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

Abstract

The present invention relates to a photosensitive resin composition, a photosensitive resin film produced using the 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, in which 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

[Technical field]

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive resin film produced using the same, and a color filter. [Background technology]

[0002] 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 including color filters, photodiodes, and amplifiers.

[0003] Recently, CIS for mobile devices is required to have more pixels and more cameras, and the demand for thinner and smaller image sensors is increasing. To meet this demand, photosensitive resin compositions (Photoresist, PR) for CIS color filters need to realize smaller pixels while forming fine patterns.

[0004] However, as the size of the pixels that make up the color filters for CIS becomes smaller, the signal-to-noise ratio (SNR) becomes a major issue. The driving method of CIS is that external light passes through the color filter and the passed light is converted into an electrical signal via a photodiode, so a decrease in pixel size means a decrease in the amount of light incident on each pixel. In addition, as the pixel size decreases, the distance between pixels also becomes shorter, so the light that passes through adjacent pixels can act as noise.

[0005] In general, among the red, green, and blue photosensitive resin compositions constituting the color filter of a CIS device, the green photosensitive resin composition is applied first to form a pattern, and then the blue or red photosensitive resin composition is applied thereon, and finally the red or blue photosensitive resin composition is applied to form a pattern. At this time, since the red or blue photosensitive resin composition is applied between the uneven pattern formed by the lower green photosensitive resin composition, the degree of filling the gap between the patterns varies depending on the flow characteristics of the composition, and in fact, the thickness difference between the red or blue composition patterns formed between the green composition patterns may be large. The larger the thickness g, the darker the color, and the smaller the thickness g, the lighter the color, so the thickness is an important factor in forming a signal of the color indicated by the pattern, and the uniformity of the thickness of the pattern plays a decisive role in driving the CIS device.

[0006] In relation to this, after manufacturing the CIS device, it is necessary to check the SNR characteristics and ensure that not only is the SNR of the chip that constitutes one pixel high, but also that the SNR variation (Spatial SNR, S.SNR) of the chips present on the entire substrate is uniform. Summary of the Invention [Problem to be solved by the invention]

[0007] One embodiment is to provide a photosensitive resin composition that has a small step between a pattern and a resin film when a photosensitive resin film is formed on a patterned substrate, for the purpose of improving the SNR variation (S.SNR) of a CIS.

[0008] Another embodiment provides a photosensitive resin film produced using the photosensitive resin composition.

[0009] Another embodiment provides a color filter manufactured using the photosensitive resin film. [Means for solving the problem]

[0010] One embodiment provides a photosensitive resin composition comprising (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, in which a weight ratio of the binder resin to the photopolymerizable compound (binder resin / photopolymerizable compound) is 60 / 40 or more, the binder resin has a weight average molecular weight of 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.

[0011] When a photosensitive resin film is formed on a patterned substrate using the photosensitive resin composition, the step height according to the following Equation 1 may be 1,000 Å or less. [Formula 1] (Step)=A+BC

[0012] In the above formula 1, A is the pattern height of the patterned substrate, B is the maximum height of the photosensitive resin film formed in the patterned region of the patterned substrate, and C is the minimum height of the photosensitive resin film formed in the patterned region of the patterned substrate where no pattern is present.

[0013] The colorant may include a blue pigment, a violet pigment, or a combination thereof.

[0014] The photosensitive resin film may be blue and the pattern on the substrate may be green.

[0015] The acid value of the binder resin may be 30 KOHmg / g to 100 KOHmg / g.

[0016] The binder resin may be a hydrophobic acrylic binder resin.

[0017] The viscosity of the hexafunctional photopolymerizable compound at 25° C. may be 5,500 to 8,000 cps.

[0018] The bifunctional photopolymerizable compound may have a viscosity at 25° C. of 600 to 700 cps.

[0019] The solvent may include propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof.

[0020] The photosensitive resin composition may contain, relative to the total amount of the photosensitive resin composition, 0.5% by weight to 15% by weight of the (A) binder resin, 0.1% by weight to 10% by weight of the (B) photopolymerizable compound, 0.1% by weight to 10% by weight of the (C) photopolymerization initiator, 0.5% by weight to 15% by weight of the colorant, and the balance being the (E) solvent.

[0021] The photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

[0022] Another embodiment provides a photosensitive resin film produced using the photosensitive resin composition.

[0023] In still another embodiment, there is provided a color filter including the photosensitive resin film.

[0024] Yet another embodiment provides a CMOS image sensor including the color filter.

[0025] Further details of other aspects of the present invention are included in the following detailed description. Effect of the Invention

[0026] By forming a photosensitive resin film on a patterned substrate using a photosensitive resin composition according to one embodiment, the step between the pattern and the resin film is small, thereby improving the SNR variation (S.SNR) of the CIS. [Brief description of the drawings]

[0027] [Figure 1] 1A and 1B are schematic diagrams for explaining a step between a pattern and a resin film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail, but are given by way of example only and are not intended to limit the present invention, which is defined only by the scope of the claims that follow.

[0029] Unless otherwise specified in this specification, "substitution" means that at least one hydrogen atom in the compound is replaced with a halogen atom (F, Cl, Br, I), a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amine group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. It means that the alkyl group is substituted with an alkyl group having from 2 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms, an aryl group having from 6 to 30 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, a cycloalkenyl group having from 3 to 20 carbon atoms, a cycloalkynyl group having from 3 to 20 carbon atoms, a heterocycloalkyl group having from 2 to 20 carbon atoms, a heterocycloalkenyl group having from 2 to 20 carbon atoms, a heterocycloalkynyl group having from 2 to 20 carbon atoms, or a combination thereof.

[0030] Unless otherwise specified in this specification, the terms "heterocycloalkyl group," "heterocycloalkenyl group," "heterocycloalkynyl group," and "heterocycloalkylene group" mean that at least one N, O, S, or P heteroatom is present in the ring system of a cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene, respectively.

[0031] Unless otherwise specified in this specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0032] Unless otherwise defined herein, "combination" means blending or copolymerization, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization and random copolymerization.

[0033] Unless otherwise defined in a chemical formula herein, when no chemical bond is drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded to that position.

[0034] Additionally, unless otherwise defined in this specification, "*" means a moiety connected to the same or different atoms or chemical formulae.

[0035] (Photosensitive resin composition) One embodiment provides a photosensitive resin composition that reduces the step between a pattern and a resin film when a photosensitive resin film is formed on a patterned substrate for the purpose of improving the SNR variation (S.SNR) of a CIS.

[0036] Specifically, Fig. 1 is a schematic diagram for explaining the step between the pattern and the resin film. When a photosensitive resin film is formed on a patterned substrate, a difference occurs between the height (A+B) corresponding to the sum of the substrate pattern height (A) and the maximum height (B) of the photosensitive resin film formed in the region of the substrate where the pattern exists, and the minimum height (C) of the photosensitive resin film formed in the region of the substrate where the pattern does not exist.

[0037] The step between the pattern and the resin film is influenced by the types and ratios of transparent materials that contribute to pattern formability, such as binder resin, photopolymerizable compound, and solvent, rather than by pigments that are directly linked to color.

[0038] In relation to this, one embodiment provides a photosensitive resin composition comprising (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, in which a 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.

[0039] The photosensitive resin film may be blue and the pattern on the substrate may be green.

[0040] The colorant may include a blue pigment, a violet pigment, or a combination thereof, and such colorant may be used to produce a blue photosensitive resin film.

[0041] When a photosensitive resin film is formed on a patterned substrate using the photosensitive resin composition, the step height according to the following Equation 1 may be 1,000 Å or less: [Formula 1] (Step)=A+BC

[0042] In the above formula 1, A is the pattern height of the patterned substrate, B is the maximum height of the photosensitive resin film formed in the patterned region of the patterned substrate, and C is the minimum height of the photosensitive resin film formed in the patterned region of the patterned substrate where no pattern is present.

[0043] In the experiment, coating was performed on the substrate with the pattern at a rotation speed that could produce a consistent thickness for each sample, then SB was performed on a hot plate at 100°C, and the thickness of the area coated with PR only was measured using a TENCOR device. The surface profile was then measured using Park System's AFM (Atomic Force Microscopy) device for the area around the 1.4μm pattern. When the line profile was measured along the cross section passing through the pattern through the surface profile data acquired using the AFM device, the ΔY (nm) value of the highest and lowest points was the step difference between the pattern and the resin film.

[0044] The ΔY (nm) value is the same as the step height according to Equation 1 above.

[0045] As mentioned above, the thicker the thickness, the darker the color, and the thinner the thickness, the lighter the color. Therefore, the thickness uniformity of the pattern plays a crucial role in the operation of a CMOS image sensor (CIS), as it is an important factor in forming a signal of the color indicated by the pattern.

[0046] In the photosensitive resin composition of the embodiment, the step height calculated by Equation 1 can be controlled 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 adjusting the multiple factors.

[0047] In particular, the larger the weight ratio of the binder resin / photopolymerizable compound is within the range of 60 / 40 or more, the smaller the weight average molecular weight of the binder resin is within the range of 9,000 g / mol or less and approaches 4,000 g / mol, and the more the hexafunctional photopolymerizable compound is essentially contained and a bifunctional photopolymerizable compound is added and the amount of the added compound is controlled to be closer to 50 / 50, the smaller the step calculated by Equation 1 becomes.

[0048] The factors that affect the step will be described below.

[0049] SNR can be improved by adjusting the transmission spectrum of the pigment or dye in the visible light region. The overlapping region of the transmission spectra of the red, green, and blue colors that make up the color filter is called crosstalk, which can act as noise in different colors, so it is important to design the transmission spectrum to minimize this. Crosstalk can be improved by mixing yellow pigments in the case of red and green, and violet pigments in the case of blue.

[0050] In addition to the transmission spectrum, there are other ways to improve light efficiency through surface properties. When a photosensitive resin composition forms a fine pattern, surface roughness can affect SNR, and after it is applied onto a silicon wafer, thickness deviation between the corners and center of the wafer, and the occurrence of spots and striations can affect S.SNR. This can be improved by changing the type, ratio, and content of resins, monomers, solvents, additives, etc., which are transparent materials that contribute to pattern formation rather than pigments directly linked to color.

[0051] Weight ratio of binder resin / photopolymerizable compound In one embodiment, the greater the weight ratio of the binder resin / photopolymerizable compound is within a range of 60 / 40 or more, the smaller the step calculated by Equation 1 becomes.

[0052] Specifically, the weight ratio of the binder resin to the photopolymerizable compound may be 60 / 40 or more, or 70 / 30 or more, and may be less than 100 / 1.

[0053] (A) Binder resin In one embodiment, the weight average molecular weight of the binder resin is in the range of 9,000 g / mol or less and closer to 4,000 g / mol, so that the step calculated by Equation 1 is smaller.

[0054] Specifically, the weight average molecular weight of the binder resin may be 4,000 g / mol or more and 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.

[0055] When the weight average molecular weight of the binder resin is within the above range, the binder resin has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

[0056] 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.

[0057] The binder resin may be a hydrophobic acrylic binder resin.

[0058] The binder resin may be a copolymer of 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.

[0059] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0060] The first ethylenically unsaturated monomer may be contained 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.

[0061] Examples of the second ethylenically unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, and vinyl benzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; cyanide vinyl compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These may be used alone or in combination of two or more.

[0062] Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but are not limited thereto. These may be used alone or in combination of two or more kinds.

[0063] 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 included in the above range, the color filter can be produced with excellent developability and improved crosslinking properties, resulting in excellent surface smoothness.

[0064] (B) Photopolymerizable compound In one embodiment, the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound (first photopolymerizable compound) and a difunctional photopolymerizable compound (second photopolymerizable compound).

[0065] The more the bifunctional photopolymerizable compound is added and the amount of the compound added is controlled so as to be closer to 50 / 50, the lower the step calculated by the formula 1 becomes.

[0066] Specifically, when the bifunctional photopolymerizable compound (second photopolymerizable compound) is added, the weight ratio of the first / second photopolymerizable compound may be 50 / 50 or more and 75 / 25 or less.

[0067] The functional groups contained in each of the hexafunctional photopolymerizable compound and the difunctional photopolymerizable compound may be (meth)acrylate groups.

[0068] The hexafunctional photopolymerizable compound may be dipentaerythritol hexaacrylate (DPHA) represented by the following chemical formula and having a viscosity at 25° C. of 5,500 cps to 8,000 cps.

[0069] [ka]

[0070] The bifunctional photopolymerizable compound may be BPA(EO)10DA Bisphenol A(EO)10 Diacrylate, which is represented by the following chemical formula and has a viscosity of 600 cps to 700 cps at 25°C.

[0071] [ka]

[0072] In the above chemical formula, m+n=10.

[0073] The photopolymerizable compound may be contained 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 contained within the above range, curing upon exposure occurs sufficiently in the pattern formation step, and the obtained pattern has excellent reliability and excellent developability in an alkaline developer.

[0074] (C) Photopolymerization initiator The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, and may be, 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.

[0075] Examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0076] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0077] Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0078] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0079] 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, azine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-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.

[0080] 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, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-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.

[0081] As the photopolymerization initiator, in addition to the above compounds, carbazole-based compounds, diketone compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, fluorene-based compounds, and the like can be used.

[0082] The photoinitiator may be used in conjunction with a photosensitizer, which absorbs light, becomes excited, and then transfers the energy to initiate a chemical reaction.

[0083] Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0084] The photopolymerization initiator may be contained 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 contained within the above range, curing upon exposure occurs sufficiently in the pattern formation process, and the obtained pattern can have excellent reliability, and the pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiator can be prevented.

[0085] (D) Coloring agent In one embodiment, the colorant may include a blue pigment, a violet pigment, or a combination thereof.

[0086] Examples of the blue pigment include copper phthalocyanine pigments such as CI Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3, CI Blue Pigment 15:4, CI Blue Pigment 15:5, CI Blue Pigment 16, and the like.

[0087] Examples of the purple pigment include CI Violet Pigment 1, CI Violet Pigment 19, CI Violet Pigment 23, CI Violet Pigment 27, CI Violet Pigment 28, CI Violet Pigment 29, CI Violet Pigment 30, CI Violet Pigment 32, CI Violet Pigment 37, CI Violet Pigment 40, CI Violet Pigment 42, CI Violet Pigment 50, or combinations thereof.

[0088] In addition, red pigments, green pigments, yellow pigments, black pigments, etc. may be further included.

[0089] Examples of the red pigment include CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, and the like.

[0090] Examples of the green pigment include CI Green Pigment 7, CI Green Pigment 36, CI Green Pigment 58, CI Green Pigment 59, and the like.

[0091] Examples of the yellow pigment include isoindoline pigments such as CI Yellow Pigment 139, quinophthalone pigments such as CI Yellow Pigment 138, nickel complex pigments such as CI Yellow Pigment 150, and the like.

[0092] Examples of the black pigment include aniline black, perylene black, titanium black, carbon black, etc. The pigment may be used alone or in combination of two or more. For example, the pigment may be a yellow pigment, a green pigment, or a mixture thereof.

[0093] The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion liquid. Such a pigment dispersion liquid may be composed of the pigment, a solvent, a dispersant, a dispersion resin, and the like.

[0094] The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like. Among these, propylene glycol methyl ether acetate is preferred.

[0095] The dispersant promotes uniform dispersion of the pigment in the dispersion liquid, and nonionic, anionic, or cationic dispersants can 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, alkylamide alkylene oxide adduct, alkylamine, etc. can be used alone or in combination of two or more kinds.

[0096] The dispersing resin may be an acrylic resin containing a carboxyl group, which can improve not only the stability of the pigment dispersion liquid but also the patternability of the pixels.

[0097] The colorant may further include an organic solvent soluble dye.

[0098] Examples of the organic solvent-soluble dye include triarylmethane compounds, anthraquinone compounds, benzylidene compounds, xanthene compounds, phthalocyanine compounds, azaporphyrin compounds, and indigo compounds.

[0099] 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 within this weight ratio range, chemical resistance, durability, and maximum absorption wavelength can be controlled within appropriate ranges, and high brightness and light-dark ratio can be achieved with desired color coordinates.

[0100] The colorant may be contained in an amount of 0.5% by weight to 15% by weight, for example, 1% by weight to 10% by weight, based on the total amount of the photosensitive resin composition of the embodiment. When the colorant is contained within the above range, the pattern has excellent color reproduction, curability, and adhesion.

[0101] (E) Solvent As the solvent, a substance that is compatible with but does not react with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator can be used.

[0102] Examples of the solvent include alcohols such as methanol and ethanol, ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl 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, 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, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl ethyl ... ketones such as methyl n-butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters such as methyl lactate and ethyl lactate; oxyacetate alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetate alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxypropionate methyl; 3-oxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, 3-alkoxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate,2-alkoxypropionic acid alkyl esters such as methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0103] Among these, in consideration of compatibility and reactivity, propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof can be used as the solvent.

[0104] The solvent may be contained in an amount of, 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 coatability, and a coating film with excellent flatness can be obtained.

[0105] (F) Other additives The photosensitive resin composition may further include at least one additive selected from malonic acid, 3-amino-1,2-propanediol, a coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, and a radical polymerization initiator in order to prevent spots and spots during application, improve leveling performance, and prevent the generation of residues due to undevelopment.

[0106] The additives can be easily adjusted according to the desired physical properties.

[0107] The coupling agent may be a silane-based coupling agent. Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, gamma methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, gamma isocyanate propyl triethoxysilane, gamma glycidoxypropyl trimethoxysilane, and beta epoxycyclohexyl)ethyl trimethoxysilane. These may be used alone or in combination of two or more.

[0108] Specifically, the silane coupling agent can be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

[0109] In addition, the photosensitive resin composition for color filters may further include a surfactant, for example, a fluorine-based surfactant, if necessary.

[0110] Examples of the fluorosurfactant include F-482, F-484, F-478, etc., manufactured by DIC Corporation, but are not limited thereto.

[0111] The surfactant is preferably contained in an amount of 0.01% by weight to 5% by weight, more preferably 0.01% by weight to 2% by weight, based on the total amount of the photosensitive resin composition. If the amount is outside the above range, a problem of foreign matter being generated after development may occur, which is undesirable.

[0112] The photosensitive resin composition may contain other additives such as antioxidants and stabilizers in a certain amount within a range that does not impair the physical properties.

[0113] (Photosensitive resin film) According to another embodiment, there is provided a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment.

[0114] The method for producing the photosensitive resin film is as follows.

[0115] The above-mentioned photosensitive resin composition is applied onto a glass substrate by a suitable method such as spin coating, roller coating, or spray coating to a thickness of, for example, 0.5 um to 10 um to form a photosensitive resin composition layer.

[0116] The photosensitive resin composition layer can be converted into a photosensitive resin film by baking at 80 to 100°C for 170 to 190 seconds using a hot plate, exposing to light at a power of 450 to 470 mJ using an exposure device, and then baking at 210 to 250°C for 3 to 10 minutes.

[0117] The photosensitive resin film may have a transmittance of 85% or more, specifically 97% or more, for example 90% or more, in the wavelength range of 480 to 620 nm. The photosensitive resin film may have a transmittance of 15% or less, specifically 13% or less, for example 10% or less, in the wavelength range of less than 480 nm and in the wavelength range of more than 620 nm.

[0118] The photosensitive resin film can have a small thickness while reaching the above-mentioned spectroscopic target. Specifically, the thickness of the photosensitive resin film can 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.

[0119] (Color filter) According to another embodiment, there is provided a color filter produced using the above-mentioned photosensitive resin composition.

[0120] The color filter is manufactured in the following manner.

[0121] The above-mentioned photosensitive resin composition is applied onto a glass substrate using an appropriate method such as spin coating, roller coating, or spray coating to a thickness of, for example, 0.5 um to 10 um to form a photosensitive resin composition layer.

[0122] Next, the substrate on which the photosensitive resin composition layer is formed is irradiated with light so as to form a pattern required for a color filter. The light used for irradiation can be UV, electron beams or X-rays, and for example, UV in the range of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. The irradiating step can also be performed using a photoresist mask. After performing the irradiating step in this manner, the photosensitive resin composition layer irradiated with light is treated with a developer.

[0123] At this time, the non-exposed parts of the photosensitive resin composition layer dissolve, forming a pattern required for the color filter. This process is repeated according to the number of colors required to obtain a color filter having a desired pattern. In addition, if the image pattern obtained by development in the above process is cured by heating or exposure to actinic radiation, the crack resistance, solvent resistance, etc. can be improved.

[0124] According to another embodiment, there is provided a CMOS image sensor including the color filter described above. EXAMPLES

[0125] The present invention will be described in more detail below with reference to examples. However, the following examples are merely preferred examples of the present invention, and the present invention is not limited to the following examples.

[0126] (Reference example) Preparation of photosensitive resin composition Various materials were mixed according to the compositions shown in the following Tables 1 to 3 to prepare photosensitive resin compositions according to Reference Examples 1 to 15.

[0127] Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, and then the binder resin, photopolymerizable compound, and additives were added thereto and stirred at room temperature for 60 minutes. Next, a pigment dispersion was added as a colorant to the reaction product obtained and stirred at room temperature for 30 minutes. Next, the product was filtered twice to remove impurities, thereby preparing a photosensitive resin composition (solid content: 11.4 wt%).

[0128] [Table 1]

[0129] [Table 2]

[0130] [Table 3]

[0131] The substances listed in Tables 1 to 3 above are as follows. (A) Binder resin (A-1) Hydrophobic acrylic binder resin 1 (acid value: 34 KOH mg / 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 KOH mg / 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 KOH mg / 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 KOH mg / g, molecular weight: 13,000 g / mol, double bond equivalent: 330 g / mol, product name: RY-92-M15, manufacturer: Showadenko)

[0132] (B) Photopolymerizable compound (B-1) Hexafunctional photopolymerizable compound 1 represented by the following chemical formula (viscosity: 5500-8000cps@25°C, substance name: dipentaerythritol hexaacrylate (DPHA), manufacturer: Nippon Kayaku)

[0133] [ka]

[0134] (B-2) Bifunctional photopolymerizable compound 1 represented by the following chemical formula (viscosity: 600-700cps@25℃, substance name: BPA(EO)10DA Bisphenol A(EO)10 Diacrylate, product name: M2100, manufacturer: Bigen Shoji)

[0135] [ka]

[0136] In the above chemical formula, m+n=10.

[0137] (B-3) Hexafunctional photopolymerizable compound 2 represented by the following chemical formula (viscosity: 6950cps@25℃, substance name: Di-pentaerythritol Polyacrylate, product name: A-9550, manufacturer: Shin-Nakamura)

[0138] [ka]

[0139] In the above chemical formula, R is a hydrogen atom or *-(C=O)CH=CH2.

[0140] (B-4) Hexafunctional photopolymerizable compound 3 represented by the following chemical formula (viscosity: 900 to 2000 cps @ 25°C, product name: DPCA60, manufacturer: Nippon Kayaku)

[0141] [ka]

[0142] (B-5) Hexafunctional photopolymerizable compound 4 (viscosity: 390 cps@25℃, product name: A-DPH-6E, manufacturing company: Shin Nakamura)

[0143] [ka]

[0144] In the above chemical formula, a+b+c+d+e+f=6.

[0145] (B-6) Difunctional photopolymerizable compound 2 (viscosity: 600~700cps@25℃, substance name: Ethoxylated bisphenol A diarylate, product name: ABPE-20, manufacturing company: Shin Nakamura)

[0146] [ka]

[0147] In the above chemical formula, m+n=2.

[0148] (B-7) Tetrafunctional photopolymerizable compound (viscosity: 230cps@25℃, substance name: ethoxylated diglycerin tetraacrylate, product name: DGE4A, manufacturer: Kyoeisha)

[0149] [ka]

[0150] In the above chemical formula, a+b+c+d=4.

[0151] (C) Photopolymerization initiator (C-1) Oxime-based initiator (OXE-01 type, product name: SPI03, manufacturer: Samyangsha)

[0152] (D) Coloring agent (D-1) Pigment dispersion mixed in a ratio of Blue Pigment B15:6 / Violet Pigment V23=77 / 23 (Product name: BA1442, Manufacturer: Sanyo)

[0153] (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)

[0154] (F) Additives (F-1) Antioxidant 4-Methoxyphenol (MHQ, Manufacturer: Weifang TongRun Chem) (F-2) Fluorosurfactant (F-556, manufacturer: DIC) (F-3) Silane coupling agent (KBM-503, manufacturer: ShinEtsu)

[0155] (Evaluation method) A photosensitive resin film was formed on a patterned substrate using each of the photosensitive resin compositions according to Reference Examples 1 to 15, and the step between the pattern and the resin film and the SNR were evaluated. The specific evaluation method was as follows.

[0156] (1) Method of evaluating the step between the pattern and the resin film: First, Green PR was coated on an 8-inch silicon wafer substrate that had been surface-treated with an APL solution using MIKASA's coating equipment so that it could show a thickness of 4500A. After soft-baking (SB) on a hot plate at 100°C, pattern exposure was performed on an i-line stepper under exposure conditions of dose 600ms / Focus: -0.2um. The thickness was measured using a TENCOR device in the exposure process, and development was performed to show the pattern. A TMAH solution was used as the developer, and the time (seconds) at which the pattern was shown (BP) was measured. At this time, BP was about 5 seconds or less. After development and water washing processes, the pattern thickness was measured, and the pattern substrate was hard-baked (HB) on a hot plate at 230°C for 5 minutes to complete the pattern formation.

[0157] After coating at a rotation speed that can produce a consistent thickness for each sample on the substrate with the green pattern formed, SB was performed on a hot plate at 100°C, and the thickness of the area coated with only Blue PR was measured using a TENCOR device. The surface profile was then measured using an AFM (Atomic Force Microscopy) device from Park System for the area around the 1.4um pattern. When the line profile was measured along the cross section passing through the green pattern using the surface profile data obtained using the AFM device, the ΔY (nm) value of the highest and lowest points was the step difference between the green pattern and the blue resin film.

[0158] The ΔY (nm) value is the same as the step height according to Equation 1 above.

[0159] Evaluation 1: Effect of the weight ratio of binder resin / photopolymerizable compound First, in order to confirm the influence of the weight ratio of binder resin / photopolymerizable compound, Reference Examples 1 to 5 will be referred to.

[0160] [Table 4]

[0161] [Table 5]

[0162] It can be seen from Tables 4 and 5 that the difference in level between the pattern and the resin film varies 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, the difference in level between the pattern and the resin film decreases as the weight ratio of the binder resin / photopolymerizable compound increases.

[0163] Evaluation 2: Effect of weight average molecular weight of binder resin In order to confirm the influence of the weight average molecular weight of the binder resin, Reference Examples 3 and 6 to 8 are referred to.

[0164] [Table 6]

[0165] [Table 7]

[0166] It can be seen from Tables 6 and 7 that the difference in level between the pattern and the resin film varies 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, the difference in level between the pattern and the resin film decreases as the molecular weight of the binder increases.

[0167] Evaluation 3: Effects of adding a bifunctional or tetrafunctional photopolymerizable compound Reference Examples 9 to 12 are referred to in order to confirm the effect of adding a bifunctional photopolymerizable compound or a tetrafunctional photopolymerizable compound.

[0168] [Table 8]

[0169] [Table 9]

[0170] From Tables 8 and 9, it can be seen that the step between the pattern and the resin film changes by adding a bifunctional photopolymerizable compound or a tetrafunctional photopolymerizable compound. Specifically, when other conditions such as the weight ratio of binder resin / photopolymerizable compound, the type of binder resin, and the type of hexafunctional photopolymerizable compound are the same, it can be seen that the step between the pattern and the resin film is reduced by adding a bifunctional photopolymerizable compound or a tetrafunctional photopolymerizable compound. Furthermore, when a bifunctional photopolymerizable compound is added rather than a tetrafunctional photopolymerizable compound, the step between the pattern and the resin film is further reduced to less than 1350 Å.

[0171] Evaluation 4: Effect of changing the type of 6-functional photopolymerizable compound In order to confirm the influence of changing the type of hexafunctional photopolymerizable compound, Reference Examples 13 to 15 are referred to.

[0172] [Table 10]

[0173] [Table 11]

[0174] It can be seen from Tables 10 and 11 that the step between the pattern and the resin film changes when the type of hexafunctional photopolymerizable compound is changed. Specifically, when other conditions such as the weight ratio of binder resin / photopolymerizable compound, the type of binder resin, the type of bifunctional photopolymerizable compound, and the amount added are the same, the step between the pattern and the resin film is reduced when the type of hexafunctional photopolymerizable compound is changed.

[0175] (Example) Preparation of photosensitive resin composition Photosensitive resin compositions according to Examples 1 to 4 were prepared by mixing various materials according to the compositions shown in Table 12 below.

[0176] Specifically, after dissolving the photopolymerization initiator in the solvent, the mixture was stirred at room temperature for 30 minutes, and then the binder resin, the photopolymerizable compound, and the additives were added thereto and stirred at room temperature for 60 minutes. Next, a pigment dispersion was added as a colorant to the reaction product obtained and the mixture was stirred at room temperature for 30 minutes. Next, the product was filtered twice to remove impurities, thereby preparing a photosensitive resin composition.

[0177] [Table 12]

[0178] The materials used in Table 12 above are as described above.

[0179] Rating 5: Multiple factors affect Examples 1 to 4 were evaluated in the same manner as described above.

[0180] [Table 13]

[0181] [Table 14]

[0182] According to Tables 13 and 14, in Examples 1 to 4, by comprehensively considering multiple factors, it can be seen that the step between the pattern and the resin film was significantly reduced to 1,000 Å or less. Specifically, the step between the pattern and the resin film was significantly reduced to 1,000 Å or less as the weight ratio of the binder resin / photopolymerizable compound became larger within the range of 60 / 40 or more, as the weight average molecular weight of the binder resin approached 4,000 g / mol within the range of 9,000 g / mol or less, and as the amount of a bifunctional photopolymerizable compound added while containing a hexafunctional photopolymerizable compound as an essential component was controlled to approach 50 / 50.

[0183] Although the above describes a preferred embodiment of the present invention, the present invention is not limited thereto, and can be embodied in various modified forms within the scope of the claims, the detailed description of the invention, and the accompanying drawings, which of course also fall within the scope of the present invention.

Claims

1. (A) binder resin; (B) photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant; and (E) Solvent Including, a 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, wherein the photopolymerizable compound is a hexafunctional photopolymerizable compound alone or a mixture of a hexafunctional photopolymerizable compound and a difunctional photopolymerizable compound.

2. When a photosensitive resin film is formed on a patterned substrate using the photosensitive resin composition, the step height according to the following Equation 1 is 1,000 Å or less, [Formula 1] (step)=A+B-C In the above formula 1, 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, 2. The photosensitive resin composition according to claim 1, wherein C is the minimum height of the photosensitive resin film formed in a pattern-free area of ​​the patterned substrate.

3. The photosensitive resin composition of claim 2 , wherein the colorant comprises a blue pigment, a violet pigment, or a combination thereof.

4. The photosensitive resin composition according to claim 2 , wherein the photosensitive resin film is blue and the pattern on the substrate is green.

5. 2. The photosensitive resin composition according to claim 1, wherein the binder resin has an acid value of 30 KOHmg / g to 100 KOHmg / g.

6. The photosensitive resin composition according to claim 1 , wherein the binder resin is a hydrophobic acrylic binder resin.

7. 2. The photosensitive resin composition according to claim 1, wherein the viscosity of the hexafunctional photopolymerizable compound at 25° C. is 5,500 to 8,000 cps.

8. 2. The photosensitive resin composition according to claim 1, wherein the bifunctional photopolymerizable compound has a viscosity of 600 to 700 cps at 25°C.

9. 2. The photosensitive resin composition of claim 1, wherein the solvent comprises propylene glycol monomethyl ether acetate, n-butyl acetate, ethylene glycol dimethyl ether, or a combination thereof.

10. The photosensitive resin composition contains, relative to the total amount of the photosensitive resin composition, The (A) binder resin is 0.5% by weight to 15% by weight, The photopolymerizable compound (B) is present in an amount of 0.1% by weight to 10% by weight. 0.1% by weight to 10% by weight of the (C) photopolymerization initiator, The (D) colorant is 0.5% by weight to 15% by weight, and The remaining amount of the (E) solvent The photosensitive resin composition according to claim 1 .

11. The photosensitive resin composition according to claim 1, further comprising malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

12. A photosensitive resin film produced by using the photosensitive resin composition according to any one of claims 1 to 11.

13. A color filter comprising the photosensitive resin film of claim 12.

14. A CMOS image sensor comprising the color filter of claim 13.

Images