KR20230127064A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present description relates to a photosensitive resin composition, and a photosensitive resin film and a color filter manufactured using the same. One embodiment provides a red photosensitive resin composition comprising (A) a colorant; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerizable initiator; and (E) a solvent, wherein the colorant includes a pigment dispersion, and the pigment dispersion includes, based on 100 wt% of a total pigment, 50 to 80 wt% of red pigment 254, C.I., 20 to 40 wt% of a yellow pigment 139, and 0.1 to 10 wt% of a green pigment 58 C.I..

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film and a color filter prepared using the photosensitive resin composition.

An image sensor corresponds to a semiconductor that converts photons into electrons to be displayed on a display or stored in a storage device.

The image sensor is classified into a charge coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor according to a manufacturing process and an application method.

The complementary metal oxide semiconductor image sensor (CMOS Image Sensor, CIS) is a non-memory semiconductor that converts an image received by a camera into a digital signal, and is a collection of pixels such as color filters, photodiodes, and amplifiers.

A silicon-based photodiode used in the image sensor has sensitivity to near infrared rays. For this reason, image quality is corrected by adding a near-infrared cut filter to the image sensor. However, due to the performance of the silicon-based photodiode, the infrared cut filter, etc., a deviation may occur in image quality realized by an image sensor including them.

One embodiment is to provide a red photosensitive resin composition that is less affected by near-infrared rays in order to realize image quality by an image sensor at a constant level regardless of the performance of a silicon-based photodiode, an infrared cut filter, or the like.

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

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

One embodiment includes (A) a colorant; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the colorant comprises a pigment dispersion, and the pigment dispersion comprises C.I. 50% to 80% by weight of red pigment 254, C.I. 20% to 40% by weight of yellow pigment 139, C.I. A red photosensitive resin composition comprising 0.1% by weight to 10% by weight of the green pigment 58 is provided.

Out of 100% by weight of the total pigment, C.I. 57% to 67% by weight of red pigment 254, C.I. 30% to 35% by weight of yellow pigment 139, C.I. 1.5% to 9% by weight of green pigment 58.

The pigment dispersion may further include a dispersing agent, a dispersing resin, a dispersing medium, or a combination thereof.

The dispersant may have an amine value of 100 mgKOH/g or less (however, greater than 0 mgKOH/g).

The pigment dispersion may have a pigment content of 40% to 80% by weight according to Equation 1 below:

[Equation 1]

Pigment content = 100 * p/b

In Equation 1, p is the weight of the pigment solids in the pigment dispersion, and b is the weight of the total solids in the pigment dispersion.

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

The total solid content in the pigment dispersion may be 10 wt % to 40 wt %.

The D50 particle diameter of the total solid content in the pigment dispersion may be 15 nm to 70 nm.

The pigment dispersion contains 10% to 20% by weight of the total pigments, 0.1% to 5% by weight of the dispersant, and 0.1% to 5% by weight of the dispersion resin, based on the total amount of the pigment dispersion. and may include the dispersion medium as the remainder.

Upon spectroscopic analysis of a red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, Equation 2 below may be satisfied:

[Equation 2]

70 ≤ A/B ≤ 100

In Equation 2, A is the transmittance of the red photosensitive resin film at a wavelength of 725 nm, and B is the transmittance of the red photosensitive resin film at a wavelength of 625 nm.

Upon spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, the transmittance at a wavelength of 430 nm may be 5% or less (however, greater than 0%).

Upon spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, the transmittance at a wavelength of 560 nm may be 3.5% or less (however, greater than 0%).

The binder resin may include an acrylic binder resin.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, (A) 5% to 70% by weight of the colorant; 0.1% to 20% by weight of the (B) binder resin; 0.1% to 20% by weight of the (C) photopolymerizable compound; 0.1% to 5% by weight of the (D) photopolymerization initiator; and (E) the remainder of the solvent.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

In another embodiment, a red photosensitive resin film prepared using the red photosensitive resin composition is provided.

In another embodiment, a red color filter including the red photosensitive resin layer is provided.

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

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

The red photosensitive resin composition according to one embodiment has little effect on near-infrared rays, and thus image quality by an image sensor can be implemented at a constant level regardless of the performance of a silicon-based photodiode, an infrared cut filter, or the like.

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

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom in a compound is 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, No group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt. , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group , A C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a substituent of a combination thereof.

Unless otherwise specified herein, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" mean cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl, respectively. It means that at least one N, O, S or P heteroatom exists in the ring compound of ene.

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

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

In the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Chemical Formulas 4-1 to 4-11 is included in the backbone of the resin.

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

(Photosensitive Resin Composition)

One embodiment includes (A) a colorant; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the colorant includes a pigment dispersion, and the pigment dispersion, in 100% by weight of the total pigment, contains C.I. 50% to 80% by weight of red pigment 254, C.I. 20% to 40% by weight of yellow pigment 139, C.I. A red photosensitive resin composition comprising 0.1% by weight to 10% by weight of the green pigment 58 is provided.

The red photosensitive resin composition according to one embodiment has little effect on near-infrared rays, and thus image quality by an image sensor can be implemented at a constant level regardless of the performance of a silicon-based photodiode, an infrared cut filter, or the like.

Hereinafter, each component included in the red photosensitive resin composition of one embodiment will be described in detail.

(A) colorant

The red photosensitive resin composition of one embodiment includes a pigment dispersion as a pigment type photosensitive resin composition. The pigment dispersion includes a red pigment (R) to realize red color, and further includes a yellow pigment (Y) and a green pigment (G) to block wavelengths in the near infrared region.

In particular, as the red pigment, C.I. Red pigment 254 (R254) is used, and C.I. Yellow pigment 139 (Y139) is used, and C.I. while using Green Pigment 58 (G58); When the content of each pigment is limited to 50 wt% to 80 wt% (R254), 20 wt% to 40 wt% (Y139), and 0.1 wt% to 10 wt% (Y139) in 100 wt% of the total pigment, red It is possible to harmoniously implement the implementation effect and the wavelength blocking effect of the near-infrared region.

Specifically, as the red pigment, C.I. Red pigment 254 (R254) corresponds to a compound represented by the following formula A, and has a diketopyrrolopyrrole (DPP) structure, thereby exhibiting high absorbance in the wavelength range of 470 nm to 570 nm compared to other red pigments. While exhibiting, there is an effect of expressing excellent coloring power.

[Formula A]

The C.I. Red pigment 254 is in the range of 50% by weight or more, 53% by weight or more, 55% by weight or more, or 57% by weight or more based on 100% by weight of the total pigment in order to realize a red color of the photosensitive resin composition and a resin film prepared using the same. Within, it can be used in excess compared to pigments of other colors.

However, the C.I. Red pigment 254, since the content of pigments providing a wavelength blocking effect in the near infrared region should decrease as its content increases, 80% by weight or less, 75% by weight or less, 70% by weight or less out of 100% by weight of the total pigment Or it can be used within the range of 67% by weight or less.

As the yellow pigment, C.I. Yellow pigment 139 (Y139) corresponds to the compound represented by the following formula B, and has an isoindoline structure, thereby exhibiting high absorbance in the wavelength range of 400 nm to 500 nm compared to other yellow pigments. It has the effect of expressing excellent coloring power.

[Formula B]

The C.I. Yellow pigment 139 (Y139) is used in an amount of 20% by weight or more, 25% by weight or more, 27% by weight or more based on 100% by weight of the total pigment in order to impart a wavelength blocking effect in the near infrared region to the photosensitive resin composition and the resin film prepared using the same. It can be used within the range of % or more or 30% by weight or more.

However, the C.I. As the content of yellow pigment 139 (Y139) increases, the content of the pigment implementing red color should decrease, so 40% by weight or less, 38% by weight or less, 36% by weight or less, or 35% by weight or less based on 100% by weight of the total pigment. It can be used within the range of weight % or less.

As the green pigment, C.I. Green Pigment 58 (G58) corresponds to the compound represented by Formula C, and has a Phthalocyanine structure, thereby exhibiting high absorbance in the wavelength range of 650 nm to 680 nm compared to other green pigments and excellent coloring power has the effect of expressing

[Formula C]

In Formula C, a and b are each independently an integer of 0 to 4.

The C.I. Green pigment 58 (G58) is used in an amount of 0.1% by weight or more, 0.5% by weight or more, and 1% by weight, based on 100% by weight of the total pigment, in order to impart a wavelength blocking effect in the near-infrared region to the photosensitive resin composition and a resin film prepared using the same. It can be used within the range of % or more or 1.5% by weight or more.

However, the C.I. Green pigment 58 (G58), since the content of the pigment implementing red color should decrease as its content increases, 10% by weight or less, 9.5% by weight or less, 9.3% by weight or less, or 9% by weight or less based on 100% by weight of the total pigment. It can be used within the range of weight % or less.

The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion. The pigment dispersion may further include a dispersing agent, a dispersing resin, a dispersing medium, or a combination thereof in addition to the pigment.

The dispersant helps to uniformly disperse the pigment in the dispersion, and each of a nonionic, anionic or cationic dispersant may be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide adduct Water, alkyl amine, etc. may be used, and these may be used alone or in combination of two or more.

Specifically, the dispersant may include a dispersant having an amine value of 100 mgKOH/g or less (however, greater than 0 mgKOH/g), and through this, a color filter with high brightness may be implemented.

Here, the amine value is 'the number of milligrams of potassium hydroxide equivalent to hydrochloric acid required to neutralize all amines in 1 g of fat', and is classified as primary (RNH ₂ ), secondary (R ₂ NH) and tertiary (RN(CH ₃ ) ₂ , R ₂ NCH ₃ , R ₃ N) means the total amount of amines. The amine value can be obtained by dissolving a sample in neutral ethanol such as tetrahydrofuran or acetone, neutralizing titration with an ethanolic hydrochloric acid solution or perchloric acid solution, or measuring a potential difference using bromine phenol blue, crystal violet, etc. as an indicator. .

The dispersant has an amine value of 100 mgKOH/g or less, 90 mgKOH/g or less, 80 mgKOH/g or less, 70 mgKOH/g or less, 65 mgKOH/g or less, 60 mgKOH/g or less, or 55 mgKOH/g or less, and g or more, 5 mgKOH/g or more, or 10 mgKOH/g or more.

Dispersants corresponding to this are DISPERBYK-161 (amine value: 11 mgKOH/g, manufacturer: BYK company), DISPERBYK-162 (amine value: 13 mgKOH/g, manufacturer: BYK company), DISPERBYK-163 (amine value: 10 mgKOH/g , Manufacturer: BYK), DISPERBYK-164 (amine value: 18 mgKOH/g, manufacturer: BYK), DISPERBYK-166 (amine value: 20 mgKOH/g, manufacturer: BYK), DISPERBYK-167 (amine value: 13 mgKOH/ g, manufacturer: BYK), DISPERBYK-182 (amine value: 13 mgKOH/g, manufacturer: BYK), DISPERBYK-184 (amine value: 15 mgKOH/g, manufacturer: BYK), DISPERBYK-185 (amine value: 17mgKOH/ g, manufacturer: BYK), DISPERBYK-2000 (amine value: 4mgKOH/g, manufacturer: BYK), DISPERBYK-2001 (amine value: 29mgKOH/g, manufacturer: BYK), DISPERBYK-2008 (amine value: 66mgKOH/g, Manufacturer: BYK), DISPERBYK-2009 (amine value: 4mgKOH/g, manufacturer: BYK), DISPERBYK-2022 (amine value: 61mgKOH/g, manufacturer: BYK), DISPERBYK-2050 (amine value: 30mgKOH/g, manufacturer: BYK Company), DISPERBYK-2055 (amine value: 40mgKOH/g, manufacturer: BYK Company), DISPERBYK-2061 (amine value: 3mgKOH/g, manufacturer: BYK Company), DISPERBYK-2150 (amine value: 57mgKOH/g, manufacturer: BYK Company) ), DISPERBYK-2155 (amine value: 48mgKOH/g, manufacturer: BYK), DISPERBYK-2163 (amine value: 10mgKOH/g, manufacturer: BYK), DISPERBYK-2164 (amine value: 14mgKOH/g, manufacturer: BYK), BYK-9077 (amine value: 48mgKOH/g, manufacturer: BYK), BYKLPN-21116 (amine value: 29mgKOH/g, manufacturer: BYK), BYKLPN-21324 (amine value: 0mgKOH/g, manufacturer: BYK), etc. can

As the dispersion resin, an acrylic resin can be used, which can improve the stability of the pigment dispersion and also improve the pattern of pixels.

Specifically, the dispersion resin may be a copolymer including a repeating unit represented by Formula 1-1 below, a repeating unit represented by Formula 1-2 below, and a repeating unit represented by Formula 1-3 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 and 1-3, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl.

The dispersion resin may have a weight average molecular weight of 10,000 to 20,000 g/mol and 80 to 200 KOHmg/g.

In addition, the dispersion resin may be a random copolymer or a block copolymer, and in the case of the latter, it may be represented by Formula 1:

In Formula 1, R ¹ and R ² are each independently a hydrogen atom or methyl; a to c are each independently an integer of 1 to 100;

The pigment dispersion may satisfy Equation 1 below. The appearance of the resin film may be improved within the range where the pigment dispersion satisfies Equation 1 below, but if this is not satisfied, the appearance of the resin film may be deteriorated:

[Equation 1]

Pigment content = 100 * p/b

In Equation 1, p is the weight of the pigment solids in the pigment dispersion, and b is the weight of the total solids in the pigment dispersion.

Specifically, out of 100% by weight of the total solids (eg, total pigments, dispersants, dispersion resins, etc.) excluding the dispersion medium in the pigment dispersion, the content of the pigment solids (total pigment solids) is 40% to 80% by weight, It may be more specifically 45% to 80% by weight, more specifically 50% to 80% by weight, such as 60% to 78% by weight.

As the dispersion medium, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), ethylene glycol ethyl acetate (ethylene glycol ethyl acetate, EGA), cyclohexanone, 3-methoxy-1-butanol, or a combination thereof may be used. Specifically, as the dispersion medium, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), or a combination thereof may be used.

The D50 particle diameter of the total solid content (eg, total pigment, dispersant, dispersion resin, etc.) excluding the dispersion medium in the pigment dispersion is 15 nm to 70 nm, specifically 20 nm to 65 nm, more specifically 25 nm to 60 nm, For example, it may be 35 nm to 55 nm. Within this range, it can be appropriately used for semiconductors, display devices, and the like.

The content of the total solid content (eg, total pigment, dispersant, dispersion resin, etc.) excluding the dispersion medium in the pigment dispersion is 10% to 40% by weight, specifically 12% to 30% by weight, based on 100% by weight of the pigment dispersion. %, more specifically from 15% to 25% by weight.

In addition, the pigment dispersion contains 10% to 20% by weight, specifically 12% to 18% by weight of the pigment solids (total pigments) with respect to the total amount of the pigment dispersion; 0.1% to 5% by weight, specifically 1% to 4% by weight of the dispersant; 0.1% to 5% by weight, specifically 1% to 4% by weight of the dispersion resin; The dispersion medium may be included as the remainder.

As this range is satisfied, the red photosensitive resin composition of one embodiment may exhibit excellent coloring strength.

Upon spectroscopic analysis of a red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, Equation 2 below may be satisfied:

[Equation 2]

70 ≤ A/B ≤ 100

In Equation 2, A is the transmittance of the red photosensitive resin film at a wavelength of 725 nm, and B is the transmittance of the red photosensitive resin film at a wavelength of 625 nm.

Specifically, the lower limit of Equation 2 may be 70, 71, 72, 74 or 75, and the upper limit may be 100, 99, 98, 97, 96 or 95.

In addition, upon spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, the transmittance at a wavelength of 430 nm may be 5% or less (however, greater than 0%), , transmittance at a wavelength of 560 nm may be 3.5% or less (however, greater than 0%).

When the results of spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition satisfy the above descriptions, the effect on near-infrared rays is small, so that silicon-based photodiodes, infrared cut-off filters, etc. Regardless of performance, image quality by an image sensor can be implemented at a certain level.

(B) binder resin

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

Specifically, the acrylic binder resin may be a copolymer including a repeating unit represented by Formula 2-1 below, a repeating unit represented by Formula 2-2 below, and a repeating unit represented by Formula 2-3 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 and 2-3, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl.

The acrylic binder resin may have a weight average molecular weight of 6,000 to 10,000 g/mol, 30 to 50 KOHmg/g, and a double bond equivalent of 300 to 400 g/mol.

In addition, the acrylic binder resin may be a random copolymer or a block copolymer, and in the case of the latter, it may be represented by Formula 2:

[Formula 2]

In Formula 1, R ³ and R ⁴ are each independently a hydrogen atom or methyl; d to f are each independently an integer of 1 to 100;

The red photosensitive resin composition of one embodiment includes the acrylic binder resin represented by Chemical Formula 1 as the first acrylic binder resin, and further comprises a second acrylic binder resin, an epoxy binder resin, a cardo binder resin, or a combination thereof. can include

The second acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and includes one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

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

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, or vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds, such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the second acrylic resin include (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, but are not limited thereto, and these can be used alone or in combination of two or more. may be

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

The binder resin may improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may include, for example, a phenol novolak epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is limited thereto It is not.

Furthermore, the binder resin including the epoxy-based binder resin secures dispersion stability of a colorant such as a pigment, which will be described later, and helps to form a pixel having a desired resolution during a developing process.

The 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, film remaining rate and chemical resistance may be greatly improved.

The epoxy equivalent weight of the epoxy-based binder resin may be 150 g/eq to 200 g/eq. When an epoxy-based binder resin having an epoxy equivalent within the above range is included in the binder resin, there is an advantageous effect in improving the curing degree of the formed pattern and fixing the colorant in the patterned structure.

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

The cardo-based binder resin may include a repeating unit represented by Chemical Formula 3 below.

[Formula 3]

In 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 (where R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following any one of the linking groups represented by Chemical Formulas 4-1 to 4-11;

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In 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.)

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid dianhydride moiety;

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

The cardo-based binder resin may include a functional group represented by Chemical Formula 5 at at least one of both terminals.

[Formula 5]

In Formula 5,

Z ³ may be represented by Formulas 5-1 to 5-7 below.

[Formula 5-1]

(In 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.)

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

(In 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.)

[Formula 5-6]

[Formula 5-7]

The cardo-based binder resin may be, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylene tetracarboxylic acid dianhydride , anhydride compounds such as tetrahydrofurantetracarboxylic acid dianhydride and tetrahydrophthalic acid anhydride; Glycol compounds, such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

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

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

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

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

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

(C) photopolymerizable compound

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

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

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

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

The photopolymerizable compound may be treated with an acid anhydride or modified ethylene oxide to impart better developability.

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 during exposure in the pattern forming process, resulting in excellent reliability and excellent developability with an alkaline developer.

(D) photopolymerization initiator

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

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

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

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

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

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

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

The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt %, specifically 0.5 wt % to 4 wt %, for example, 0.1 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, excellent reliability can be obtained due to sufficient curing during exposure in the pattern forming process, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to the unreacted initiator A decrease in transmittance can be prevented.

(D) solvent

As the solvent, materials that have compatibility with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator but do not react may be used.

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

Among these, considering compatibility and reactivity, 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 2-hydroxy ethyl propionate; carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone may be used.

The solvent may be included in a balance amount, 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, it is possible to obtain a coating film having excellent coatability of the photosensitive resin composition and excellent flatness.

(F) other additives

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; Surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

The additives can be easily adjusted according to desired physical properties.

The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Isocyanate propyl triethoxysilane, (gamma) glycidoxy propyl trimethoxysilane, (beta) epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be specifically used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for color filters may further include a surfactant, for example, a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactant include F-556, F-482, F-484, and F-478 manufactured by DIC, but are not limited thereto.

The surfactant is preferably included in an amount of 0.01% to 5% by weight and more preferably in an amount of 0.01% to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, it is not preferable to cause a problem in that foreign substances are generated after development.

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

The photosensitive resin composition may 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 prepared using the red photosensitive resin composition according to the embodiment is provided.

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

A method of manufacturing the color filter is as follows.

For example, the photosensitive resin composition layer is formed by applying the photosensitive resin composition to an appropriate thickness on a glass substrate using an appropriate method such as spin coating, roller coating, or spray coating.

Subsequently, light is irradiated to form a pattern required for a color filter on the substrate on which the photosensitive resin composition layer is formed. As a light source used for irradiation, UV, electron beam, or X-ray may be used, and for example, UV in a range of 190 nm to 450 nm, specifically, 200 nm to 400 nm may be irradiated. In the irradiation step, a photoresist mask may be further used. After performing the irradiation step in this way, 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 to form a pattern required for the color filter. By repeating this process according to the number of colors required, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, etc., crack resistance, solvent resistance, and the like 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, but the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

(Preparation of Pigment Dispersion)

Preparation Example 1: R254 Pigment Dispersion

15 parts by weight of R254 as a red pigment represented by the following formula A, 3 parts by weight of DISPERBYK-2022 (amine value: 61 mgKOH/g, manufacturer: BYK) as a dispersant, RY-117 as a dispersing resin (manufacturer: Showa Denko, molecular weight: 10,000 g / mol, acid value 130 KOHmg / g) 1.5 parts by weight, propylene glycol methyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich) 72.5 parts by weight, propylene glycol methyl ether (PGME, manufacturer: Sigma-Aldrich) 8 parts by weight were mixed An R254 pigment dispersion was obtained using zirconia beads and a shaker (manufacturer: skandex). The D50 of the solid content in the R254 pigment dispersion is 51 nm.

Preparation Example 2: Y139 Pigment Dispersion

12 parts by weight of Y139 as a yellow pigment represented by the following formula B, 4 parts by weight of DISPERBYK-2022 (amine value: 61 mgKOH/g, manufacturer: BYK) as a dispersant, RY-117 as a dispersing resin (manufacturer: Showa Denko, molecular weight: 10,000 g / mol, acid value 130 KOHmg / g) 4 parts by weight, propylene glycol methyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich) 72 parts by weight, propylene glycol methyl ether (PGME, manufacturer: Sigma-Aldrich) 8 parts by weight were mixed A Y139 pigment dispersion was obtained using zirconia beads and a shaker (manufacturer: skandex). The D50 of the solid content in the Y139 pigment dispersion was 35 nm.

[Formula B]

Preparation Example 3: R254 and G58 Pigment Dispersion

13 parts by weight of R254 as a red pigment represented by Formula A, 2 parts by weight of G58 as a green pigment represented by Formula C, 3 parts by weight of DISPERBYK-2022 (amine value: 61 mgKOH/g, manufacturer: BYK) as a dispersant, dispersion resin As RY-117 (manufacturer: Showa Denko, molecular weight: 10,000 g/mol, acid value 130 KOHmg/g) 1.5 parts by weight, propylene glycol methyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich) 72.5 parts by weight, propylene glycol methyl ether (PGME, manufacturer: Sigma-Aldrich) 8 parts by weight were mixed to obtain R254 and G58 pigment dispersions using zirconia beads and a shaker (manufacturer: skandex). The D50 of the solids in the R254 and G58 pigment dispersions is 49 nm.

[Formula C]

In Formula C, a and b are each independently an integer of 0 to 4.

(Preparation of photosensitive resin composition)

Examples 1 to 8 and Comparative Examples 1 to 4

A photosensitive resin composition was prepared by mixing with the compositions shown in Tables 1 to 3.

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

(Unit: % by weight) ingredient material name solid content
(weight%) Example 1 Example 2 Example 3 Example 4 (A) colorant A-1 19.5 31.71 24.35 0.00 30.33 A-2 20 23.55 23.55 24.70 25.38 A-3 19.5 7.45 15.97 37.18 7.37 (B) binder resin B-1 38.5 1.54 1.37 1.65 1.48 (C) photopolymerizable compound C-1 100 1.38 1.23 1.48 1.33 (D) photopolymerization initiator D-1 100 0.16 0.15 0.18 0.16 (E) solvent E-1 - 34.19 33.36 34.80 33.94 (F) additives F-1 100 0.02 0.02 0.02 0.02

(Unit: % by weight) ingredient material name solid content
(weight%) Example 5 Example 6 Example 7 Example 8 (A) colorant A-1 19.5 31.29 26.24 24.94 23.62 A-2 20 23.92 23.92 22.73 21.53 A-3 19.5 7.57 12.61 11.99 11.35 (B) binder resin B-1 38.5 1.52 1.52 1.97 2.41 (C) photopolymerizable compound C-1 100 1.37 1.37 1.77 2.17 (D) photopolymerization initiator D-1 100 0.16 0.16 0.21 0.26 (E) solvent E-1 - 34.14 34.14 36.38 38.63 (F) additives F-1 100 0.02 0.02 0.02 0.02

(Unit: % by weight) ingredient material name solid content
(weight%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) colorant A-1 19.5 26.10 49.30 37.70 0.00 A-2 20 39.88 10.88 25.38 10.88 A-3 19.5 0.00 0.00 0.00 49.30 (B) binder resin B-1 38.5 1.02 1.94 1.48 1.94 (C) photopolymerizable compound C-1 100 0.91 1.74 1.33 1.74 (D) photopolymerization initiator D-1 100 0.11 0.21 0.16 0.21 (E) solvent E-1 - 31.96 35.92 33.94 35.92 (F) additives F-1 100 0.02 0.02 0.02 0.02

Each component used in Tables 1 to 3 is as follows.

(A) colorant

(A-1) R254 pigment dispersion (Preparation Example 1)

(A-2) Y139 Pigment Dispersion (Preparation Example 2)

(A-3) R254 and G58 pigment dispersion (Preparation Example 3)

(B) binder resin

(B-1) RY-92 (manufacturer: Showa Denko, molecular weight: 6,000 g/mol, acid value: 35 KOHmg/g, double bond equivalent: 350 g/mol) and propylene glycol methyl ether acetate (PGMEA) as an acrylic binder resin , manufacturer: Sigma-Aldrich) containing a dispersion (solid content: 38.5% by weight)

(C) photopolymerizable compound

(C-1) dipentaerythritol hexaacrylate (DPHA, manufacturer: Nippon Explosives)

(D) photopolymerization initiator

(D-1) Oxime-based initiator (product name: SPI-03, manufacturer: Samyang Corporation)

(E) solvent

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

(F) additives

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

For reference, for Examples 1 to 8 and Comparative Examples 1 to 4, the total pigment content (Equation 1) in 100% by weight of the total solid content in the pigment dispersion is summarized in Tables 4 to 6 below.

Example 1 Example 2 Example 3 Example 4 Each pigment content in total pigment solids
(weight%) R254 66.35 65.08 57.09 63.87 Y139 31.93 31.29 34.13 34.43 G58 1.73 3.63 8.78 1.71 PWC (% by weight) 60 61.2 58.9 60

Example 5 Example 6 Example 7 Example 8 Each pigment content in total pigment solids
(weight%) R254 65.80 64.63 64.63 64.63 Y139 32.44 32.44 32.44 32.44 G58 1.75 2.92 2.92 2.92 PWC (% by weight) 60 60 57 54

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Each pigment content in total pigment solids
(weight%) R254 45.63 85.32 65.57 73.94 Y139 54.37 14.68 34.43 14.68 G58 0 0 0 11.38 PWC (% by weight) 60 60 60 60

(Evaluation: evaluation of transmittance and low exposure lifting)

(1) Preparation of color filter specimens

The “photosensitive” resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 4 were coated on an 8-inch glass substrate using a spin coater (Mikasa, Opticoat MS-A150), and then coated with a hot-plate at 100 °C. Soft-baking was performed for 180 seconds at ° C., and exposure was performed by irradiating light for 1000 msec with an i-line stepper (Nikon Corp., NSR-2005i10C). The exposed substrate was developed by a spray & puddle method in a 0.19% TMAH aqueous solution at room temperature, and then hard-baked on a hot-plate at 200° C. for 5 minutes. Accordingly, a color filter specimen having a 5800 Å-thick photosensitive resin film formed on the glass substrate was obtained.

(2) Evaluation of transmittance

Using the color filter specimen obtained above, a light transmission spectrum in the visible region was measured using a microspectrophotometery (model name: Lvmicro-Z, manufactured by Lambda Vison Inc., Japan). Transmittances at 430 nm, 560 nm, 625 nm and 725 nm were obtained, and the results are shown in Table 2 below.

(3) Evaluation of low exposure lifting

The failure of the pixel pattern to remain adhered to the substrate at inappropriate and low exposure energy is called low exposure lifting. In this evaluation, light was irradiated for 100 msec with an i-line stepper (Nikon Co., NSR-2005i10C) to evaluate patterns having a size of 0.8 μm, and the results are shown in Table 7 below.

430 nm transmittance 560 nm transmittance (725 nm transmittance)
/(625 nm transmittance)
[Equation 2] low exposure lifting Example 1 2.0 1.9 94.1 non-occurrence Example 2 2.1 2.0 85.9 non-occurrence Example 3 4.3 3.1 75.8 non-occurrence Example 4 3.2 1.7 94.7 non-occurrence Example 5 3.0 1.3 89.4 non-occurrence Example 6 3.0 1.4 85.1 non-occurrence Example 7 3.2 1.6 86.0 non-occurrence Example 8 4.1 2.1 87.3 non-occurrence Comparative Example 1 1.0 8.8 102.5 - Comparative Example 2 5.4 1.1 107.0 - Comparative Example 3 2.8 1.4 111.2 - Comparative Example 4 6.9 2.0 64.2 generation

According to Table 7, the color filter specimens including the photosensitive resin films prepared using the photosensitive resin compositions of Examples 1 to 8 had (725 nm transmittance)/(625 nm transmittance) 70 to 100, specifically 85 to 85 nm. 95, which satisfies Equation 2 above.

On the other hand, the color filter specimens including the photosensitive resin films prepared using the photosensitive resin compositions of Comparative Examples 1 to 4 had (725 nm transmittance)/(625 nm transmittance) less than 70 or greater than 100, resulting in the above-mentioned Equation 2 is not satisfied.

Furthermore, color filter specimens including photosensitive resin films prepared using the photosensitive resin compositions of Examples 1 to 8 had a transmittance of 5% or less at a wavelength of 430 nm and a transmittance of 3.5% or less at a wavelength of 560 nm. am.

On the other hand, color filter specimens including photosensitive resin films prepared using the photosensitive resin compositions of Comparative Examples 1 to 4 had a transmittance of more than 5% at a wavelength of 430 nm or a transmittance of 3.5% at a wavelength of 560 nm. exceed

Overall, the red photosensitive resin composition of one embodiment, represented by the photosensitive resin compositions of Examples 1 to 8, has little effect on near-infrared rays, regardless of the performance of a silicon-based photodiode, an infrared cut filter, etc., by an image sensor. Image quality can be implemented at a certain level.

In addition, based on Examples 1 to 8, the transmittance may be controlled within a desired range by adjusting the compounding ratio of components constituting the red photosensitive resin composition of one embodiment, such as a pigment dispersion.

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

Claims (18)

(A) a colorant;
(B) a binder resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator; and
(E) contains a solvent;
The colorant includes a pigment dispersion,
The pigment dispersion contains 50 wt% to 80 wt% of CI red pigment 254, 20 wt% to 40 wt% of CI yellow pigment 139, and 0.1 wt% to 0.1 wt% of CI green pigment 58, based on 100 wt% of the total pigment. containing 10% by weight,
A red photosensitive resin composition.
According to claim 1,
In 100% by weight of the total pigment, 57% to 67% by weight of CI red pigment 254, 30% to 35% by weight of CI yellow pigment 139, and 1.5% to 9% by weight of CI green pigment 58 A red photosensitive resin composition comprising:
According to claim 1,
The pigment dispersion further comprises a dispersing agent, a dispersing resin, a dispersing medium, or a combination thereof, the red photosensitive resin composition.
According to claim 3,
The dispersant has an amine value of 100 mgKOH/g or less (however, greater than 0 mgKOH/g), a red photosensitive resin composition.
According to claim 3,
The pigment dispersion has a pigment content of 40% to 80% by weight according to Equation 1 below, a red photosensitive resin composition:
[Equation 1]
Pigment content = 100 * p/b
In Equation 1 above,
p is the weight of the pigment solids in the pigment dispersion,
b is the weight of total solids in the pigment dispersion.
According to claim 3,
The dispersion medium is a red photosensitive resin composition comprising propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), or a combination thereof.
According to claim 3,
The total solid content in the pigment dispersion is 10% by weight to 40% by weight, the red photosensitive resin composition.
According to claim 3,
The D50 particle diameter of the total solids in the pigment dispersion is 15 nm to 70 nm, the red photosensitive resin composition.
According to claim 3,
The pigment dispersion, relative to the total amount of the pigment dispersion,
10% to 20% by weight of the total pigment,
0.1% to 5% by weight of the dispersant,
0.1% to 5% by weight of the dispersion resin,
Comprising the dispersion medium as the remainder,
A red photosensitive resin composition.
According to claim 1,
Upon spectroscopic analysis of a red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, a red photosensitive resin composition satisfying Equation 2 below:
[Equation 2]
70 ≤ A/B ≤ 100
In Equation 2 above,
A is the transmittance of the red photosensitive resin film at a wavelength of 725 nm,
B is the transmittance of the red photosensitive resin film at a wavelength of 625 nm.
According to claim 10,
Upon spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, the transmittance at a wavelength of 430 nm is 5% or less (however, greater than 0%), the red photosensitive resin composition.
According to claim 10,
Upon spectroscopic analysis of the red photosensitive resin film having a thickness of 5500 Å to 6000 Å prepared using the red photosensitive resin composition, the transmittance at a wavelength of 560 nm is 3.5% or less (however, greater than 0%), the red photosensitive resin. composition.
According to claim 1,
The binder resin is a red photosensitive resin composition comprising an acrylic binder resin.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
5% to 70% by weight of the (A) colorant;
0.1% to 20% by weight of the (B) binder resin;
0.1% to 20% by weight of the (C) photopolymerizable compound;
0.1% to 5% by weight of the (D) photopolymerization initiator; and
The remaining amount of the above (E) solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; And a photosensitive resin composition further comprising at least one additive selected from a radical polymerization initiator.
A red photosensitive resin film prepared using the red photosensitive resin composition according to any one of claims 1 to 15.
A red color filter comprising the red photosensitive resin film of claim 16 .
A CMOS image sensor comprising the red color filter of claim 17 .