WO2024048893A1 - Photosensitive resin composition, photosensitive resin layer manufactured using same, and color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a photosensitive resin layer manufactured using same, and a color filter. Specifically, one embodiment provides a photosensitive resin composition comprising: (A) a binder resin; (B) a photopolymerizable compound; (C) a colorant; (D) a photopolymerization initiator; and (E) a solvent, wherein the weight ratio of the binder resin to the photopolymerizable compound (binder resin/photopolymerizable compound) is 60/40 or more, the weight average molecular weight of the binder resin is 4,000 g/mol to 9,000 g/mol, and the photopolymerizable compound is a hexafunctional photopolymerizable compound alone, or a mixture of a hexafunctional photopolymerizable compound and a bifunctional photopolymerizable compound.

Description

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

This description relates to a photosensitive resin composition, a photosensitive resin film and a color filter manufactured using the same.

A CMOS image sensor (CIS) is a non-memory semiconductor that converts images received by a camera into digital signals and is a collection of pixels such as color filters, photo diodes, and amplifiers.

Recently, CIS for mobile devices requires more pixels and more cameras, increasing the demand for thinner and smaller image sensors. To meet this demand, CIS's photosensitive resin composition (Photoresist, PR) for color filters needs to realize smaller pixels while forming fine patterns.

However, as the size of the pixels that make up the color filter for CIS gets smaller, the signal-to-noise ratio (SNR) becomes an important issue. Since the driving method of CIS is based on the principle that light from the outside is transmitted through a color filter and the transmitted light is converted into an electrical signal while passing through a photo diode, a decrease in the size of the pixel means that the amount of light incident per unit pixel decreases. This means it is decreasing. Additionally, as the size of a pixel decreases, the distance between pixels becomes closer, so light transmitted from adjacent pixels may act as noise.

Generally, among the red, green, and blue photosensitive resin compositions that make up the color filter of a CIS device, the green photosensitive resin composition is applied first to form a pattern, followed by the blue or red photosensitive resin composition, and finally the red or blue photosensitive resin composition. This is applied to form a pattern. At this time, the red or blue photosensitive resin composition is applied between the uneven patterns formed by the lower green photosensitive resin composition, so the degree of filling between the patterns varies depending on the rheological properties of the composition, resulting in the actual red or blue composition pattern formed between the green composition patterns. There may be a large difference in thickness. Thickness is an important factor in forming the signal of the color represented by the pattern because the thicker the color, the darker the color, and the thinner the color, the lighter the color. Therefore, the thickness uniformity of the pattern plays a decisive role in driving the CIS device.

In this regard, by checking the SNR characteristics after manufacturing the CIS device, not only the SNR of the chip forming one pixel is high, but also the SNR distribution (Spatial SNR, S.SNR) of the chips present in the entire substrate is high. You need to make sure it appears evenly.

One embodiment is to provide a photosensitive resin composition that has a low level difference between the pattern and the resin film when forming a photosensitive resin film on a patterned substrate for the purpose of improving SNR distribution (S. SNR) of CIS.

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

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

One embodiment includes (A) a binder resin; (B) photopolymerizable compound; (C) photopolymerization initiator; (D) colorant; and (E) a solvent; The weight ratio of the binder resin to the photopolymerizable compound (binder resin/photopolymerizable compound) is 60/40 or more; The weight average molecular weight of the binder resin is 4,000 g/mol to 9,000 g/mol; The photosensitive resin composition is provided in which the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound and a bifunctional photopolymerizable compound.

When forming a photosensitive resin film using the photosensitive resin composition on a patterned substrate, the step according to Equation 1 below may be 1,000 Å or less:

[Equation 1]

(step difference)=A+B-C

In Equation 1, A is the height of the pattern of the patterned substrate, B is the maximum height of the photosensitive resin film formed in the area where the pattern of the patterned substrate exists, and C is the height of the pattern of the patterned substrate. This is the lowest height of the photosensitive resin film formed in the area not covered.

The colorant may include a blue pigment, a purple pigment, or a combination thereof.

The photosensitive resin film may be blue, and the pattern of the substrate may be green.

The acid value of the binder resin may be 30 KOHmg/g to 100 KOHmg/g.

The binder resin may be a hydrophobic acrylic binder resin.

The viscosity of the hexafunctional photopolymerizable compound at 25°C may be 5,500 to 8,000 cps.

The viscosity of the bifunctional photopolymerizable compound at 25° C. may be 600 to 700 cps.

The solvent is propylene glycol monomethyl ether acetate (PGMEA), n-Butyl Acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof. It can be included.

The photosensitive resin composition includes 0.5% by weight to 15% by weight of the (A) binder resin, based on the total amount of the photosensitive resin composition; 0.1% to 10% by weight of the (B) photopolymerizable compound; (C) 0.1% to 10% by weight of photopolymerization initiator; 0.5% to 15% by weight of the (D) colorant; And it may include the remaining amount of the solvent (E).

The photosensitive resin composition further contains malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent containing a vinyl group or (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. It can be included.

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

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

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

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

When a photosensitive resin film is formed on a patterned substrate using the photosensitive resin composition according to one embodiment, the step difference between the pattern and the resin film is formed to be low, and thus the SNR distribution (S. SNR) of the CIS can be improved.

Figure 1 is a schematic diagram for explaining the level difference between the pattern and the resin film.

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 the compound is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, or already. 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. , C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise specified herein, “heterocycloalkyl group”, “heterocycloalkenyl group”, “heterocycloalkynyl group”, and “heterocycloalkylene group” refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl group, respectively. It means that at least one hetero atom of N, O, S or P is present in the ring compound of ren.

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

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

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

Additionally, unless otherwise defined herein, “*” means a portion connected to the same or different atom or chemical formula.

(Photosensitive resin composition)

One embodiment provides a photosensitive resin composition that has a low level difference between the pattern and the resin film when forming a photosensitive resin film on a patterned substrate for the purpose of improving SNR distribution (S. SNR) of CIS.

Specifically, Figure 1 is a schematic diagram for explaining the level difference between the pattern and the resin film. When a photosensitive resin film is formed on a patterned substrate, a height (A+B) corresponding to the sum of the pattern height (A) of the substrate and the maximum height (B) of the photosensitive resin film formed in the area where the pattern of the substrate exists is , a difference occurs in the minimum height (C) of the photosensitive resin film formed in the area where the pattern of the substrate does not exist.

The level difference between the pattern and the resin film is affected by the type and ratio of transparent materials that contribute to pattern formation, such as binder resin, photopolymerizable compound, and solvent, rather than pigments directly related to color.

In this regard, one embodiment includes (A) a binder resin; (B) photopolymerizable compound; (C) photopolymerization initiator; (D) colorant; and (E) a solvent; The weight ratio of the binder resin to the photopolymerizable compound (binder resin/photopolymerizable compound) is 60/40 or more; The weight average molecular weight of the binder resin is 4,000 g/mol to 9,000 g/mol; The photosensitive resin composition is provided in which the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound and a bifunctional photopolymerizable compound.

The photosensitive resin film may be blue, and the pattern of the substrate may be green.

The colorant may include a blue pigment, a purple pigment, or a combination thereof, and a blue photosensitive resin film can be manufactured using such a colorant.

When forming a photosensitive resin film using the photosensitive resin composition on a patterned substrate, the step difference according to Equation 1 below may be 1,000 Å or less:

[Equation 1]

(step difference)=A+B-C

In Equation 1, A is the height of the pattern of the patterned substrate, B is the maximum height of the photosensitive resin film formed in the area where the pattern of the patterned substrate exists, and C is the height of the pattern of the patterned substrate. This is the lowest height of the photosensitive resin film formed in the area not covered.

Experimentally, after coating is performed at an rpm that can produce a certain thickness for each sample on a patterned substrate, SB is performed on a 100C hot plate, and the thickness of the portion where only PR is coated is measured using TENCOR equipment. Afterwards, the surface profile of the area surrounding the 1.4um pattern was measured using Park Systems' AFM (Atomic Force Microscopy) equipment. When the line profile is measured along the cross section passing through the pattern using surface profile data acquired through AFM equipment, the ΔY (nm) value of the highest and lowest parts becomes the step difference between the pattern and the resin film.

The ΔY (nm) value is the same as the step according to Equation 1 described above.

As mentioned earlier, the thicker the color, the darker the color, and the thinner the color, the lighter it is, so it is an important factor in forming the signal of the color represented by the pattern. Therefore, the thickness uniformity of the pattern is important for the CMOS image sensor (CIS). It plays a decisive role in driving.

The photosensitive resin composition of one embodiment can control the step according to Equation 1 to 1,000 Å or less, specifically 998 Å or less, 996 Å or less, 994 Å or less, 992 Å or less, or 990 Å or less by controlling the multiple factors. You can.

In particular, as the weight ratio of the binder resin/photopolymerizable compound becomes larger in the range of 60/40 or more, and as the weight average molecular weight of the binder resin decreases closer to 4,000 g/mol in the range of 9,000 g/mol or less, the hexafunctional It essentially includes a photopolymerizable compound, but as a bifunctional photopolymerizable compound is added, the closer the addition amount is controlled to 50/50, the lower the step according to Equation 1 above.

Hereinafter, we will look at the factors affecting the step difference.

SNR can be improved by adjusting the transmission spectrum of the pigment or dye in the visible light region. The overlapping area in the transmission spectrum of red, green, and blue that makes up the color filter is called crosstalk, and since this can act as noise for different colors, it is important to design the transmission spectrum to minimize this. do. Crosstalk can be improved by mixing yellow pigment for red and green, and using violet pigment for blue.

In addition to the transmission spectrum, there is an improvement direction that increases light efficiency through surface characteristics. When the photosensitive resin composition forms a fine pattern, the roughness of the surface can affect the decrease in SNR, and after it is applied on a silicon wafer, the thickness deviation between the edge and center of the wafer, the presence or absence of stains and striations, etc. affect the S.SNR. can be given. This can be improved by changing the type, ratio, and content of transparent materials such as resin, monomer, solvent, and additives that contribute to pattern formation rather than pigments directly related to color.

Weight ratio of binder resin/photopolymerizable compound

In one embodiment, as the weight ratio of the binder resin/photopolymerizable compound increases in the range of 60/40 or more, the step difference according to Equation 1 becomes lower.

Specifically, the weight ratio of the binder resin/photopolymerizable compound may be 60/40 or more or 70/30 or more, but less than 100/1.

(A) Binder resin

In one embodiment, as the weight average molecular weight of the binder resin decreases closer to 4,000 g/mol in the range of 9,000 g/mol or less, the step according to Equation 1 becomes lower.

Specifically, the weight average molecular weight of the binder resin may be 4,000 g/mol or more, but 9,000 g/mol or less, 8,000 g/mol or less, 7,000 g/mol or less, or 6,000 g/mol or less.

When the weight average molecular weight of the binder resin is within the above range, it has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

The acid value of the binder resin may be 30 KOHmg/g to 100 KOHmg/g. When the acid value of the binder resin is within the above range, excellent pixel resolution can be obtained.

The binder resin may be a hydrophobic acrylic binder resin.

The binder resin is a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing one or more acrylic repeating units.

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

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight, based on the total amount of the alkali-soluble resin.

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

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

The binder resin may be included in an amount of 0.5% by weight to 15% by weight, for example, 1% by weight to 5% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability is excellent when manufacturing a color filter, and crosslinking properties are improved to obtain excellent surface smoothness.

(B) Photopolymerizable compound

In one embodiment, the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound (a first photopolymerizable compound) and a bifunctional photopolymerizable compound (a second photopolymerizable compound).

As the difunctional photopolymerizable compound is added, the closer the addition amount is controlled to 50/50, the lower the level difference according to Equation 1 becomes.

Specifically, when adding the bifunctional photopolymerizable compound (second photopolymerizable compound), the weight ratio of the first/second photopolymerizable compound may be 50/50 or more and 75/25 or less.

The functional group included in each of the hexafunctional photopolymerizable compound and the bifunctional photopolymerizable compound may be a (meth)acrylate group.

The hexafunctional photopolymerizable compound may be dipentaerythritol hexaacrylate (DPHA), which is represented by the following formula and has a viscosity of 5,500 cps to 8,000 cps at 25°C.

The bifunctional photopolymerizable compound is represented by the following formula and has a viscosity of 600 cps to 700 cps at 25 ° C. )10 Diacrylate).

In the above formula, m+n=10.

The photopolymerizable compound may be included in an amount of 0.1% by weight to 15% by weight, for example, 0.5% by weight to 5% by weight, 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 to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.

(C) Photopolymerization initiator

The photopolymerization initiator is an initiator commonly 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. You can use it.

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

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

Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.

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

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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, etc.

Examples of the oxime-based compounds include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime) )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime-O- Acetate, etc. can be mentioned.

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

The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, for example, 1% by weight to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure during the pattern formation process to obtain excellent reliability, the heat resistance, light resistance, and chemical resistance of the pattern are excellent, resolution and adhesion are also excellent, and there is no damage from unreacted initiators. Deterioration of transmittance can be prevented.

(D) Colorant

In one embodiment, the colorant may include a blue pigment, a purple pigment, or a combination thereof.

Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Copper phthalocyanine pigments such as blue pigment 16 and the like can be mentioned.

Examples of the purple pigment include C.I. Violet pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet Pigment 27, C.I. Violet Pigment 28, C.I. Violet Pigment 29, C.I. Violet Pigment 30, C.I. Violet Pigment 32, C.I. Violet Pigment 37, C.I. Violet Pigment 40, C.I. Violet Pigment 42, C.I. Violet Pigment 50 or a combination thereof may be mentioned.

In addition, red pigment, green pigment, yellow pigment, black pigment, etc. may be further included.

Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89, etc. can be mentioned.

Examples of the green pigment include C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green pigment 59, etc. can be mentioned.

Examples of the yellow pigment include C.I. Isoindoline pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. and nickel complex pigments such as yellow pigment 150.

Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. The above pigments can be used alone or in a mixture of two or more. For example, the pigment may be a yellow pigment, a green pigment, or a mixture thereof.

The pigment may be included in the photosensitive resin composition for a color filter in the form of a dispersion. This pigment dispersion may be composed of the pigment, solvent, dispersant, dispersion resin, etc.

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

The dispersant helps the pigment to be uniformly dispersed in the dispersion, and nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycol or its ester, polyoxy alkylene, 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 addition. Water, alkyl amine, etc. can be used, and these can be used alone or in a mixture of two or more types.

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

The colorant may further include an organic solvent-soluble dye.

Examples of the organic solvent-soluble dye include triarylmethane-based compounds, anthraquinone-based compounds, benzylidene-based compounds, xanthene-based compounds, phthalocyanine-based compounds, azaporphyrin-based compounds, and indigo-based compounds.

When the dye and the pigment are mixed and used, they can be mixed at a weight ratio of 1:9 to 9:1, specifically 3:7 to 7:3. When mixed in the above weight ratio range, chemical resistance, durability, and maximum absorption wavelength can be controlled to an appropriate range, and high luminance and contrast ratio can be expressed at the desired color coordinate.

Based on the total amount of the photosensitive resin composition of the embodiment, the colorant may be included in an amount of 0.5% by weight to 15% by weight, for example, 1% by weight to 10% by weight. When the colorant is included within the above range, the color reproduction rate is excellent, and the curability and adhesion of the pattern are excellent.

(E) Solvent

The solvent may be a material 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; 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; Alkyl oxyacetic acid esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 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 propionate esters such as methyl 2-oxy-2-methyl propionate, ethyl 2-oxy-2-methyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as ethyl methyl propionate; esters such as ethyl 2-hydroxy propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxy acetate, and 2-hydroxy-3-methyl methyl butanoate; Keto acid esters such as ethyl pyruvate, and others include N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, considering compatibility and reactivity, the solvents include propylene glycol monomethyl ether acetate (PGMEA), n-Butyl Acetate (n-BA), and ethylene glycol dimethyl ether (Ethylene). glycol Dimethyl ether), or a combination thereof may be used.

The solvent may be included in the remaining amount, for example, 70% by weight to 90% by weight, for example, 80% by weight to 90% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has excellent applicability and a coating film with excellent flatness can be obtained.

(F) Other additives

The photosensitive resin composition contains malonic acid to prevent stains or spots upon application, to improve leveling performance, and to prevent the creation of residues due to non-development; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Surfactants; and at least one additive selected from radical polymerization initiators.

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 methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Examples include isocyanate propyl triethoxysilane, γ glycidoxy propyl trimethoxysilane, and β epoxycyclohexyl)ethyltrimethoxysilane, and these can be used alone or in a mixture of two or more types.

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

Additionally, the photosensitive resin composition for a color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary.

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

The surfactant is preferably contained in an amount of 0.01 wt% to 5 wt%, and more preferably in an amount of 0.01 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If it is outside the above range, it is undesirable because it may cause problems with foreign substances occurring after development.

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

(Photosensitive resin film)

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

The manufacturing method of the photosensitive resin film is as follows.

A photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 um to 10 um, using an appropriate method such as spin coating, roller coating, or spray coating, on a glass substrate.

Baking is performed at 80 to 100°C for 170 to 190 seconds using a hot-plate, exposure is performed at a power of 450 to 470 mJ using an exposure machine, and then the heating plate is heated to 210 to 250°C. The photosensitive resin composition layer can be converted into a photosensitive resin film by baking on a hot-plate for 3 to 10 minutes.

The photosensitive resin film may have a transmittance of 85% or more, specifically 97% or more, for example, 90% or more in a wavelength range of 480 to 620 nm. In addition, the photosensitive resin film may have a transmittance in a wavelength range of less than 480 nm and a transmittance in a wavelength range of more than 620 nm, respectively, of 15% or less, specifically 13% or less, for example, 10% or less.

The photosensitive resin film may have a small thickness while reaching the above spectral target. Specifically, the thickness of the photosensitive resin film may be 0.5 um or less, specifically 0.45 um or less, more specifically 0.4 um or less, for example, 0.35 um or less.

(color filter)

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

The manufacturing method of the color filter is as follows.

A photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 um to 10 um, using an appropriate method such as spin coating, roller coating, or spray coating, on a glass substrate.

Next, light is irradiated to the substrate on which the photosensitive resin composition layer is formed to form a pattern necessary for a color filter. As a light source used for irradiation, UV, electron beams, or The above irradiation process can also be performed by further using a photoresist mask. After performing this irradiation process, the photosensitive resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed portion of the photosensitive resin composition layer is dissolved, thereby forming a pattern necessary for the color filter. By repeating this process according to the number of colors required, a color filter with a desired pattern can be obtained. In addition, crack resistance, solvent resistance, etc. can be improved by heating the image pattern obtained through development in the above process again or curing it by irradiation with actinic rays.

According to another implementation, a CMOS image sensor including the above-described color filter is provided.

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

(reference example)

Preparation of photosensitive resin composition

Photosensitive resin compositions according to Reference Examples 1 to 15 were prepared by mixing the compositions shown in Tables 1 to 3 below.

Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, then a binder resin, photopolymerizable compound and additives were added thereto and stirred at room temperature for 60 minutes. Then, the pigment dispersion as a colorant was added to the obtained reaction product and stirred at room temperature for 30 minutes. The product was then filtered twice to remove impurities, thereby preparing a photosensitive resin composition (solid content: 11.4% by weight).

(Unit: weight%)

		Solid content (% by weight)	Reference example 1	Reference example 2	Reference example 3	Reference example 4	Reference example 5
(A) Binder resin	A-1	38.5	-	1.496	3.740	4.488	5.236
	A-2	37.8	-	-	-	-	-
	A-3	39.3	-	-	-	-	-
	A-4	38.8	-	-	-	-	-
(B) Photopolymerizable compound	B-1	100	2.880	2.304	1.440	1.152	0.864
	B-2	100	-	-	-	-	-
B-3	100	-	-	-	-	-
B-4	100	-	-	-	-	-
B-5	100	-	-	-	-	-
B-6	100	-	-	-	-	-
B-7	100	-	-	-	-	-
Binder resin/photopolymerizable compound weight ratio		-	0/100	20/80	50/50	60/40	70/30
(C) Photopolymerization initiator	C-1	100	0.547	0.547	0.547	0.547	0.547
(D) Colorant	D-1	18.04	43.234	43.234	43.234	43.234	43.234
(E) Solvent	E-1	-	17.546	16.626	15.245	14.785	14.325
	E-2	-	26.580	26.580	26.580	26.580	26.580
	E-3	-	8.860	8.860	8.860	8.860	8.860
(F) Additives	F-1	One	0.044	0.044	0.044	0.044	0.044
	F-2	10	0.200	0.200	0.200	0.200	0.200
	F-3	100	0.109	0.109	0.109	0.109	0.109

(Unit: weight%)

		Solid content (% by weight)	Reference example 6	Reference example 7	Reference example 8	Reference example 9	Reference example 10
(A) Binder resin	A-1	38.5				3.740	3.740
	A-2	37.8	3.809
	A-3	39.3		3.664
	A-4	38.8			3.711
(B) Photopolymerizable compound	B-1	100	1.440	1.440	1.440	1.080	0.720
	B-2	100				0.360	0.720
	B-3	100
	B-4	100
	B-5	100
	B-6	100
	B-7	100
Binder resin/photopolymerizable compound weight ratio		-	0/100	50/50	50/50	50/50	50/50
(C) Photopolymerization initiator	C-1	100	0.547	0.547	0.547	0.547	0.547
(D) Colorant	D-1	18.04	43.234	43.234	43.234	43.234	43.234
(E) Solvent	E-1	-	15.176	15.322	15.274	15.245	15.245
	E-2	-	26.580	26.580	26.580	26.580	26.580
	E-3	-	8.860	8.860	8.860	8.860	8.860
(F) Additives	F-1	One	0.044	0.044	0.044	0.044	0.044
	F-2	10	0.200	0.200	0.200	0.200	0.200
	F-3	100	0.109	0.109	0.109	0.109	0.109

(Unit: weight%)

		Solid content (% by weight)	Reference example 6	Reference example 7	Reference example 8	Reference example 9	Reference example 10
(A) Binder resin	A-1	38.5	3.740	3.740	3.740	3.740	3.740
	A-2	37.8
	A-3	39.3
	A-4	38.8
(B) Photopolymerizable compound	B-1	100	0.720	0.720
	B-2	100			0.720	0.720	0.720
	B-3	100			0.720
	B-4	100				0.720
	B-5	100					0.720
	B-6	100	0.720
	B-7	100		0.720
Binder resin/photopolymerizable compound weight ratio		-	0/100	50/50	50/50	50/50	50/50
(C) Light curing initiator	C-1	100	0.547	0.547	0.547	0.547	0.547
(D) Colorant	D-1	18.04	43.234	43.234	43.234	43.234	43.234
(E) Solvent	E-1	-	15.245	15.245	15.245	15.245	15.245
	E-2	-	26.580	26.580	26.580	26.580	26.580
	E-3	-	8.860	8.860	8.860	8.860	8.860
(F) Additives	F-1	One	0.044	0.044	0.044	0.044	0.044
	F-2	10	0.200	0.200	0.200	0.200	0.200
	F-3	100	0.109	0.109	0.109	0.109	0.109

The materials listed in Tables 1 to 3 above are as follows.

(A) Binder resin

(A-1) Hydrophobic acrylic binder resin 1 (acid value: 34 KOHmg/g, molecular weight: 9,000 g/mol, double bond equivalent: 340 g/mol, product name: RY-92-M10, manufacturer: Showadenko)

(A-2) Hydrophobic acrylic binder resin 2 (acid value: 38 KOHmg/g, molecular weight: 4,000 g/mol, double bond equivalent: 360 g/mol, product name: RY-92-M4, manufacturer: Showadenko)

(A-3) Hydrophobic acrylic binder resin 3 (acid value: 90 KOHmg/g, molecular weight: 6,000 g/mol, double bond equivalent: 500 g/mol, product name: RY-99, manufacturer: Showadenko)

(A-4) Hydrophobic acrylic binder resin 4 (acid value: 35 KOHmg/g, molecular weight: 13,000 g/mol, double bond equivalent: 330 g/mol, product name: RY-92-M15, manufacturer: Showadenko)

(B) Photopolymerizable compound

(B-1) Hexafunctional photopolymerizable compound 1 represented by the following formula (viscosity: 5500~8000 cps @25℃, substance name: dipentaerythritol hexaacrylate (DPHA), manufacturer: Nippon Gunpowder)

(B-2) Bifunctional photopolymerizable compound 1 represented by the following formula (viscosity: 600~700 cps @25℃, material name: BPA(EO)10DA Bisphenol A (EO)10 Diacrylate, product name: M2100, manufacturer: Miwon Corporation )

In the above formula, m+n=10.

(B-3) Hexafunctional photopolymerizable compound 2 represented by the following formula (viscosity: 6950cps @25℃, substance name: Di-pentaerythritol Polyacrylate, product name: A-9550, manufacturer: Shinnakamura)

In the above formula, R is a hydrogen atom or *-(C=O)CH=CH ₂ .

(B-4) Hexafunctional photopolymerizable compound 3 represented by the following formula (viscosity: 900~2000 cps @25℃, product name: DPCA60, manufacturer: Nippon Explosives)

(B-5) Hexafunctional photopolymerizable compound 4 (viscosity: 390 cps @25℃, product name: A-DPH-6E, manufacturer: Shinnakamura)

In the above formula, a+b+c+d+e+f=6.

(B-6) Bifunctional photopolymerizable compound 2 (Viscosity: 600~700 cps @25℃, substance name: Ethoxylated bisphenol A diarylate, product name: ABPE-20, manufacturer: Shinnakamura)

In the above formula, m+n=2.

(B-7) Tetrafunctional photopolymerizable compound (viscosity: 230 cps @25℃, substance name: Ethoxylated diglycerin tetraacrylate, product name: DGE4A, manufacturer: Gongyeongsa)

In the above formula, a+b+c+d=4.

(C) Photopolymerization initiator

(C-1) Oxime-based initiator (OXE-01 series, product name: SPI03, manufacturer: Samyang Corporation)

(D) Colorant

(D-1) Blue Pigment B15:6 / Violet Pigment V23 = Pigment dispersion mixed at a ratio of 77/23 (Product name: BA1442, Manufacturer: Sanyo)

(E) Solvent

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

(E-2) n-butyl acetate (n-BA, manufacturer: ENF)

(E-3) Ethylene glycol dimethyl ether (Product name: EDM-S, Manufacturer: Toho Chemical)

(F) Additives

(F-1) Antioxidant 4-Methoxyphenol (MHQ, Manufacturer: Weifang TongRun Chem)

(F-2) Fluorine-based surfactant (F-556, manufacturer: DIC)

(F-3) Silane-based coupling agent (KBM-503, manufacturer: ShinEtsu)

(Assessment Methods)

A photosensitive resin film was formed on the patterned substrate using each photosensitive resin composition according to Reference Examples 1 to 15, and the step difference and S.SNR between the pattern and the resin film were evaluated. The specific evaluation method is as follows.

(1) How to evaluate the level difference between the pattern and the resin film: First, coat Green PR on an 8-inch silicon wafer substrate surface-treated with APL solution using a MIKASA coating machine to produce a thickness of 4500A, and pre-bake it on a 100C hot plate ( After proceeding with Softbake, SB, pattern exposure is performed on the i-line stepper under the exposure conditions of Dose: 600ms/Focus: -0.2um. In the exposure process, the thickness was measured using TENCOR equipment and then developed to reveal a pattern. TMAH solution was used as a developer, and the time (seconds) for the pattern to appear (BP) was measured. At this time, BP is about 5 seconds or less. After developing and washing processes, the pattern thickness was measured, and the patterned substrate was baked (Hardbake, HB) on a hot plate at 230C for 5 minutes to complete pattern formation.

After coating was performed at an rpm that could produce a certain thickness for each sample on the substrate on which the green pattern was formed, SB was performed on a 100C hot plate, and the thickness of the area where only Blue PR was coated was measured using TENCOR equipment. Afterwards, the surface profile of the area surrounding the 1.4um pattern was measured using Park Systems' AFM (Atomic Force Microscopy) equipment. When the line profile is measured along the cross section passing through the green pattern using surface profile data acquired through AFM equipment, the ΔY (nm) value of the highest and lowest parts becomes the step difference between the green pattern and the blue resin film.

The ΔY (nm) value is the same as the step according to Equation 1 described above.

Evaluation 1: Binder Effect of weight ratio of resin/photopolymerizable compound

First, look at Reference Examples 1 to 5 to determine the effect of the weight ratio of binder resin/photopolymerizable compound.

	Binder resin/light polymerization monomer weight ratio	binder resin		1st photopolymerization monomer		Second photopolymerization monomer		1st/2nd photopolymerizability monomer weight ratio
		Mw (g/mol)	Sanga (KOHmg/g)	Number of functional groups	viscosity (cps)	Number of functional groups	viscosity (cps)
Reference example 1	0/100	9000	34	6 sensuality	5500 ~8000	-	-	-
Reference example 2	20/80	9000	34	6 sensuality	5500~8000	-	-	-
Reference example 3	50/50	9000	34	6 sensuality	5500~8000	-	-	-
Reference example 4	60/40	9000	34	6 sensuality	5500~8000	-	-	-
Reference example 5	70/30	9000	34	6 sensuality	5500~8000	-	-	-

	Resin film thickness (㎚)	Pattern and resin film level difference (Equation 1)
Reference example 1	4600	1733
Reference example 2	4598	1633
Reference example 3	4465	1421
Reference example 4	4600	1312
Reference example 5	4450	1067

According to Tables 4 and 5, it can be seen that the pattern and resin film level differ depending on the weight ratio of the binder resin/photopolymerizable compound. Specifically, when other conditions, such as the type of binder resin and the type of photopolymerizable compound, are the same, it can be seen that as the weight ratio of binder resin/photopolymerizable compound increases, the level difference between the pattern and the resin film decreases.

Evaluation 2: Effect of weight average molecular weight of binder resin

To determine the effect of the weight average molecular weight of the binder resin, look at Reference Examples 3 and 6 to 8.

	Binder resin/light polymerization monomer weight ratio	binder resin		1st photopolymerization monomer		Second photopolymerization monomer		1st/2nd photopolymerization monomer weight ratio
		Mw (g/mol)	Sanga (KOHmg/g)	Number of functional groups	viscosity (cps)	Number of functional groups	viscosity (cps)
Reference example 6	50/50	4000	38	6 sensuality	5500 ~8000	-	-	-
Reference example 7	50/50	6000	90	6 sensuality	5500~8000	-	-	-
Reference example 3	50/50	9000	34	6 sensuality	5500~8000	-	-	-
Reference example 8	50/50	13000	35	6 sensuality	5500~8000	-	-	-

	Resin film thickness (㎚)	Pattern and resin film level difference (Equation 1)
Reference example 6	4421	1054
Reference example 7	4598	1115
Reference example 3	4465	1421
Reference example 8	4450	1480

According to Tables 6 and 7 above, it can be seen that the pattern and resin film level differ depending on the weight average molecular weight of the binder resin. Specifically, when other conditions such as the weight ratio of binder resin/photopolymerizable compound and the type of photopolymerizable compound are the same, it can be seen that as the molecular weight of the binder increases, the difference between the pattern and the resin film decreases.

Evaluation 3: Effect of adding bifunctional or tetrafunctional photopolymerizable compounds

In order to determine the effect of adding a bifunctional or tetrafunctional photopolymerizable compound, Reference Examples 9 to 12 are examined.

	Binder resin/light polymerization monomer weight ratio	binder resin		1st photopolymerization monomer		Second photopolymerization monomer		First/second photopolymerizable compound weight ratio
		Mw (g/mol)	Sanga (KOHmg/g)	Number of functional groups	viscosity (cps)	Number of functional groups	viscosity (cps)
Reference example 9	50/50	9000	34	6 sensuality	5500 ~8000	2sensuality	600~700	75/25
Reference example 10	50/50	9000	34	6 sensuality	5500~8000	2sensuality	600~700	50/50
Reference example 11	50/50	9000	34	6 sensuality	5500~8000	2sensuality	700	50/50
Reference example 12	50/50	9000	34	6 sensuality	5500~8000	4 sensuality	230	50/50

	Resin film thickness (㎚)	Pattern and resin film level difference (Equation 1)
Reference example 9	4481	1324
Reference example 10	4454	1223
Reference example 11	4570	1193
Reference example 12	4469	1431

According to Tables 8 and 9, it can be seen that the pattern and resin film level difference change depending on the addition of the difunctional photopolymerizable compound or the tetrafunctional photopolymerizable compound. Specifically, when other conditions such as the weight ratio of binder resin/photopolymerizable compound, type of binder resin, and type of hexafunctional photopolymerizable compound are the same, the pattern and It can be seen that the resin film level difference is lowered. Furthermore, when adding a bifunctional photopolymerizable compound rather than a tetrafunctional photopolymerizable compound, the step between the pattern and the resin film is further lowered to less than 1350 Å.

Evaluation 4: Impact of changing the type of hexafunctional photopolymerizable compound

To determine the effect of changing the type of hexafunctional photopolymerizable compound, look at Reference Examples 13 to 15.

	Binder resin/light polymerization monomer weight ratio	binder resin		1st photopolymerization monomer		Second photopolymerization monomer		First/second photopolymerizable compound weight ratio
		Mw (g/mol)	Sanga (KOHmg/g)	Number of functional groups	viscosity (cps)	Number of functional groups	viscosity (cps)
Reference example 13	50/50	9000	34	6 sensuality	6950	2sensuality	600 ~700	50/50
Reference example 14	50/50	9000	34	6 sensuality	900~2000	2sensuality	600~700	50/50
Reference example 15	50/50	9000	34	6 sensuality	390	2sensuality	600~700	50/50

	Resin film thickness (㎚)	Pattern and resin film level difference (Equation 1)
Reference example 13	4572	1200
Reference example 14	4571	1360
Reference example 15	4595	1324

According to Tables 10 and 11, it can be seen that the pattern and resin film level difference change depending on the type of hexafunctional photopolymerizable compound. Specifically, when other conditions such as the weight ratio of binder resin/photopolymerizable compound, type of binder resin, and type and addition amount of difunctional photopolymerizable compound are the same, the pattern and resin are changed by changing the type of hexafunctional photopolymerizable compound. It can be seen that the level difference is lowered.

(Example)

Preparation of photosensitive resin composition

Photosensitive resin compositions according to Examples 1 to 4 were prepared by mixing the compositions shown in Table 12 below.

Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, then a binder resin, photopolymerizable compound and additives were added thereto and stirred at room temperature for 60 minutes. Then, the pigment dispersion as a colorant was added to the obtained reaction product and stirred at room temperature for 30 minutes. Then, the product was filtered twice to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%)

		Solid content (% by weight)	Example 1	Example 2	Example 3	Example 4
(A) Binder resin	A-1	38.5	-	-	-	-
	A-2	37.8	4.571	5.333	5.333	5.333
	A-3	39.3	-	-	-	-
	A-4	38.8	-	-	-	-
(B) Photopolymerizable compound	B-1	100	1.152	0.864	0.648	0.432
	B-2	100	-	-	0.216	0.432
	B-3	100	-	-	-	-
	B-4	100	-	-	-	-
	B-5	100	-	-	-	-
	B-6	100	-	-	-	-
	B-7	100	-	-	-	-
Binder resin/photopolymerizable compound weight ratio		-	0/100	60/40	70/30	70/30
(C) Photopolymerization initiator	C-1	100	0.547	0.547	0.547	0.547
(D) Colorant	D-1	18.04	43.234	43.234	43.234	43.234
(E) Solvent	E-1	-	14.702	14.228	14.228	14.228
	E-2	-	26.580	26.580	26.580	26.580
	E-3	-	8.860	8.860	8.860	8.860
(F) Additives	F-1	One	0.044	0.044	0.044	0.044
	F-2	10	0.200	0.200	0.200	0.200
	F-3	100	0.109	0.109	0.109	0.109

The materials used in Table 12 are as described above.

Assessment 5: Multi-factorial impact

Examples 1 to 4 were evaluated in the same manner as described above.

	Binder resin/light polymerization monomer weight ratio	binder resin		1st photopolymerization monomer		Second photopolymerization monomer		1st/2nd photopolymerizability monomer weight ratio
		Mw (g/mol)	Sanga (KOHmg/g)	Number of functional groups	viscosity (cps)	Number of functional groups	viscosity (cps)
Example 1	60/40	4000	38	6 sensuality	5500 ~8000	-	-	-
Example 2	70/30	4000	38	6 sensuality	5500~8000	-	-	-
Example 3	70/30	4000	38	6 sensuality	5500~8000	2sensuality	600 ~700	75/25
Example 4	70/30	4000	38	6 sensuality	5500~8000	2sensuality	600~700	50/50

	Resin film thickness (㎚)	Pattern and resin film level difference (Equation 1)
Example 1	4555	990
Example 2	4450	952
Example 3	4474	943
Example 4	4592	915

According to Tables 13 and 14, it can be seen that Examples 1 to 4 significantly reduced the step between the pattern and the resin film to 1,000 Å or less by comprehensively considering multiple factors. Specifically, the binder resin/photopolymerizable compound As the weight ratio becomes larger in the range of 60/40 or more, and as the weight average molecular weight of the binder resin decreases closer to 4,000 g/mol in the range of 9,000 g/mol or less, the hexafunctional photopolymerizable compound is necessarily included, but the bifunctional As the photopolymerizable compound is added and the amount added is controlled closer to 50/50, the difference between the pattern and the resin film is significantly lowered to 1,000 Å or less.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and this also applies to the present invention. It is natural that it falls within the scope of the invention.

Claims (14)

1. (A) Binder resin;

   (B) photopolymerizable compound;

   (C) photopolymerization initiator;

   (D) colorant; and

   (E) Solvent

   Including;

   The weight ratio of the binder resin to the photopolymerizable compound (binder resin/photopolymerizable compound) is 60/40 or more;

   The weight average molecular weight of the binder resin is 4,000 g/mol to 9,000 g/mol;

   The photosensitive resin composition in which the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound and a bifunctional photopolymerizable compound.
2. According to paragraph 1,

   When forming a photosensitive resin film using the photosensitive resin composition on a patterned substrate, the photosensitive resin composition has a step difference of 1,000 Å or less according to Equation 1 below:

   [Equation 1]

   (step difference)=A+B-C

   In Equation 1 above,

   A is the pattern height of the patterned substrate,

   B is the maximum height of the photosensitive resin film formed in the patterned area of the patterned substrate,

   C is the minimum height of the photosensitive resin film formed in the area where the pattern of the patterned substrate does not exist.
3. According to paragraph 2,

   The colorant is a photosensitive resin composition comprising a blue pigment, a purple pigment, or a combination thereof.
4. According to paragraph 2,

   The photosensitive resin film is blue, and the pattern of the substrate is green.
5. According to paragraph 1,

   The photosensitive resin composition wherein the binder resin has an acid value of 30 KOHmg/g to 100 KOHmg/g.
6. According to paragraph 1,

   A photosensitive resin composition wherein the binder resin is a hydrophobic acrylic binder resin.
7. According to paragraph 1,

   A photosensitive resin composition wherein the hexafunctional photopolymerizable compound has a viscosity of 5,500 to 8,000 cps at 25°C.
8. According to paragraph 1,

   A photosensitive resin composition wherein the bifunctional photopolymerizable compound has a viscosity of 600 to 700 cps at 25°C.
9. According to paragraph 1,

   The solvent is propylene glycol monomethyl ether acetate (PGMEA), n-Butyl Acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof. A photosensitive resin composition comprising:
10. According to paragraph 1,

    The photosensitive resin composition is, with respect to the total amount of the photosensitive resin composition,

    (A) 0.5% to 15% by weight of binder resin;

    0.1% to 10% by weight of the (B) photopolymerizable compound;

    (C) 0.1% to 10% by weight of photopolymerization initiator;

    0.5% to 15% by weight of the (D) colorant; and

    (E) residual amount of solvent

    A photosensitive resin composition containing a.
11. According to paragraph 1,

    The photosensitive resin composition further contains malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent containing a vinyl group or (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. A photosensitive resin composition comprising:
12. A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 11.
13. A color filter comprising the photosensitive resin film of claim 12.
14. A CMOS image sensor including the color filter of claim 13.

Images