitric acid was added, and the mixture was stirred at 40°C for 4 hours. This was left to cool, washed with water, and mixed again with water to prepare 10 L of slurry. 769.2 g of a 13% aqueous sodium hypochlorite solution was added and stirred at 40°C for 6 hours. This was left to cool, washed with water, mixed again with water to prepare 10 L of slurry, 38.1 g of dye represented by the following formula 6-1 was added, stirred at 40°C for 1 hour, and then 10.1 g of aluminum sulfate was further added. It was stirred at 40°C for 1 hour. This was left to cool, washed with water, filtered and dried to obtain a yellow pigment coated with a dye represented by the following formula 6-1.

Production example 2

It was the same as Preparation Example 1, except that the dye represented by Formula 7-1 was used instead of the dye represented by Formula 6-1.

Production example 3

It was the same as Preparation Example 1, except that the dye represented by Formula 8-1 was used instead of the dye represented by Formula 6-1.

(Photosensitive resin composition production)

The components mentioned below were mixed in the composition shown in Table 1 below and stirred for 6 hours to prepare photosensitive resin compositions according to Examples 1 to 3, Comparative Examples 1, and Comparative Examples 2. Specifically, the photopolymerization initiator content was accurately measured, the solvent was added, and the mixture was sufficiently stirred until the initiator was completely dissolved. Afterwards, the binder resin and photopolymerizable monomer were sequentially added, and then stirred for another hour. Afterwards, other additives were added, a colorant (pigment dispersion liquid) was added, and finally the entire composition was stirred for more than 2 hours to prepare a photosensitive resin composition.

(Unit: g) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) Binder resin 0.5 0.5 0.5 0.27 0.5 (B) Photopolymerizable monomer 1.1 1.1 1.1 0.63 1.1 (C) Photopolymerization initiator 0.2 0.2 0.2 0.13 0.2 (D) Colorant (D-1) 29.3 29.3 29.3 29.3 29.3 (D-2) - - - 21.0 21.0 (D-3) 21.0 - - - - (D-4) - 21.0 - - - (D-5) - - 21.0 - - (D-6) - - - 0.84 - (E) Solvent 47.5 47.5 47.5 47.5 47.5 (F) Other additives 0.2 0.2 0.2 0.2 0.2

(A) Binder resin

Acrylic binder resin (RY-117, Showa Denko)

(B) Photopolymerizable monomer

Dipentaerythritol hexa(meth)acrylate (DPHA, Japan Explosives)

(C) Photopolymerization initiator

SPI-03 (Samyang Company)

(D) Colorant

(D-1) Red pigment (CI-254-P71, SAKATA company)

(D-2) Yellow pigment (BJ1144, SANYO)

(D-3) Coating dye of Preparation Example 1

(D-4) Coating dye of Preparation Example 2

(D-5) Coating dye of Preparation Example 3

(D-6) Dye of Synthesis Example 1

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA, Biryong Co., Ltd.)

(F) Other additives

Surfactant (F-554 (using 10% dilution), DIC)

(evaluation)

Pattern evaluation

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1 and 2 were spin-coated on an 8'' silicon wafer and soft-baked at about 100°C for 3 minutes to obtain a thickness of about 0.6㎛. It was applied with . Then, after cooling at room temperature for 60 seconds, light was irradiated at 1000 msec with an i-line stepper (Nikon, NSR-2005i10C) to induce a photocuring reaction in the photosensitive portion. The exposed substrate was developed using a puddle method in a 0.3% TMAH aqueous solution at room temperature, and then washed with pure solvent for 120 seconds. Afterwards, it was dried at room temperature and post-baked at 200°C for 5 minutes to obtain a patterned specimen. After forming the pattern specimen, the 1.4um pattern CD was measured using CD-SEM (Hitachi, S-9380-2), and the results are shown in Figures 3 to 7 below.

From Figures 3 to 7, it can be seen that a photosensitive resin film with excellent patterning properties can be obtained by using the photosensitive resin composition according to one embodiment.

Transmittance evaluation

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1, and 2 were spin-coated on an 8'' glass wafer, soft-baked at about 100°C for 3 minutes, and then baked at room temperature. After cooling for 60 seconds, light was irradiated for 1000 msec with an i-line stepper (Nikon, NSR-2005i10C) to induce a photocuring reaction in the photosensitive area. The exposed substrate was developed using a puddle method in a 0.3% TMAH aqueous solution at room temperature, and then washed with pure solvent for 120 seconds. Afterwards, it was dried at room temperature and post-baked at 200°C for 5 minutes to obtain a 0.6㎛ specimen. The transmittance of the obtained specimen was measured using a transmittance device, and the results are shown in Figure 2.

From Figure 2, it can be seen that transmittance can be minimized in the 500nm to 540nm wavelength range by using the photosensitive resin composition according to one embodiment.

The present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art will be able to form other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

Claims (17)

(A) binder resin,
(B) photopolymerizable monomer,
(C) photopolymerization initiator,
(D) colorant and
(E) Solvent
Including,
The colorant includes an organic pigment coated with a dye,
The dye is a photosensitive resin composition comprising at least one of the following Chemical Formulas 1 to 5 as a functional group.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 1 to 5,
R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, provided that R ¹ and R ² are not hydrogen atoms at the same time,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.
According to paragraph 1,
The dye is a photosensitive resin composition having a moiety represented by the following formula M-1:
[Formula M-1]

R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁵ and R ⁶ may each independently be fused with a nitrogen atom to form a nitrogen-containing fused ring.
According to paragraph 2,
The formula M-1 is a photosensitive resin composition represented by the following formula M-1-1 or formula M-1-2.
[Formula M-1-1]

[Formula M-1-2]

In the formulas M-1-1 and M-1-2,
R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
_and ^_
[Formula X-1]

According to paragraph 1,
The dye is a photosensitive resin composition having a moiety represented by the following formula M-2.
[Formula M-2]

According to paragraph 1,
The dye is a photosensitive resin composition represented by any one of the following formulas 6 to 8:
[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8,
R ⁵ to R ⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁹ is a functional group represented by at least one of Formulas 1 to 5 above.
According to paragraph 1,
The dye is a photosensitive resin composition represented by any one of the following formulas 6-1 to 8-1.
[Formula 6-1]

[Formula 7-1]

[Formula 8-1]

According to paragraph 1,
The dye is a photosensitive resin composition having a maximum absorbance within a wavelength range of 500 nm to 540 nm.
According to paragraph 1,
The organic pigment is a photosensitive resin composition including red pigment, green pigment, yellow pigment, or a combination thereof.
According to paragraph 1,
The colorant includes an organic pigment coated with the dye and an organic pigment not coated with the dye,
A photosensitive resin composition in which the organic pigment coated with the dye is contained in a smaller amount than the organic pigment not coated with the dye.
According to paragraph 1,
The binder resin is a photosensitive resin composition including a cardo-based binder resin and an acrylic-based binder resin.
According to paragraph 1,
The photosensitive resin composition is, with respect to the total amount of the photosensitive resin composition,
(A) 0.1% by weight to 10% by weight of binder resin,
(B) 0.5% to 5% by weight of photopolymerizable monomer,
(C) 0.1% to 5% by weight of photopolymerization initiator,
20% to 70% by weight of the (D) colorant, and
(E) residual amount of solvent
A photosensitive resin composition containing a.
According to paragraph 1,
The photosensitive resin composition further includes malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, or a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 12.
A color filter comprising the photosensitive resin film of claim 13.
A CMOS image sensor comprising the photosensitive resin film of claim 13.
A display device including the color filter of claim 14.
A camera including the CMOS image sensor of claim 15.