KR20240138874A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a color filter. One embodiment provides a red photosensitive resin composition comprising (A) a colorant including a pigment dispersion, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Here, the pigment dispersion comprises a mixed pigment of a red pigment, a yellow pigment, and a green pigment; a tertiary amine dispersant; and a dispersion medium.

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

The present invention relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a color filter.

Image sensors are semiconductors that convert photons into electrons so that they can be displayed on a display or stored in a storage device.

The above image sensors are classified into charge coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors depending on the manufacturing process and application method.

The above complementary metal oxide semiconductor image sensor (CMOS Image Sensor, CIS) is a non-memory semiconductor that converts the image received by the camera into a digital signal, and is an assembly of pixels such as a color filter, photodiode, and amplifier.

The silicon-based photodiode used in the image sensor above has sensitivity to near-infrared rays. For this reason, a near-infrared blocking filter is added to the image sensor to correct the image quality. However, the image quality implemented by the image sensor including these may vary depending on the performance of the silicon-based photodiode, the infrared blocking filter, etc.

Meanwhile, the near-infrared blocking filter may include a color filter manufactured using a pigment-type photosensitive resin composition. Here, depending on the type of pigment, the light resistance, dispersibility, and storage stability of the pigment-type photosensitive resin composition may deteriorate, which may cause manufacturing defects when manufacturing a color filter and a near-infrared blocking filter.

One embodiment is to provide a red photosensitive resin composition having excellent light resistance, dispersibility, storage stability, etc.

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

Another embodiment is to provide a color filter manufactured using the above red photosensitive resin film.

One embodiment provides a red photosensitive resin composition comprising (A) a colorant including a pigment dispersion, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the pigment dispersion comprises a mixed pigment of a red pigment, a yellow pigment, and a green pigment; a tertiary amine dispersant; and a dispersion medium.

The above green pigment may be C.I. Green Pigment 36, C.I. Green Pigment 58, or a combination thereof.

The above yellow pigment may be C.I. yellow pigment 139.

The above red pigment may be C.I. Red Pigment 254.

The mixed pigment may include, based on the total amount of the mixed pigment, 0.1 to 10 wt% of the green pigment; 10 to 50 wt% of the yellow pigment; and 40 to 80 wt% of the red pigment.

The above mixed pigment may have a PWC in the range of 40 to 80 wt% according to the following mathematical formula 1:

[Mathematical formula 1]

Pigment weight content (PWC) = 100 * p / b

In the above mathematical expression 1, p is the weight of only the mixed pigment in the total amount of the red photosensitive resin composition, and b is the total weight of the solid content in the total amount of the red photosensitive resin composition.

The above mixed pigment may be included in an amount of 10 wt% to 20 wt% based on the total amount of the pigment dispersion.

The above green pigment may be included in an amount of 0.1 wt% to 10 wt% based on the total amount of the red photosensitive resin composition.

The above tertiary amine dispersant may have an amine value of 100 mgKOH/g or less (but more than 0 mgKOH/g).

The above tertiary amine dispersant may be included in an amount of 0.1 wt% to 10 wt% based on the total amount of the pigment dispersion.

The above tertiary amine dispersant may be included in an amount of 0.01 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.

The above pigment dispersion may further contain a dispersion resin.

The above pigment dispersion may be included in an amount of 1 wt% to 10 wt% based on the total amount of the pigment dispersion.

The above pigment dispersion may be included in an amount of 0.1 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.

The total solid content in the pigment dispersion may be 10 to 30 wt%.

The particle size of the total solid content in the pigment dispersion may be from 15 nm to 70 nm.

The dispersion medium may include propylene glycol monomethyl ether acetate (PGME), propylene glycol monomethyl ether (PGME), or a combination thereof.

The pigment dispersion may be included in an amount of 40 wt% to 80 wt% based on the total amount of the red photosensitive resin composition of one embodiment.

The above binder resin may include an acrylic binder resin.

The photosensitive resin composition may include, based on the total amount of the photosensitive resin composition, 40 to 80 wt% of the (A) colorant; 0.1 to 5 wt% of the (B) binder resin; 0.1 to 5 wt% of the (C) photopolymerizable compound; 0.1 to 5 wt% of the (D) photopolymerization initiator; and the remainder of the (E) solvent.

The above red photosensitive resin composition may further include at least one (F) additive selected from malonic acid; 3-amino-1,2-propanediol; a coupling agent including a vinyl group or a (meth)acryloxy group; a leveling agent; a surfactant; and a radical polymerization initiator.

Another embodiment provides a red photosensitive resin film manufactured using the red photosensitive resin composition.

Another embodiment provides a red color filter comprising the red photosensitive resin film.

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

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

The red photosensitive resin composition of one embodiment exhibits excellent light resistance, dispersibility, storage stability, etc., through the combination of the mixed pigment and the tertiary amine dispersant, thereby suppressing defects during the manufacture of a near-infrared blocking filter and a color filter, and contributing to consistent image quality of an image sensor.

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, "substitution" means that at least one hydrogen atom in a compound 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 C30 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, It means substituted with a C2 to C20 heterocycloalkynyl group or a combination thereof.

Unless otherwise specified herein, the terms “heterocycloalkyl group”, “heterocycloalkenyl group”, “heterocycloalkynyl group” and “heterocycloalkylene group” mean a ring compound of cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene, respectively, in which at least one heteroatom of N, O, S or P is present.

Unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”.

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 4-1 to 4-11 is included in the backbone of the resin.

Additionally, unless otherwise defined herein, “＊” means a part that is connected to the same or different atoms or chemical formulas.

(Photosensitive resin composition)

One embodiment provides a red photosensitive resin composition comprising (A) a colorant including a pigment dispersion, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Here, the pigment dispersion comprises a mixed pigment of a red pigment, a yellow pigment, and a green pigment; and a tertiary amine dispersant.

The red photosensitive resin composition of one embodiment has little influence on near-infrared rays, and thus can realize image quality by an image sensor at a constant level regardless of the performance of a silicon-based photodiode, an infrared blocking filter, etc.

Furthermore, the red photosensitive resin composition of one embodiment exhibits excellent light resistance, dispersibility, storage stability, etc., through the combination of the mixed pigment and the tertiary amine dispersant, thereby suppressing defects during the manufacture of a near-infrared blocking filter and a color filter, and contributing to consistent image quality of an image sensor.

Hereinafter, each component included in the red photosensitive resin composition of one embodiment is specifically described.

[(A) Colorant]

A red photosensitive resin composition of one embodiment is a pigment type photosensitive resin composition, which includes a pigment dispersion.

mixed pigment

The above pigment dispersion contains a red pigment (R) to implement a red color, while further containing a yellow pigment (Y) and a green pigment (G) to block wavelengths in the near-infrared region.

Specifically, with respect to the total amount of the mixed pigment, it may include 0.1 wt% to 10 wt% of the green pigment; 10 wt% to 40 wt% of the yellow pigment; and 50 wt% to 80 wt% of the red pigment. In this range, the wavelength blocking effect in the near-infrared region by the yellow pigment and the green pigment can be harmonized with the red implementation effect by the red pigment.

The above green pigment can be used in a small amount compared to the above yellow pigment and the above red pigment.

The above green pigment can be used in an amount of 0.1 wt% or more, 1 wt% or more, or 2 wt% or more, and 10 wt% or less, 5 wt% or less, or 3 wt% or less, based on the total amount of the mixed pigment. In this range, the photosensitive resin composition and the resin film manufactured using the same can be provided with a near-infrared blocking function.

As the above green pigment, a phthalocyanine-based green pigment represented by the following chemical formula A can be used.

[Chemical Formula A]

In the above chemical formula A, M is Cu or Zn; a and b are each independently an integer from 0 to 4.

The above phthalocyanine-based green pigment exhibits excellent coloring power while exhibiting high absorbance in the wavelength range of 650 nm to 680 nm compared to green pigments of other series.

Among the above phthalocyanine-based green pigments, C.I. green pigment 36 (G36) represented by the following chemical formula A-1, C.I. green pigment 58 (G58) represented by the following chemical formula A-2, or a combination thereof can be used:

[Chemical Formula A-1]

[Chemical Formula A-2]

In the above chemical formulas A-1 and A-2, a and b are each independently an integer from 0 to 4.

The above C.I. green pigment 36 (G36) contains Cu as a central metal, and thus has better light resistance, dispersibility, etc. than C.I. green pigment 58 (G58) containing Zn as a central metal.

Accordingly, the C.I. green pigment 36 (G36) can maintain excellent light resistance, dispersibility, etc. even when the storage period of the pigment dispersion is long compared to the C.I. green pigment 58 (G58), thereby suppressing defects during the manufacture of color filters and near-infrared blocking filters and contributing to consistent image quality of the image sensor.

The above yellow pigment can be used in a larger amount than the above green pigment and in a smaller amount than the above red pigment.

The above yellow pigment can be used in an amount of 10 wt% or more, 15 wt% or more, 20 wt% or more, or 30 wt% or more, and 50 wt% or less, 40 wt% or less, 35 wt% or less, or 25 wt% or less, based on the total amount of the mixed pigment. In this range, the photosensitive resin composition and the resin film manufactured using the same can be provided with a near-infrared blocking function.

As the above yellow pigment, C.I. yellow pigment 139 (Y139) represented by the following chemical formula B can be used. This is an isoindoline-based yellow pigment, and has the effect of exhibiting high absorbance in the wavelength range of 400 nm to 500 nm compared to yellow pigments of other series, while also exhibiting excellent coloring power.

[Chemical Formula B]

The above red pigment can be used in excess of the pigments of the above green pigment and the above yellow pigment.

The above red pigment can be used in an amount of 40 wt% or more, 50 wt% or more, or 60 wt% or more, and 80 wt% or less, or 70 wt% or less, based on the total amount of the mixed pigment. In this range, a red color can be imparted to the photosensitive resin composition and the resin film manufactured using the same.

As the above red pigment, C.I. red pigment 254 (R254) represented by the following chemical formula C can be used:

[Chemical formula C]

This is a diketopyrrolopyrrole (DPP) red pigment, and compared to other series of red pigments, it exhibits high absorbance in the wavelength range of 470 nm to 570 nm while also exhibiting excellent coloring power.

Among the total solid content excluding the dispersion medium in the pigment dispersion, the PWC according to the following mathematical formula 1 may be 40 wt% or more, 45 wt% or more, or 50 wt% or more, but 80 wt% or less, or 75 wt% or less.

[Mathematical formula 1]

Pigment weight content (PWC) = 100 * p / b

In the above mathematical expression 1, p is the weight of only the mixed pigment in the total amount of the red photosensitive resin composition, and b is the total weight of the solid content in the total amount of the red photosensitive resin composition.

Additionally, the mixed pigment may be included in an amount of 10 wt% to 20 wt% based on the total amount of the pigment dispersion.

Additionally, the green pigment may be included in an amount of 0.1 wt% to 10 wt% based on the total amount of the red photosensitive resin composition.

When the above ranges are satisfied, the appearance of the near-infrared blocking filter and the color filter can be improved.

Tertiary amine dispersant

A red photosensitive resin composition of one embodiment comprises a tertiary amine dispersant.

The above tertiary amine dispersant functions as a ‘dispersant’ that helps the mixed pigment to be uniformly dispersed within the pigment dispersion.

Furthermore, the tertiary amine dispersant, as a dispersant containing a 'tertiary amine', exhibits excellent light resistance, dispersibility, storage stability, etc. compared to 'primary amine', 'secondary amine', 'quaternary amine', or a mixed dispersant thereof, thereby suppressing defects during the manufacture of a near-infrared blocking filter and a color filter and contributing to a consistent image quality of an image sensor.

In particular, the tertiary amine dispersant can minimize side reactions caused by a green pigment (e.g., G36 described below) included in the mixed pigment, and can exhibit excellent light resistance, dispersibility, storage stability, etc.

Specifically, the tertiary amine dispersant may include a dispersant having an amine value of 100 mgKOH/g or less (but more than 0 mgKOH/g), thereby enabling the implementation of a high-brightness color filter.

In principle, the 'amine value' is 'the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize all the amines in 1 g of oil', and means the total amount of primary (RNH ₂ ), secondary (R ₂ NH), tertiary (RN(CH ₃ ) ₂ , R ₂ NCH ₃ , R ₃ N), and quaternary (RN(CH ₃ ) ₃ , R ₂ N(CH ₃ ) ₂ , R ₃ NCH ₃ , R ₄ N) amines. However, since the red photosensitive resin composition of one embodiment uses the 'tertiary amine' dispersant as the dispersant, it means only the total amount of tertiary (RN(CH ₃ ) ₂ , R ₂ NCH ₃ , R ₃ N) amines.

The above amine value can be obtained by dissolving the sample in neutral ethanol such as tetrahydrofuran or acetone, and then neutralizing and titrating with an ethanolic hydrochloric acid solution or perchloric acid solution using bromphenol blue, crystal violet, etc. as an indicator, or by measuring the potential difference.

The above tertiary amine dispersant may have an amine value of 100 mgKOH/g or less, 90 mgKOH/g or less, 80 mgKOH/g or less, 70 mgKOH/g or less, 60 mgKOH/g or less, 50 mgKOH/g or less, 40 mgKOH/g or less, 30 mgKOH/g or less, or 20 mgKOH/g or less, and 0 mgKOH/g or more, 5 mgKOH/g or more, or 10 mgKOH/g or more.

Dispersants applicable to this include BYK JET-1951 (amine value: 18 mgKOH/g, manufacturer: BYK), EFKA 4310 (amine value: 19 mgKOH/g, manufacturer: BASF), etc.

The above-mentioned tertiary amine dispersant can be contained in an amount of 0.1 wt% to 10 wt% based on the total amount of the pigment dispersion.

Additionally, the tertiary amine dispersant may be contained in an amount of 0.01 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.

When the above ranges are satisfied, excellent dispersibility can be exhibited.

Dispersed resin

The above pigment dispersion may further include a dispersion resin as a solid component in addition to the mixed pigment and the tertiary amine dispersant.

The dispersion resin may be an acrylic dispersion resin, which can not only improve the stability of the pigment dispersion but also improve the patternability of the pixel. The dispersion resin may have a weight average molecular weight of 10,000 to 20,000 g/mol and 80 to 200 KOHmg/g.

The above-mentioned dispersion resin may be included in an amount of 1 wt% to 10 wt% based on the total amount of the pigment dispersion.

Additionally, the dispersion resin may be included in an amount of 0.1 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.

When the above ranges are satisfied, the adhesion of the mixed pigment can be increased.

Total solid content in pigment dispersion

The content of the total solid content (mixed pigment, dispersant, dispersion resin, etc.) excluding the dispersion medium in the pigment dispersion may be 10 wt% to 40 wt%, specifically 12 wt% to 30 wt%, and more specifically 15 wt% to 25 wt%, based on 100 wt% of the pigment dispersion. By satisfying this range, the red photosensitive resin composition of one embodiment can exhibit excellent tinting power.

Particle size of total solids in pigment dispersion

The particle size of the dispersed total solid of the pigment dispersion may be from 15 nm to 70 nm, specifically from 20 nm to 65 nm, more specifically from 25 nm to 60 nm, for example from 35 nm to 55 nm. In this range, it can be suitably used in semiconductors, display devices, and the like.

Here, the “particle size” was measured 5 to 10 times using a particle size analysis device, and the average of the measured values was used.

Dispersant

The above pigment dispersion may use propylene glycol monomethyl ether acetate (PGME), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol or a combination thereof as a dispersion medium.

Specifically, as the dispersion medium, propylene glycol monomethyl ether acetate (PGME), propylene glycol monomethyl ether (PGME), or a combination thereof, which are the same as the (E) solvent described below, can be used.

Content of pigment dispersion (colorant) in total amount of red photosensitive resin composition

The pigment dispersion (colorant) may be included in an amount of 40 wt% to 80 wt%, specifically 50 wt% to 75 wt%, for example 55 wt% to 60 wt%, based on the total amount of the red photosensitive resin composition of one embodiment. When the colorant is included within the above range, the combination of the mixed pigment and the tertiary amine dispersant may excellently exhibit light resistance, dispersibility, storage stability, etc., thereby suppressing defects during the manufacture of a near-infrared blocking filter and a color filter, and contributing to consistent image quality of the image sensor.

[ (B) Binder resin]

The above photosensitive resin composition may further include a binder resin, and the binder resin may include an acrylic binder resin.

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

The 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 second acrylic resin include, but are not limited to, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like. These may be used singly or in combination of two or more.

The above binder resin may further include an epoxy-based binder resin.

The above binder resin can improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may include, but is not limited to, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or a combination thereof.

Furthermore, the binder resin including the above epoxy-based binder resin ensures dispersion stability of a coloring agent such as a pigment, which will be described later, and helps form pixels of a desired resolution during the developing process.

The above epoxy-based binder resin may be included in an amount of 1 wt% to 10 wt%, for example, 5 wt% to 10 wt%, based on the total amount of the binder resin. When the epoxy-based binder resin is included in the above range, the film remaining rate and chemical resistance may be significantly improved.

The epoxy equivalent weight of the above epoxy binder resin may be 150 g/eq to 200 g/eq. When the epoxy binder resin having an epoxy equivalent weight within the above range is included in the binder resin, there is a beneficial effect on improving the hardening degree of the formed pattern and fixing the colorant within the structure where the pattern is formed.

The above binder resin may further include a cardo-based binder resin.

The above-mentioned cardo-based binder resin may include a repeating unit represented by the following chemical formula 3.

[Chemical Formula 3]

In the above chemical formula 3,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ (wherein, R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), or any one of the linking groups represented by the following chemical formulae 4-1 to 4-11,

[Chemical Formula 4-1]

[Chemical Formula 4-2]

[Chemical Formula 4-3]

[Chemical Formula 4-4]

[Chemical Formula 4-5]

(In the above chemical formula 4-5,

R ^a 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 4-6]

[Chemical Formula 4-7]

[Chemical Formula 4-8]

[Chemical Formula 4-9]

[Chemical Formula 4-10]

[Chemical Formula 4-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer from 0 to 4.

The above-mentioned cardo-based binder resin may include a functional group represented by the following chemical formula 5 at at least one of both terminals.

[Chemical Formula 5]

In the above chemical formula 5,

Z ³ can be represented by the following chemical formulas 5-1 to 5-7.

[Chemical Formula 5-1]

(In the above chemical formula 5-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Chemical Formula 5-2]

[Chemical Formula 5-3]

[Chemical Formula 5-4]

[Chemical Formula 5-5]

(In the above chemical formula 5-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Chemical Formula 5-6]

[Chemical Formula 5-7]

The above-mentioned cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds such as benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; a glycol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; a phosphorus compound such as triphenylphosphine; And it can be produced by mixing two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the above-mentioned cardo-based binder resin is used together with the aforementioned acrylic-based binder resin, a photosensitive resin composition having excellent adhesion and high resolution and high brightness characteristics can be obtained.

The weight average molecular weight of the above-mentioned cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 3,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the above-mentioned cardo-based binder resin is within the above range, pattern formation is performed well without residue during color filter production, there is no loss of film thickness during development, and a good pattern can be obtained.

The above-mentioned cardo-based binder resin can have an acid value of 100 mgKOH/g to 140 mgKOH/g.

The above binder resin can be dissolved in a solvent described below in a solid form to form a photosensitive resin composition. In this case, the binder resin in a solid form can be about 10 wt% to 50 wt%, for example, 20 wt% to 40 wt%, based on the total amount of the binder resin solution dissolved in the solvent.

The above binder resin may be included in an amount of 0.1 wt% to 5 wt%, specifically 1 wt% to 4 wt%, for example 1 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, the developability is excellent during the manufacture of a color filter, and the crosslinking property is improved, so that excellent surface smoothness can be obtained.

[(C) Photopolymerizable compound]

As the above photopolymerizable compound, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond can be used.

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

The above photopolymerizable compound may be treated with an acid anhydride or may use an ethylene oxide-modified product to provide better developing properties.

The photopolymerizable compound may be included in an amount of 0.1 wt% to 5 wt%, specifically 1 wt% to 4 wt%, for example 1 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound 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.

[(D) Photopolymerization initiator]

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

Examples of the 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, and the like.

Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, 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, etc. Specific examples of the above O-acyloxime 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-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-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 also be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy.

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

The above photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, specifically 0.5 wt% to 3 wt%, for example 0.1 wt% to 1 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, sufficient curing occurs upon exposure in the pattern forming process, thereby obtaining excellent reliability, and the pattern has excellent heat resistance, light resistance, and chemical resistance, and also excellent resolution and adhesion, and can prevent a decrease in transmittance due to unreacted initiator.

[(D) solvent]

The solvent may be a substance that is compatible with, but does not react with, the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

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; alkyl acetates such as ethyl acetate and butyl acetate; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether. Propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons, such as toluene and xylene; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid esters, such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters, such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate 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-Alkoxy propionic acid alkyl esters, such as methyl 2-methoxy propionic acid, ethyl 2-methoxy propionic acid, ethyl 2-ethoxy propionic acid, and methyl 2-ethoxy propionic acid; 2-oxy-2-methyl propionic acid esters, such as methyl 2-oxy-2-methyl propionic acid, ethyl 2-oxy-2-methyl propionic acid, and ethyl 2-alkoxy-2-methyl propionic acid alkyl esters, such as methyl 2-methoxy-2-methyl propionic acid, ethyl 2-ethoxy-2-methyl propionic acid; Esters, such as ethyl 2-hydroxy propionic acid, ethyl 2-hydroxy-2-methyl propionic acid, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; Ketone acid 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, 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 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; and ketones such as cyclohexanone.

The solvent may be included as a remainder, for example, 60 wt% to 80 wt%, for example, 65 wt% to 75 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has excellent coatability and a coating film having excellent flatness can be obtained.

[(F) Other additives]

The above photosensitive resin composition may further include at least one additive selected from malonic acid; 3-amino-1,2-propanediol; a coupling agent containing a vinyl group or a (meth)acryloxy group; a leveling agent; a surfactant; and a radical polymerization initiator to prevent stains or spots during application, improve leveling performance, and prevent the generation of residues due to non-development.

The above additives can be easily adjusted according to the desired properties.

The above coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-epoxycyclohexyl)ethyl trimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The above silane coupling agent can be specifically used in an amount of 0.01 part by weight to 1 part by weight per 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for the color filter may further contain a surfactant, such as a fluorinated surfactant, if necessary.

Examples of the above fluorinated surfactants include, but are not limited to, DIC's F-556, F-482, F-484, and F-478.

The above surfactant is preferably included in an amount of 0.01 wt% to 5 wt% based on the total amount of the photosensitive resin composition, and more preferably included in an amount of 0.01 wt% to 2 wt%. If it is outside the above range, a problem of foreign substances being generated after development may occur, which is not preferable.

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 above photosensitive resin composition can be applied to a photosensitive resin composition for a color filter of a CMOS image sensor, specifically, a photosensitive resin composition for a green color filter of a CMOS image sensor.

(Red photosensitive resin film, red color filter and CMOS image sensor)

According to another embodiment, a red photosensitive resin film manufactured using a red photosensitive resin composition according to one embodiment is provided.

According to another embodiment, a red color filter manufactured using the above-described red photosensitive resin composition is provided.

The manufacturing method of the above color filter is as follows.

The photosensitive resin composition described above is applied to a glass substrate using an appropriate method such as spin coating, roller coating, or spray coating, for example, to an appropriate thickness to form a photosensitive resin composition layer.

Next, light is irradiated on the substrate on which the photosensitive resin composition layer is formed so as to form a pattern required for the color filter. UV, electron rays or X-rays can be used as a light source used for the irradiation, and for example, UV in the range of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. The irradiation process can also be performed further using a photoresist mask. After performing the irradiation process as described above, the photosensitive resin composition layer irradiated with the light source is treated with a developing solution. At this time, the unexposed portion of the photosensitive resin composition layer is dissolved, thereby forming a pattern required for the color filter. By repeating this process according to the number of required colors, a color filter having a desired pattern can be obtained. In addition, if the image pattern obtained by the development in the above process is heated again or cured by irradiation with active rays, etc., crack resistance, solvent resistance, etc. can be improved.

According to another embodiment, a CMOS image sensor including the red color filter is provided.

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

(Preparation of pigment dispersion)

Manufacturing example 1

As a green pigment, 0.4 parts by weight of C.I. green pigment 36 (G36) represented by the chemical formula A-1; As a yellow pigment, 4.6 parts by weight of C.I. yellow pigment 139 (Y139) represented by the chemical formula B; As a red pigment, 9 parts by weight of C.I. red pigment 254 (R254) represented by the chemical formula C; As a tertiary amine dispersant, 0.1 parts by weight based on solids of EFKA 4310 (amine value: 19 mgKOH/g, solids content 50%, manufacturer: BASF); As a dispersion resin, 5.9 parts by weight based on solids of RY-92; Propylene glycol methyl ether acetate (PGMEA) and propylene glycol methyl ether (PGME) were added as dispersants at a weight ratio of 90:10 and mixed using zirconia beads and a shaker (manufactured by skandex), thereby preparing a pigment dispersion. The solid content in the pigment dispersion is 20 wt% and its particle size is 49 nm.

Manufacturing example 2

A pigment dispersion was prepared in the same manner as in Manufacturing Example 1, except that 1 part by weight based on solids of EFKA 4310 (amine value: 19 mgKOH/g, solids content 50%, manufacturer: BASF) was used as a tertiary amine dispersant and 5 parts by weight based on solids of RY-92 was used as a dispersing resin.

Manufacturing example 3

A pigment dispersion was prepared in the same manner as in Manufacturing Example 1, except that 3 parts by weight based on solid content of EFKA 4310 (amine value: 19 mgKOH/g, solid content 50%, manufacturer: BASF) was used as a tertiary amine dispersant; and 3 parts by weight based on solid content of RY-92 was used as a dispersing resin.

Manufacturing example 4

A pigment dispersion was prepared in the same manner as in Manufacturing Example 1, except that 5 parts by weight based on solid content of EFKA 4310 (amine value: 19 mgKOH/g, solid content 50%, manufacturer: BASF) was used as a tertiary amine dispersant and 1 part by weight based on solid content of RY-92 was used as a dispersing resin.

Manufacturing example 5

A pigment dispersion was prepared in the same manner as in Manufacturing Example 3, except that 3 parts by weight of BYK JET-9151 (amine value: 18 mgKOH/g, acid value: 8 mgKOH/g, solids 100%, manufacturer: BYK) was used as a tertiary amine dispersant.

Manufacturing example 6

A pigment dispersion was prepared in the same manner as in Manufacturing Example 3, except that 0.4 weight part of C.I. green pigment 58 (G58) represented by the chemical formula A-2 was used as a green pigment.

Manufacturing Comparison Example 1

A pigment dispersion was prepared in the same manner as in Manufacturing Example 3, except that 3 parts by weight of PB-824 (amine value: 17 mgKOH/g, acid value: 21 mgKOH/g, solids 100%, manufacturer: Ajinomoto Co., Ltd.) was used as a first-class amine dispersant instead of a third-class amine dispersant.

Manufacturing Comparison Example 2

A pigment dispersion was prepared in the same manner as in Manufacturing Example 3, except that 3 parts by weight of EFKA 7701 (amine value: 40 mgKOH/g, solid content 100%, manufacturer: BASF) was used as a secondary amine dispersant instead of a tertiary amine dispersant.

Manufacturing Comparison Example 3

A pigment dispersion was prepared in the same manner as in Manufacturing Example 3, except that 3 parts by weight of BYK-LP N21234 (amine value: 70 mgKOH/g, solid content 100%, manufacturer: BYK) was used as a quaternary amine dispersant instead of a tertiary amine dispersant.

For reference, the compositions of Manufacturing Examples 1 to 6 and Comparative Manufacturing Examples 1 to 3 are shown in Tables 1 and 2 below.

(Unit: weight%) Solid content (weight%) Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 R254 100 9 9 9 9 9 Y139 100 4.6 4.6 4.6 4.6 4.6 G36 100 0.4 0.4 0.4 0.4 0.4 Tertiary amine dispersant 50 0.2 2 6 10 3 Dispersed resin 38.5 15.3 13.0 7.8 2.6 7.8 PGMEA - 63.45 63.9 64.98 66.06 67.68 PGME - 7.05 7.1 7.22 7.34 7.52 total 20.0 100 100 100 100 100 note Types of dispersants Tertiary amine dispersant, EFKA 4310 Tertiary amine dispersant, EFKA 4310 Tertiary amine dispersant, EFKA 4310 Tertiary amine dispersant, EFKA 4310 Tertiary Amine Dispersant, BYK JET-9151 Types of green pigments G36 G36 G36 G36 G36

(Unit: weight%) Solid content (weight%) Manufacturing example 6 Manufacturing Comparison Example 1 Manufacturing Comparison Example 2 Manufacturing Comparison Example 3 red pigment 100 9 9 9 9 yellow pigment 100 4.6 4.6 4.6 4.6 green pigment 100 0.4 0.4 0.4 0.4 Dispersant 100 3 3 3 3 Dispersed resin 38.5 7.8 7.8 7.8 7.8 PGMEA - 24.8 24.8 24.8 24.8 PGME - 67.68 67.68 67.68 67.68 total 20.0 7.52 7.52 7.52 7.52 note Types of dispersants Tertiary amine dispersant, EFKA 4310 1st class amine dispersant,
PB-824 Secondary amine dispersant,
EFKA 7701 Quaternary amine dispersant, BYK-LP N21234 Types of green pigments G58 G36 G36 G36

(Preparation of photosensitive resin composition)

Examples 1 to 6 and Comparative Examples 1 to 3

A photosensitive resin composition was prepared by mixing the compositions shown in Tables 3 and 4.

Specifically, after dissolving the photopolymerization initiator in the solvent, the mixture was stirred at room temperature for 30 minutes, and then a photopolymerizable compound was added thereto, followed by stirring at room temperature for 60 minutes. Subsequently, a colorant (pigment dispersion) and a binder resin were added to the obtained reactant, followed by stirring at room temperature for 30 minutes. Additionally, an additive was added, followed by stirring at room temperature for 30 minutes. Subsequently, the product was filtered twice to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%) ingredient Material name Example 1 Example 2 Example 3 Example 4 Example 5 (A) Colorant
(pigment dispersion) A-1 58.64 - - - - A-2 - 58.64 - - - A-3 - - 58.64 - - A-4 - - - 58.64 - A-5 - - - - 58.64 A-6 - - - - - A-7 - - - - - A-8 - - - - - A-9 - - - - - (B) Binder
profit B-1 2.34 2.34 2.34 2.34 2.34 (C) Photopolymerizable compound C-1 1.1 1.1 1.1 1.1 1.1 (D) Photopolymerization initiator B-1 0.11 0.11 0.11 0.11 0.11 (E) Solvent E-1 37.75 37.75 37.75 37.75 37.75 (F) Additive F-1 0.02 0.02 0.02 0.02 0.02 F-2 0.04 0.04 0.04 0.04 0.04

(Unit: weight%) ingredient Material name Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Colorant
(pigment dispersion) A-1 - - - - A-2 - - - - A-3 - - - - A-4 - - - - A-5 - - - - A-6 58.64 - - - A-7 - 58.64 - - A-8 - - 58.64 - A-9 - - - 58.64 A-10 - (B) Binder
profit B-1 2.34 2.34 2.34 2.34 (C) Photopolymerizable compound C-1 1.1 1.10 1.10 1.10 (D) Photopolymerization initiator B-1 0.11 0.11 0.11 0.11 (E) Solvent E-1 37.75 37.75 37.75 37.75 (F) Additive F-1 0.02 0.02 0.02 0.02 F-2 0.04 0.04 0.04 0.04

The components used in Tables 3 and 4 above are as follows.

(A) Colorant

(A-1) Pigment dispersion of manufacturing example 1

(A-2) Pigment dispersion of manufacturing example 2

(A-3) Pigment dispersion of manufacturing example 3

(A-4) Pigment dispersion of manufacturing example 4

(A-5) Pigment dispersion of manufacturing example 5

(A-6) Pigment dispersion of manufacturing example 6

(A-7) Pigment dispersion of comparative manufacturing example 1

(A-8) Pigment dispersion of comparative manufacturing example 2

(A-9) Pigment dispersion of comparative manufacturing example 3

(B) Binder resin

(B-1) A dispersion (solid content: 38.5 wt%) containing RY-92 (manufacturer: Showa Denko, molecular weight: 5,900 g/mol, acid value: 33 KOHmg/g, double bond equivalent: 350 g/mol) as an acrylic binder resin and propylene glycol methyl ether acetate (PGMEA).

(C) Photopolymerizable compound

(C-1) Dipentaerythritol hexaacrylate (DPHA, manufacturer: Nippon Gunyaku)

(D) Photopolymerization initiator

(D-1) Oxime initiator (Product name: SPI-03, Manufacturer: Samyang Corporation)

(E) Solvent

(E-1) Propylene glycol monomethyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich)

(F) Additive

(F-1) Fluorine surfactant (F-556, manufacturer: DIC)

(F-2) Non-amino silane coupling agent (KBM503, manufacturer: Shin-etsu)

(evaluation)

Color filter specimens were prepared from the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3, and the light resistance and bonding of each color filter specimen were evaluated. The evaluation results are shown in Table 5 below.

(1) Manufacturing of color filter specimens

The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were coated on an 8-inch glass substrate using a spin coater (Mikasa, Opticoat MS-A150), followed by soft baking at 100°C for 180 seconds using a hot plate and exposure to light for 1000 msec using an i-line stepper (Nikon, NSR-2005i10C). The exposed substrate was developed in a 0.19% TMAH aqueous solution at room temperature by spray & puddle, and then hard-baked at 200°C for 5 minutes on a hot plate. Thus, a color filter specimen having a 6000 Å thick photosensitive resin film formed on a glass substrate was obtained.

(2) Light resistance evaluation

The color filter specimens obtained above were treated in a xenon test chamber (model name Xe-1, manufacturer Q-Lab, USA) at an illuminance of 0.68 W/m ² based on 420 nm and a temperature of 60°C for 70 hours.

The transmittance before and after the light treatment was measured above, and the value with the largest absolute value of change between 380 and 780 nm was judged as the change in transmittance before and after the light treatment (△Transmittance). For reference, if the change in transmittance before and after the light treatment (△Transmittance) is 5 or less, the light resistance can be considered good.

(3) Color filter defect evaluation

A 0.6um x 0.6um mask width x height pattern was formed on the entire surface of an 8-inch Si substrate (the distance between patterns was 1.0um), and the number of color filter defects was counted using an AIT (Auto Inspection Tester, model number AIT-XP, manufacturer KLA-Tencor).

In addition, defects were evaluated even after the photosensitive resin composition was treated in an oven at 40°C for 7 days.

Light resistance Color filter defect △Transmittance Before processing 40℃ oven 7 days
After processing Defect growth rate
(40℃ oven for 7 days)
Before and after treatment (%) Example 1 1.2 54 80 148 Example 2 1.8 51 75 147 Example 3 2.2 42 55 131 Example 4 2.1 45 64 142 Example 5 2.0 57 69 121 Example 6 8.8 69 96 139 Comparative Example 1 2.7 81 281 347 Comparative Example 2 3.2 90 286 318 Comparative Example 3 6.9 39 334 856

According to Table 5 above, the color filter specimens of Examples 1 to 6 have an absolute value of the change in transmittance (△transmittance) before and after light treatment of 5 or less, indicating good light resistance compared to the color filter specimens of Comparative Examples 1 to 3.

In addition, the color filter specimens of Examples 1 to 6 have fewer defects themselves, and even after treatment in an oven at 40°C for 7 days, they have fewer defects and a low rate of increase, so that fewer defects are induced compared to the color filter specimens of Comparative Examples 1 to 3.

Through this, it can be seen that the color filter specimens of one embodiment represented by Examples 1 to 6 excellently exhibit light resistance, dispersibility, storage stability, etc., by using a pigment dispersion containing a mixed pigment of a red pigment, a yellow pigment, and a green pigment; and a tertiary amine dispersant as a colorant. Furthermore, the color filter specimens of one embodiment represented by Examples 1 to 6 can suppress defects during the manufacturing of a near-infrared blocking filter and a color filter, and contribute to constant image quality of an image sensor.

Meanwhile, in the color filter specimens of Examples 1 to 6, C.I. Green Pigment 36 (G36), C.I. Green Pigment 58 (G58), or a combination thereof can be used. Among these, C.I. Green Pigment 36 (G36) contains Cu as a central metal, and thus has better light resistance, dispersibility, etc. than C.I. Green Pigment 58 (G58) containing Zn as a central metal.

Based on the above results, the type of components constituting the red photosensitive resin composition, their mixing ratio, etc. can be adjusted to control the effect within the desired range.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications may be made within the scope of the claims, the detailed description of the invention, and the attached drawings, which also fall within the scope of the present invention.

Claims (20)

(A) a colorant comprising a pigment dispersion,
(B) Binder resin,
(C) photopolymerizable compound,
(D) a photopolymerization initiator, and
(E) containing a solvent,
The above pigment dispersion is
A mixed pigment of red pigment, yellow pigment, and green pigment;
tertiary amine dispersant; and
Containing a dispersion medium
Red photosensitive resin composition.
In the first paragraph,
A red photosensitive resin composition wherein the green pigment is CI Green Pigment 36, CI Green Pigment 58, or a combination thereof.
In the first paragraph,
The above yellow pigment is a red photosensitive resin composition which is CI yellow pigment 139.
In the first paragraph,
The above red pigment is a red photosensitive resin composition which is CI red pigment 254.
In the first paragraph,
The above mixed pigment, with respect to the total amount of the above mixed pigment,
0.1 to 10 wt% of the above green pigment;
10 to 50 wt% of the above yellow pigment; and
Containing 40 to 80 wt% of the above red pigment
Red photosensitive resin composition.
In the first paragraph,
A red photosensitive resin composition, wherein the mixed pigment is contained in an amount of 10 to 20 wt% based on the total amount of the pigment dispersion.
In the first paragraph,
A red photosensitive resin composition, wherein the green pigment is contained in an amount of 0.1 wt% to 10 wt% based on the total amount of the red photosensitive resin composition.
In the first paragraph,
The above mixed pigment is a red photosensitive resin composition having 40 to 80 wt% of PWC according to the following mathematical formula 1:
[Mathematical formula 1]
Pigment weight content (PWC) = 100 * p / b
In the above mathematical expression 1,
p is the weight of only the mixed pigment in the total amount of the above red photosensitive resin composition,
b is the total weight of the solid content in the total amount of the above red photosensitive resin composition.
In the first paragraph,
A red photosensitive resin composition, wherein the tertiary amine dispersant is contained in an amount of 0.1 wt% to 10 wt% based on the total amount of the pigment dispersion.
In the first paragraph,
A red photosensitive resin composition, wherein the tertiary amine dispersant is contained in an amount of 0.01 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.
In the first paragraph,
The above pigment dispersion is a red photosensitive resin composition further comprising a dispersion resin.
In Article 11,
A red photosensitive resin composition, wherein the dispersion resin is included in an amount of 1 to 10 wt% based on the total amount of the pigment dispersion.
In Article 11,
A red photosensitive resin composition, wherein the above-mentioned dispersion resin is contained in an amount of 0.1 wt% to 5 wt% based on the total amount of the red photosensitive resin composition.
In the first paragraph,
A red photosensitive resin composition having a total solid content in the pigment dispersion of 10 to 30 wt%.
In the first paragraph,
A red photosensitive resin composition having a particle size of the total solid content in the pigment dispersion of 15 nm to 70 nm.
In the first paragraph,
The above binder resin is a red photosensitive resin composition which is an acrylic binder resin.
In the first paragraph,
The photosensitive resin composition, with respect to the total amount of the photosensitive resin composition,
40 to 80 wt% of the above (A) colorant;
0.1 wt% to 5 wt% of the above (B) binder resin;
0.1 wt% to 5 wt% of the photopolymerizable compound (C);
0.1 wt% to 5 wt% of the above (D) photopolymerization initiator; and
Above (E) solvent residue
A red photosensitive resin composition comprising:
A red photosensitive resin film manufactured using the red photosensitive resin composition of any one of claims 1 to 17.
A red color filter comprising a red photosensitive resin film of claim 18.
A CMOS image sensor comprising a red color filter of claim 19.