KR102815437B1 - 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

[화학식 2]

[화학식 3]

[화학식 4]

[화학식 5]

(상기 화학식 1 내지 화학식 5에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) a photosensitive resin composition comprising a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, wherein the colorant comprises an organic pigment coated with a dye, and the dye comprises at least one or more 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 comprising the photosensitive resin film, a display device comprising the color filter, and a camera comprising the CMOS image sensor are provided.
[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

(In the above chemical formulas 1 to 5, each substituent is as 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}

The present invention 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.

Image sensors are devices that read information from a subject and convert it into electrical image signals, and are used in various electronic devices such as smartphones, automobiles, laptops, and cameras. The image quality is greatly affected by the amount of light collected by the pixels that make up the sensor, and as image sensors become smaller, technology is required to increase the light reception rate (the degree to which the image sensor accepts light). To this end, technology is needed to improve the pattern (regularity/straightness) of the color filter pattern to suppress electrical and optical color mixing (crosstalk) and prevent quantum efficiency degradation.

As image sensors become increasingly smaller, color filters are becoming thinner, and accordingly, RGB color separation is required, so the pigment content is increased or dye is added to implement RGB of the spectrum. However, the problem is that durability is reduced as the pigment content is relatively reduced due to the addition of dye, which ultimately affects the transmittance of the composition and also reduces the patterning of the color filter, which is problematic.

One embodiment is to provide a photosensitive resin composition which can control a photosensitive resin composition including the pigment to have the lowest transmittance within a specific wavelength range by coating an organic pigment with a dye having a maximum absorbance in a specific wavelength range so that the pigment includes a specific chromatic group, and can also improve the patternability of a pattern 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 embodiment is to provide a camera including the CMOS image sensor.

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

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

In the chemical formulas 1 to 5 above,

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 both hydrogen atoms,

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

[Chemical Formula M-1]

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

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

The above chemical formula M-1 can be represented by the following chemical formula M-1-1 or chemical formula M-1-2.

[Chemical formula M-1-1]

[Chemical formula M-1-2]

In the above chemical 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 represented by the following chemical formula X-1: chloride ion, fluoride ion, iodide ion, bromide ion, nitrate ion, hydroxide ion, perchlorate ion (ClO ₄ ^- ).

[Chemical Formula X-1]

The above dye may have a moiety represented by the following chemical formula M-2.

[Chemical Formula M-2]

The above dye can be represented by any one of the following chemical formulas 6 to 8.

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

In the chemical formulas 6 to 8 above,

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 the chemical formulas 1 to 5.

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

[Chemical Formula 6-1]

[Chemical Formula 7-1]

[Chemical Formula 8-1]

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

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

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

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

The above photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane 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 embodiment provides a camera including the CMOS image sensor.

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

A photosensitive resin composition according to one embodiment of the present invention comprises an organic pigment coated with a dye containing a specific functional group as a colorant, thereby having the lowest transmittance within a wavelength range of 500 nm to 540 nm, and is therefore suitable for application to a CMOS image sensor, and can further have a positive effect on the patternability of a color filter.

Figure 1 is a graph of the absorbance according to wavelength of the compound represented by chemical formula 6-1.
FIG. 2 is a graph showing the transmittance according to wavelength of the photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2.
FIG. 3 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using a photosensitive resin composition according to Example 1.
FIG. 4 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using a photosensitive resin composition according to Example 2.
FIG. 5 is a scanning electron microscope photograph showing a pattern photograph of a photosensitive resin film manufactured using a 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 a 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 a photosensitive resin composition according to Comparative Example 2.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims described below.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "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, "heteroarylene group" means a C3 to C20 heteroarylene group, and "alkoxylene group" means a C1 It refers to a C20 alkoxylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is substituted with 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, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 It means substituted with a C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

Additionally, unless otherwise specifically stated herein, “hetero” means that the chemical formula contains at least one heteroatom of at least one of N, O, S, and P.

Additionally, unless otherwise specifically stated herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

Unless otherwise defined herein, "combination" means a mixture or copolymerization. In addition, "copolymerization" means a block copolymerization or a random copolymer, and "copolymer" means a block copolymer or a random copolymer.

Unless otherwise defined in the chemical formulas herein, 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.

In this specification, the cardo-based resin means a resin in which at least one functional group selected from the group consisting of the following chemical formulas 9-1 to 9-11 is included in the backbone of the resin.

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

A photosensitive resin composition according to one embodiment comprises (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, wherein the colorant comprises an organic pigment coated with a dye, and the dye comprises at least one or more of the following chemical formulae 1 to 5 as a functional group. Therefore, a photosensitive resin film (cured film) manufactured using the photosensitive resin composition according to one embodiment can be applied to both a color filter and a CMOS image sensor, and can exhibit excellent performance.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

In the chemical formulas 1 to 5 above,

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 both hydrogen atoms,

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, high absorbance is advantageous in terms of light reception rate when the absorbance is high within a specific wavelength range, for example, a wavelength range of 400 nm to 700 nm, for example, a wavelength range of 500 nm to 580 nm, for example, a wavelength range of 500 nm to 540 nm. Accordingly, the photosensitive resin composition according to one embodiment can be excellently applied to a CMOS image sensor by modifying the colorant so as to have maximum absorbance within a wavelength range of 500 nm to 540 nm.

In addition, in the case of a photosensitive resin composition, the dye may melt during development during the coating, exposure, development, and curing processes, and when the dye is added instead of the binder resin, the relative content of the binder resin may decrease, resulting in poor patternability. However, according to one embodiment, by coating the dye on an organic pigment, the problem of the dye melting during development can be solved, and since a portion that does not form a pattern is replaced with the dye, it also has a positive effect on the patternability.

Each component is described in detail below.

(D) Colorant

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

[Chemical Formula M-1]

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

The above R ⁵ and R ⁶ can each independently be fused with a nitrogen atom (of the above chemical formula M-1) to form a nitrogen-containing fused ring.

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

[Chemical formula M-1-1]

[Chemical formula M-1-2]

In the above chemical 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 represented by the following chemical formula X-1: chloride ion (Cl ^- ), fluoride ion (F ^- ), iodide ion (I ^- ), bromide ion (Br ^- ), nitrate ion (NO ₃ ^- ), hydroxide ion (OH ^- ), perchlorate ion (ClO ₄ ^- ).

[Chemical Formula X-1]

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

[Chemical Formula M-2]

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

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

In the chemical formulas 6 to 8 above,

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 the chemical formulas 1 to 5.

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

[Chemical Formula 6-1]

[Chemical Formula 7-1]

[Chemical 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-type dye and/or a nonionic dye. If the dye is a cationic dye or an anionic dye, it may be difficult to control the maximum absorbance within a specific wavelength range, and may also have a negative effect on the patternability within the color filter, which may be undesirable.

Meanwhile, the dye is coated on the surface of the organic pigment, and not on the surface of the inorganic pigment such as carbon black. In the case of a photosensitive resin composition containing an inorganic pigment such as carbon black as a coloring agent, it is mainly used for the purpose of implementing a black color, and therefore, the effect intended in the present invention cannot be implemented at all. For example, the organic pigment may be a non-black organic pigment.

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

Examples of the above red pigments 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. Examples of the above green pigments 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. Examples of the above blue pigments 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. Examples of the yellow pigment include copper phthalocyanine pigments such as C.I. Yellow Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 16, etc. Examples of the yellow pigment include isoindoline pigments such as C.I. Yellow Pigment 139, quinophthalone pigments such as C.I. Yellow Pigment 138, etc., nickel complex pigments such as C.I. Yellow Pigment 150, etc. The pigments may be used alone or in mixtures of two or more thereof, 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 can be included in the photosensitive resin composition in the form of a dispersion. This pigment dispersion can be composed of the pigment, a solvent, a dispersant, a dispersion resin, etc.

Nonionic dispersants, anionic dispersants, cationic dispersants, etc. can be used as the above dispersant. Specific examples of the above dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkyl amide alkylene oxide adducts, alkyl amines, etc., and these can be used alone or in mixtures of two or more.

Examples of commercially available products of the above dispersants include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 from BYK; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 from EFKA Chemicals; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or Ajinomoto's PB711, PB821, etc.

The above dispersant may be included in an amount of 0.1 wt% to 15 wt% based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the composition has excellent dispersibility, and thus stability, developability, and patternability are excellent when manufacturing a light-shielding barrier.

The above dispersion resin can use an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patternability of the pixel.

Meanwhile, the above organic pigment can be used after being pretreated with a water-soluble inorganic salt and a wetting agent. When the above organic pigment is used after being pretreated, the average particle size of the pigment can be made finer.

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

The above-mentioned kneading can be performed at a temperature of 40°C to 100°C, and the above-mentioned filtration and washing can be performed by washing away the inorganic salt using water or the like and then filtering.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride, potassium chloride, etc. The wetting agent acts as a medium that allows the pigment and the water-soluble inorganic salt to be uniformly mixed and the pigment to be easily pulverized, and examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.; alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, etc., and these may be used alone or in combination of two or more.

The organic pigment that has undergone the above-mentioned 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-mentioned range, the stability in the pigment dispersion is excellent, and there is no concern about a decrease in pixel resolution.

As the above solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used, and among these, propylene glycol methyl ether acetate can be preferably used.

With respect to the total amount of the photosensitive resin composition, the colorant may be included in an amount of 20 to 70 wt%. When the colorant is included in the above weight ratio range, excellent heat resistance can be achieved while maintaining color characteristics.

(A) Binder resin

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

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

The weight average molecular weight of the above-mentioned cardo-based binder resin may be 1,000 g/mol to 50,000 g/mol, and specifically, may be 3,000 g/mol to 35,000 g/mol. When the weight average molecular weight of the above-mentioned cardo-based binder resin is within the above range, excellent patterning properties and developability can be obtained when manufacturing a black matrix or a light-shielding barrier.

The above-mentioned cardo-based binder resin may be a compound including a repeating unit represented by the following chemical formula 9.

[Chemical formula 9]

In the above chemical formula 9,

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

R ₂₈ and R ₂₉ can each independently be a hydrogen atom, or CH ₂ OR _a (R _a is a vinyl group, an acrylic group, or a methacrylic 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 may be any one selected from the group consisting of a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein, R _b to R _e are the same as or different from each other and are hydrogen atoms, or substituted or unsubstituted C1 to C20 alkyl groups), or compounds represented by the following chemical formulae 9-1 to 9-11,

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

[Chemical Formula 9-1]

[Chemical Formula 9-2]

[Chemical Formula 9-3]

[Chemical Formula 9-4]

[Chemical Formula 9-5]

In the above chemical 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.

[Chemical Formula 9-6]

[Chemical Formula 9-7]

[Chemical Formula 9-8]

[Chemical Formula 9-9]

[Chemical Formula 9-10]

[Chemical Formula 9-11]

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

[Chemical Formula 10]

The above tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid dianhydride. Examples of the above aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic 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, Examples thereof include, but are not limited to, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

The above acrylic binder resin comprises a first ethylenically unsaturated monomer　A resin comprising a copolymer of a second ethylenically unsaturated monomer copolymerizable therewith and one or more acrylic repeating units.

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

The above second ethylenically unsaturated monomer is selected from the group consisting of aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, 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; Examples thereof include cyanide vinyl compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; etc., and these may be used alone or in combination of two or more thereof.

Specific examples of the above acrylic binder resin include, but are not limited to, a methacrylic acid/benzyl methacrylate copolymer, a methacrylic acid/benzyl methacrylate/styrene copolymer, a methacrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, a methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like. These may be used singly or in combination of two or more.

The weight average molecular weight of the above 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.　When the weight average molecular weight of the above acrylic binder resin is within the above range, the physical and chemical properties of the black photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion to the substrate is excellent when manufacturing a light-shielding layer.

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

When the above-mentioned cardo-based binder resin and the above-mentioned acrylic-based binder resin are used in combination, the above-mentioned acrylic-based binder resin may be included in the same amount as the above-mentioned cardo-based binder resin. In this case, the development properties and process margin can be improved.

The above 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 included within the above range, the viscosity is appropriately maintained, so that patternability, processability, and developability are excellent when manufacturing a photosensitive resin film.

(B) Photopolymerizable monomer

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

The above-mentioned acrylic photopolymerizable monomer has the above-mentioned ethylenically unsaturated double bond, and thus causes sufficient polymerization upon exposure to light in the pattern forming process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the above photopolymerizable monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol Examples thereof include 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, and novolac epoxy (meth)acrylate.

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

The above photopolymerizable monomer can also be used after being treated with an acid anhydride to provide better developing properties.

The photopolymerizable monomer may be included in an amount of 0.5 wt% to 5 wt%, for example, 1 wt% to 3 wt%, relative to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, sufficient curing occurs upon exposure in the pattern forming process, resulting in excellent reliability and excellent developability in an alkaline developer.

(C) Photopolymerization initiator

The above 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 above acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibuthoxy 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

Examples of the above benzophenone compounds include benzophenone, benzoyl benzoate, 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 above thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc.

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

Examples of the above triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloro methyl)-s-triazine, 2-biphenyl 4,6-bis(trichloro methyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, Examples thereof include 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, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

Examples of the above oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-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. Specific examples of the O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-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-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butane-1-one oxime-O-acetate.

In addition to the above compound, the photopolymerization initiator may also include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene compound, etc.

The above photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt%, relative to the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently upon exposure in the pattern forming process, thereby improving the sensitivity of the manufactured photosensitive resin film.

(E) Solvent

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

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; Oxyacetate alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxyacetate alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 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-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, etc., monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate; Ketone esters such as ethyl pyruvate, etc., and also high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, 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, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, 3-methylbenzoic acid, 3-methoxybutylacetate, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, taking compatibility and reactivity into consideration, preferred examples thereof include ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol ethyl methyl 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 and propylene glycol propyl ether acetate, 3-methylbenzoic acid, and 3-methoxybutyl acetate.

The solvent may be included in a residual amount of the total amount of the photosensitive resin composition, for example, 10 wt% to 70 wt%, for example, 20 wt% to 60 wt%, for example, 25 wt% to 60 wt%. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, thereby providing excellent processability in the production of the photosensitive resin film.

(F) Other additives

Meanwhile, the photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, or a combination thereof.

The above silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to a substrate, etc.

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

The above silane coupling agent may be included in an amount of 0.01 to 10 parts by weight relative to the total amount of the photosensitive resin composition. When the silane coupling agent is included within the above range, the adhesion, storability, 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, to improve coating properties and prevent defects, if necessary.

Examples of the above fluorinated surfactants include BM Chemie's BM- ^1000® , BM- ^1100® , etc.; Dainippon Ink Chemical Industry Co., Ltd.'s Mecapac F ^142D® , Mecapac F ^172® , Mecapac F 173®, Mecapac F ^183® , Mecapac F ^554® , etc ^.; Sumitomo Reum Co., Ltd.'s Prorad FC- ^135® , Prorad FC- ^170C® , Prorad FC- ^430® , Prorad FC- ^431® , etc.; Asahi Glass Co., Ltd.'s Saffron S- ^112® , Saffron S- ^113® , Saffron S- ^131® , Saffron S- ^141® , Saffron S-145® ^, etc.; Toray Silicone Co., Ltd.'s SH- ^28PA® , SH- ^190® , SH- ^193® , SZ- ^6032® , SF- ^8428®, etc. can be used.

As the above silicone-based surfactant, those commercially available from BYK Chem under the names BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, etc. can be used.

The above surfactant can be used in an amount of 0.001 to 5 parts by weight relative to the total amount of the photosensitive resin composition. When the above surfactant is included within the above range, coating uniformity is secured, no staining occurs, and wetting for an IZO substrate or glass substrate is excellent.

In addition, other additives such as antioxidants and stabilizers may be added in a certain amount to the photosensitive resin composition as long as the physical properties are not impaired.

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

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

The method for manufacturing the above photosensitive resin film is as follows.

(1) Application and film formation stage

A photosensitive resin composition is applied to a substrate such as a glass substrate or an ITO substrate that has undergone a predetermined pretreatment using a method such as a spin or slit coating method, a roll coating method, a screen printing method, or an applicator method to a desired thickness, and then the composition is heated (prebaked) at 70°C to 110°C for 1 to 10 minutes to remove the solvent, thereby forming a coating film.

(2) Exposure stage

In order to form a necessary pattern on the obtained film, a mask is interposed, and then exposure is performed by irradiating an active line 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, argon gas lasers, etc., and in some cases, X-rays, electron beams, etc. can also be used.

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

(3) Phenomenon stage

A pattern is formed by dissolving and removing unnecessary parts using an alkaline aqueous solution as a developer, leaving only the exposed portion.

(4) Post-processing step

There is a post-heating process for obtaining an image pattern obtained by development that is superior 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-baked) 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 embodiment provides a camera including the CMOS image sensor.

Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

(Dye synthesis)

Synthesis Example 1

Manufacturer: Merck

Product Name: Rhodamine 6G

[Chemical Formula 6-1]

Synthesis Example 2

Manufacturer: TCI

Product Name: Acid Red 289

[Chemical Formula 7-1]

Synthesis Example 3

Manufacturer: Merck

Product Name: Acid Blue 25

[Chemical Formula 8-1]

(Manufacture of organic pigment dispersion coated with dye)

Manufacturing example 1

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

Manufacturing example 2

The same procedure as in Manufacturing Example 1 was followed, except that the dye represented by Chemical Formula 7-1 was used instead of the dye represented by Chemical Formula 6-1.

Manufacturing example 3

The same procedure as in Manufacturing Example 1 was followed, except that the dye represented by Chemical Formula 8-1 was used instead of the dye represented by Chemical Formula 6-1.

(Manufacture of photosensitive resin composition)

The following components 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 and Comparative Examples 1 and 2. Specifically, after the content of the photopolymerization initiator was accurately measured, the solvent was added, and the mixture was sufficiently stirred until the initiator was completely dissolved. Thereafter, the binder resin and the photopolymerizable monomer were sequentially added, and the mixture was stirred again for about 1 hour. Thereafter, other additives were added, a colorant (pigment dispersion) 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, Nippon Gunyakusha)

(C) Photopolymerization initiator

SPI-03 (Samyang)

(D) Colorant

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

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

(D-3) Covering dye of manufacturing example 1

(D-4) Covering dye of manufacturing example 2

(D-5) Covering dye of manufacturing example 3

(D-6) Dye of Synthesis Example 1

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA, Biryong Corporation)

(F) Other additives

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

(evaluation)

Pattern evaluation

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

From FIGS. 3 to 7, it can be confirmed that a photosensitive resin film with excellent patternability can be obtained by using a photosensitive resin composition according to one embodiment.

Penetration Evaluation

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

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

The present invention is not limited to the above embodiments, but can be manufactured in various different forms, and a person having ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical idea or essential characteristics of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (17)

About the total amount of photosensitive resin composition
(A) 0.1 wt% to 10 wt% of binder resin,
(B) 0.5 wt% to 5 wt% of a photopolymerizable monomer,
(C) 0.1 wt% to 5 wt% of photopolymerization initiator,
(D) 20 to 70 wt% of a colorant, and
(E) Solvent residue
Including,
The above colorant comprises an organic pigment dispersion coated with a dye,
The above dye is a photosensitive resin composition represented by any one of the following chemical formulas 6 to 8:
[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

In the chemical formulas 6 to 8 above,
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 the following chemical formulas 1 to 5,
[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

In the chemical formulas 1 to 5 above,
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 both hydrogen atoms,
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,
X is represented by the following chemical formula X-1: chloride ion, fluoride ion, iodide ion, bromide ion, nitrate ion, hydroxide ion, perchlorate ion (ClO ₄ ^- ).
[Chemical Formula X-1]

delete delete delete delete In the first paragraph,
The above dye is a photosensitive resin composition represented by any one of the following chemical formulas 6-1 to 8-1.
[Chemical Formula 6-1]

[Chemical Formula 7-1]

[Chemical Formula 8-1]

In the first paragraph,
The above dye is a photosensitive resin composition having a maximum absorbance within a wavelength range of 500 nm to 540 nm.
In the first paragraph,
A photosensitive resin composition comprising the organic pigment, a red pigment, a green pigment, a yellow pigment or a combination thereof.
In the first paragraph,
The above colorant comprises an organic pigment dispersion coated with the dye and an organic pigment dispersion not coated with the dye,
A photosensitive resin composition in which the organic pigment dispersion coated with the dye is contained in a smaller amount than the organic pigment dispersion not coated with the dye.
In the first paragraph,
The above binder resin is a photosensitive resin composition including a cardo-based binder resin and an acrylic-based binder resin.
delete In the first paragraph,
The photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane 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, 6 to 10, and 12.
A color filter comprising a photosensitive resin film of claim 13.
A CMOS image sensor comprising a photosensitive resin film of claim 13.
A display device comprising a color filter according to claim 14.
A camera comprising a CMOS image sensor of claim 15.