Photosensitive resin composition, cured layer using the same, color filter, and cmos image sensor

Abstract

Provided are a photosensitive resin composition, a cured layer formed using the same, a color filter including the cured layer, and a CMOS image sensor, the photosensitive resin composition including: a yellow pigment dispersion liquid including a compound represented by Chemical Formula 1 and a yellow pigment; a pigment; a photopolymerizable compound; a photopolymerization initiator; and a solvent.[Chemical Formula 1] (in Chemical Formula 1, each substituent is as defined in the specification).[Chemical Formula 1]

Description

Technical Field

[0001] This disclosure relates to a photosensitive resin composition, a cured layer using the same, a color filter including the cured layer, and a CMOS image sensor including the color filter. Background Technology

[0002] Among various displays, liquid crystal displays (LCDs) offer advantages such as light weight, thinness, low cost, low operating power consumption, and improved integrated circuit bonding, and are increasingly used in laptop computers, monitors, and television screens. An LCD includes a lower substrate on which a black matrix, color filters, and ITO pixel electrodes are formed, and an upper substrate on which active circuitry (including a liquid crystal layer, thin-film transistors, and capacitor layers) and ITO pixel electrodes are formed. Color filters are formed by sequentially stacking multiple color filters in pixel regions to form individual pixels, and a black matrix layer is disposed on a transparent substrate in a predetermined pattern to form boundaries between pixels. Each pixel is typically formed from three primary colors, such as red (R), green (G), and blue (B), in a predetermined order.

[0003] Pigment dispersion, one method for forming color filters, provides a colored film by repeating a series of processes, such as coating a photopolymerizable composition containing a colorant onto a transparent substrate including a black matrix, exposing the formed pattern, removing unexposed portions with a solvent, and thermally curing it. The coloring photosensitive resin composition used to manufacture color filters according to pigment dispersion typically includes an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. Pigment dispersion is actively used in the manufacture of LCDs for products such as mobile phones, laptops, monitors, and televisions.

[0004] Image sensors are components used to capture images in portable phone cameras or DSCs (digital still cameras), and can be classified into charge-coupled device (CCD) image sensors and complementary metal-oxide-semiconductor (CMOS) image sensors based on manufacturing processes and application methods. Color imaging devices using CCD or CMOS image sensors include color filters, each with filter segments for mixing red, green, and blue primary colors, achieving color separation. Recently, color filters installed in color imaging devices have pattern sizes of 2 μm or smaller, which is 1 / 100 to 1 / 200 of the pattern size of conventional color filters used in LCDs. Therefore, improving resolution and reducing pattern residue are important factors in determining device performance.

[0005] Meanwhile, in color filters made from pigment-based photosensitive resin compositions, there are limitations in brightness and contrast due to the size of the pigment particles. Furthermore, in the case of color imaging devices used in image sensors, smaller dispersed particle sizes are required to form fine patterns. To meet these requirements, attempts have been made to manufacture photosensitive resin compositions suitable for pigments by introducing dyes that do not form particles, thereby achieving color filters with improved brightness and contrast. However, in the case of dyes, compared to pigments, there are concerns about reduced brightness due to poorer durability, such as lightfastness and heat resistance. Summary of the Invention

[0006] Technical issues

[0007] One embodiment provides a photosensitive resin composition capable of achieving ultra-thin, ultra-fine patterning.

[0008] Another embodiment provides a cured layer using the photosensitive resin composition.

[0009] Another embodiment provides a color filter that includes the cured layer.

[0010] Another embodiment provides a CMOS image sensor that includes the color filter.

[0011] Technical solution

[0012] One embodiment provides a photosensitive resin composition comprising: a yellow pigment dispersion containing a compound (or a salt thereof) represented by Formula 1 and a yellow pigment, a pigment, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[0013] [Chemical Formula 1]

[0014] In chemical formula 1, X is a single bond, ether group ( -O- )or -N(R a )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (where R) aIt is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 aryl group, and R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group, provided that R 1 To R 4 One or more of them are acidic groups.

[0015] Acidic groups can be -SO3 - Carboxyl, phosphate, or phosphonic acid groups.

[0016] -N(R a )- It can be represented by the chemical formula N.

[0017] [Chemical formula N]

[0018] In the chemical formula N, L 5 It is a substituted or unsubstituted C1 to C10 alkylene group, and R 5 It is an acidic group.

[0019] Chemical formula 1 can be represented by chemical formula 1A or chemical formula 1B.

[0020] [Chemical Formula 1A]

[0021] [Chemical Formula 1B]

[0022] In chemical formula 1A and chemical formula 1B, X is a single bond, ether group ( -O- )or -N(R a )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (where R) a It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 aryl group, and R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group.

[0023] R 1 To R 4 At least two or more of them can be acidic groups.

[0024] R 1 To R 4 At least three or more of them can be acidic groups.

[0025] The acidic groups can be of the same type.

[0026] Acidic groups can be different from each other.

[0027] The compound (or its salt) may be represented by any one of chemical formulas 1-1 to 1-11.

[0028] [Chemical Formula 1-1]

[0029] [Chemical Formula 1-2]

[0030] [Chemical Formulas 1-3]

[0031] [Chemical Formulas 1-4]

[0032] [Chemical Formulas 1-5]

[0033] [Chemical Formulas 1-6]

[0034] [Chemical Formulas 1-7]

[0035] [Chemical Formulas 1-8]

[0036] [Chemical Formulas 1-9]

[0037] [Chemical Formulas 1-10]

[0038] [Chemical Formula 1-11]

[0039] The pigment may be a red pigment dispersion including a red pigment, and the photosensitive resin composition may also contain a binder resin.

[0040] Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may contain 10 wt% to 30 wt% of a yellow pigment dispersion, 20 wt% to 50 wt% of a red pigment dispersion, 1 wt% to 10 wt% of an adhesive resin, 0.1 wt% to 5 wt% of a photopolymerizable compound, 0.01 wt% to 3 wt% of a photopolymerization initiator, and the balance being a solvent.

[0041] The pigment can be a green pigment dispersion, including green pigment.

[0042] Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may contain 20 wt% to 40 wt% of a yellow pigment dispersion, 25 wt% to 55 wt% of a green pigment dispersion, 1 wt% to 10 wt% of a photopolymerizable compound, 0.1 wt% to 5 wt% of a photopolymerization initiator, and the balance being a solvent.

[0043] Another embodiment provides a cured layer manufactured using the photosensitive resin composition.

[0044] Another embodiment provides a color filter that includes the cured layer.

[0045] Another embodiment provides a CMOS image sensor that includes the color filter.

[0046] Other embodiments of the present invention are described in the following detailed description.

[0047] Beneficial effects

[0048] According to one embodiment, the photosensitive resin composition includes a yellow pigment dispersion containing a yellow pigment synergist represented by a specific structure, thus ultimately enabling the realization of color resists and CMOS image sensors capable of ultra-thin and ultra-fine patterning. Detailed Implementation

[0049] Embodiments of the invention are described in detail below. However, these are presented by way of example, and the invention is not limited thereto, but is defined only by the scope of the appended claims.

[0050] In this specification, unless otherwise specifically defined, “substituted” means that at least one hydrogen atom of a compound is replaced by a substituent of: a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, a formamidinyl group, a hydrazinyl 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 phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocyclic alkyl group, a C2 to C20 heterocyclic alkenyl group, a C2 to C20 heterocyclic alkynyl group, or a combination thereof.

[0051] In this specification, unless otherwise specifically defined, “heterocyclic alkyl,” “heterocyclic alkenyl,” “heterocyclic alkynyl,” and “heterocyclic alkylene” refer to each cyclic compound of the cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene groups containing at least one heteroatom of N, O, S, or P.

[0052] In this specification, unless otherwise specifically defined, “(meth)acrylate” means both “acrylate” and “methacrylate”.

[0053] In this specification, unless otherwise specifically defined, the term "combination" refers to a mixture or copolymer.

[0054] In the chemical formulas of this specification, unless otherwise defined, hydrogen bonds are located at the positions where chemical bonds should be shown but are not drawn.

[0055] In this specification, unless otherwise specifically defined, " "" indicates a point connecting identical or different atoms or chemical formulas.

[0056] According to one embodiment, a photosensitive resin composition comprises: a yellow pigment dispersion containing a compound represented by chemical formula 1 and a yellow pigment, a pigment, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[0057] [Chemical Formula 1]

[0058] In chemical formula 1, X is a single bond, ether group ( -O- )or -N(Ra )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (where R) a It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 aryl group, and R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group, provided that R 1 To R 4 One or more of them are acidic groups.

[0059] To promote stable dispersion and micronization of pigment dispersions, various studies are underway to achieve a constant particle size for pigments through processes such as salt milling of synthesized pigments. However, as mentioned above, in color filters manufactured from pigment-based photosensitive resin compositions, there are limitations in brightness and contrast due to the size of the pigment particles. Furthermore, in the case of color imaging devices used in image sensors, even smaller dispersed particle sizes are required to form fine patterns. To meet these requirements, there is an increasing need to manufacture photosensitive resin compositions for color filters by finely dispersing pigment particles and preparing pigment-containing dispersions that do not undergo re-aggregation, as well as dispersions containing said compounds.

[0060] In color filters manufactured from pigment-based photosensitive resin compositions, there is a limitation in coloring power due to the size of the pigment particles. Furthermore, for application in image sensors, resin compositions consisting of even smaller particles are required to form fine patterns. Additionally, improvements in the coloring of existing materials are needed for application in KrF exposure machines. Against this backdrop, after extensive research, the inventors have developed a yellow pigment derivative, namely a novel yellow pigment synergist (dispersion aid). By using a yellow pigment dispersion containing said synergist and yellow pigment, a composition capable of achieving ultra-thin, ultra-fine patterning can ultimately be provided.

[0061] Specifically, the compound represented by chemical formula 1 has one or more acidic groups at its terminals, and these acidic groups are highly polar groups, which are formed by connecting to L... a L 1 To L 4 Introducing various linking groups simultaneously at different positions in the compound represented by Formula 1 can more effectively achieve the aforementioned effects. That is, using the dispersant represented by Formula 1, which incorporates highly polar acidic groups, together with the pigment (specifically, a yellow pigment) and dispersant prevents the re-aggregation of the yellow pigment, thereby reducing the particle size of the yellow pigment and maximizing dispersion stability.

[0062] For example, the acidic group can be -SO3 - Carboxyl, phosphate, or phosphonic acid groups.

[0063] For example, -N(R a )- It can be represented by the chemical formula N.

[0064] [Chemical formula N]

[0065] In the chemical formula N, L 5 It is a substituted or unsubstituted C1 to C10 alkylene group. R 5 It is an acidic group.

[0066] when -N(R a )- When represented by the chemical formula N, since there are multiple sites in the compound according to one embodiment where acidic groups can be introduced, good flowability and dispersion stability can be maintained even when the organic pigments described later are finely dispersed, and it is easier to provide pigment dispersion aids that facilitate the realization of ultra-thin and ultra-fine patterning.

[0067] For example, chemical formula 1 can be represented by chemical formula 1A or chemical formula 1B.

[0068] [Chemical Formula 1A]

[0069] [Chemical Formula 1B]

[0070] In chemical formula 1A and chemical formula 1B, X is a single bond, ether group ( -O- )or -N(R a )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (where R) a It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 arylene group. R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group.

[0071] In chemical formula 1, by means of, as specified in chemical formula 1A or chemical formula 1B, -XL 1 -R 1 The position of the substituent can significantly improve the flowability and dispersion stability of organic pigments (especially yellow organic pigments).

[0072] For example, R 1 To R 4At least one or more of them can be acidic groups.

[0073] For example, R 1 To R 4 At least two or more of them can be acidic groups.

[0074] For example, R 1 To R 4 At least three or more of them can be acidic groups.

[0075] For example, R 1 To R 4 All of them can be acidic groups.

[0076] For example, when R 1 To R 4 When at least two or three or more of them are acidic groups, or when R 1 To R 4 When all the components are acidic groups, the types of acidic groups can be the same or different. Generally, in the case of most pigment additives, it is difficult to combine derivatives with different structures. However, since the compound according to one embodiment has a structure represented by chemical formula 1, it is advantageous to easily combine structurally different acidic groups, and the introduction positions of the acidic groups can also be controlled in a variety of ways.

[0077] For example, a compound can be represented by any of the chemical formulas 1-1 to 1-11, but is not limited to them.

[0078] [Chemical Formula 1-1]

[0079] [Chemical Formula 1-2]

[0080] [Chemical Formulas 1-3]

[0081] [Chemical Formulas 1-4]

[0082] [Chemical Formulas 1-5]

[0083] [Chemical Formulas 1-6]

[0084] [Chemical Formulas 1-7]

[0085] [Chemical Formulas 1-8]

[0086] [Chemical Formulas 1-9]

[0087] [Chemical Formulas 1-10]

[0088] [Chemical Formula 1-11]

[0089] For example, the compound can be a pigment synergist, i.e. a pigment dispersing aid.

[0090] For example, the compound can be a yellow pigment synergist, i.e., a yellow pigment dispersing aid.

[0091] For example, a yellow pigment dispersion contains a yellow pigment synergist and a yellow pigment. Here, the yellow pigment synergist may be included in an amount from 0.5 wt% to 5 wt%, depending on the total amount of the pigment dispersion. In this case, dispersion stability can be maximized by minimizing pigment reaggregation.

[0092] For example, as a yellow pigment, one could mention pigments such as Pigment Yellow 138, 139, 150, 185, etc., but it is not necessary to limit oneself to these.

[0093] Based on the total amount of the yellow pigment dispersion, the yellow pigment can be included in an amount from 5 wt% to 20 wt%. In this case, the interaction between the yellow pigment synergist and the yellow pigment becomes optimal, maximizing dispersion stability by minimizing pigment reaggregation.

[0094] For example, a yellow pigment dispersion may also contain a dispersant, a dispersing resin, and a solvent.

[0095] For example, polymeric pigment dispersants commonly used in printing inks, coatings, pigment-dispersing resist compositions for color filters, inkjet printing inks, etc., can be used as dispersants, and their type can be appropriately selected depending on the type of organic pigment used together or the type of organic solvent described later. Specifically, the dispersant helps the pigment to be uniformly dispersed in the dispersion, and any of nonionic, anionic, or cationic dispersants can be used. More specifically, polyalkylene glycols or their esters, polyoxyethylene, polyol ester epoxy alkyl adducts, alcohol epoxy alkyl adducts, sulfonates, sulfonates, carboxylates, carboxylates, alkylamide epoxy alkyl adducts, alkylamines, quaternary ammonium, etc., can be used, and these can be used alone or in mixtures of two or more.

[0096] Based on the total amount of the yellow pigment dispersion, the dispersant can be included in an amount from 1 wt% to 5 wt%. When the amount of dispersant is less than 1 wt%, the pigment dispersibility may be reduced, while when it exceeds 5 wt%, there may be concerns such as reduced developability.

[0097] For example, as a dispersion resin, an acrylic resin containing carboxyl groups can be used, which can improve the stability of the yellow pigment dispersion and also improve the patterning ability of the pixels.

[0098] Based on the total amount of the yellow pigment dispersion, the dispersing resin may be included in an amount of 3 wt% to 10 wt%.

[0099] As a solvent, ethylene glycol acetate, ethyl celecoxib, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., can be used, and propylene glycol methyl ether acetate is a desirable solvent among them.

[0100] Considering the solubility of the dispersing resin, the dispersibility of the pigment, and the coatability, based on the total amount of the yellow pigment dispersion, it is expected that these solvents will be included in the balance (e.g., 60 wt% to 90 wt%).

[0101] For example, the pigment used with the yellow pigment dispersion can be an organic pigment, such as a red or green pigment, and the organic pigment can be micronized. Micronized organic pigments can be salt-milled organic pigments. Specifically, to improve the transmittance and contrast of color filters or inkjet printing, it is desirable to micronize the organic pigment. Furthermore, it is more desirable to use a kneader or kneading device that rotates three stirring blades while undergoing revolution motion to grind the organic pigment with inorganic salt, thereby achieving a finer primary particle size. Specifically, it is desirable to use an organic pigment obtained by salt milling using a kneading device that rotates three stirring blades while undergoing revolution motion. In this case, salt milling can be performed to make the primary particle size of the pigment finer and more uniform.

[0102] Examples of red pigments include perylene pigments, anthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. Specific examples of red pigments include perylene pigments, quinacridone pigments, naphthol (AS), sicomin pigments, anthraquinones (Sudan I, II, III, R), bis azo, benzopyran, etc., but are not limited to these.

[0103] When the photosensitive resin composition according to one embodiment is a red photosensitive resin composition containing a red pigment, the red pigment may be included in the composition in the form of a pigment dispersion.

[0104] Examples of green pigments include Pigment Green 58, 59, etc., but are not limited to these.

[0105] When the photosensitive resin composition according to one embodiment is a green photosensitive resin composition containing a green pigment, the green pigment may be included in the composition in the form of a pigment dispersion.

[0106] When the pigment is red, the photosensitive resin composition may contain a binder resin, and in this case, based on the total amount of the photosensitive resin composition, the photosensitive resin composition may contain 10 wt% to 30 wt% of a yellow pigment dispersion, 20 wt% to 50 wt% of a red pigment dispersion, 1 wt% to 10 wt% of a binder resin, 0.1 wt% to 5 wt% of a photopolymerizable compound, 0.01 wt% to 3 wt% of a photopolymerization initiator, and the balance being a solvent.

[0107] When the pigment is green, the photosensitive resin composition may not contain a binder resin (a photosensitive resin composition without a binder resin), and in this case, based on the total amount of the photosensitive resin composition, the photosensitive resin composition may contain 20 wt% to 40 wt% of a yellow pigment dispersion, 25 wt% to 55 wt% of a green pigment dispersion, 1 wt% to 10 wt% of a photopolymerizable compound, 0.1 wt% to 5 wt% of a photopolymerization initiator, and the balance being a solvent.

[0108] As described above, by changing the composition of the photosensitive resin composition according to the type of pigment, a coloring photosensitive resin composition for color filters with excellent dispersibility and dispersion stability, improved tinting strength, and pattern residue suppression effect can be obtained.

[0109] The adhesive resin can be an acrylic resin.

[0110] Acrylic resin is a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer that can be copolymerized therewith, and is a resin containing at least one acryloyl repeating unit.

[0111] The first olefinic unsaturated monomer may be an olefinic unsaturated monomer containing at least one carboxyl group, and examples of said monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

[0112] Based on the total amount of acrylic adhesive resin, the first olefinic unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example 10 wt% to 40 wt%.

[0113] The second olefinic unsaturated monomers can be aromatic vinyl compounds, such as styrene, α-methylstyrene, vinyltoluene, vinylbenzene methyl ether, etc.; unsaturated carboxylic acid ester compounds, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, etc.; unsaturated aminoalkyl carboxylic acid ester compounds, such as 2-aminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, etc.; vinyl carboxylic acid ester compounds, such as vinyl acetate, vinyl benzoate, etc.; unsaturated glycidyl carboxylic acid ester compounds, such as glycidyl methacrylate, etc.; vinyl cyanide compounds, such as methacrylonitrile, etc.; unsaturated amide compounds, such as methacrylamide, etc., and these can be used alone or as a mixture of two or more.

[0114] Specific examples of acrylic resins may be (meth)acrylic acid / benzyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene copolymers, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymers, etc., but are not limited thereto, and these may be used alone or as a mixture of two or more.

[0115] For example, along with acrylic resins, adhesive resins may also contain epoxy resins.

[0116] The weight-average molecular weight of the adhesive resin can be from 3,000 g / mol to 150,000 g / mol, for example from 5,000 g / mol to 50,000 g / mol, or for example from 20,000 g / mol to 30,000 g / mol. If the weight-average molecular weight of the adhesive resin is within the above range, the photosensitive resin composition exhibits excellent physicochemical properties and suitable viscosity when manufacturing color filters, and also exhibits excellent adhesion to the substrate.

[0117] The acid value of the adhesive resin can be from 15 mgKOH / g to 60 mgKOH / g, for example, from 20 mgKOH / g to 50 mgKOH / g. If the acid value of the adhesive resin is within the above range, the resolution of the pixel pattern is improved.

[0118] Photopolymerizable compounds can be monofunctional or polyfunctional esters of (meth)acrylic acid containing at least one olefinic unsaturated double bond.

[0119] Due to the olefinic unsaturated double bonds, photopolymerizable compounds can undergo sufficient polymerization during exposure in the patterning process, resulting in patterns with excellent heat resistance, light resistance, and chemical resistance.

[0120] Specific examples of photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. Tetramethylol tetraacrylate, pentaerythritol hexamethylol acrylate, dipentaerythritol dimethylol acrylate, dipentaerythritol trimethylol acrylate, dipentaerythritol pentamethylol acrylate, dipentaerythritol hexamethylol acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane trimethylol acrylate, tri(meth)acryloyloxyethyl phosphate, phenolic epoxy (meth) acrylate, etc.

[0121] Commercially available examples of photopolymerizable compounds are shown below. Monofunctional (meth)acrylates may include Aronix M-101. ® M-111 ® M-114 ® (Toagosei Chemistry Industry Co., Ltd.); KAYARADTC-110S ® TC-120S ® (Nippon Kayaku Co., Ltd.); V-158 ® V-2311 ® (Osaka Organic Chemical Ind., Ltd.), etc. Examples of bifunctional (meth)acrylates may include Aronix M-210. ® M-240 ® M-6200 ® (Toagosei Chemistry Industry Co., Ltd.), KAYARAD HDDA ® HX-220 ® R-604 ® (Nippon Kayaku Co., Ltd.), V-260 ® V-312 ® V-335 HP ®(Osaka Organic Chemical Inc., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Aronix M-309. ® M-400 ® M-405 ® M-450 ® M-7100 ® M-8030 ® M-8060 ® (Toagosei Chemistry Industry Co., Ltd.), KAYARADTMPTA ® DPCA-20 ® DPCA-30 ® DPCA-60 ® DPCA-120 ® (Nippon Kayaku Co., Ltd.), V-295 ® V-300 ® V-360 ® V-GPT ® V-3PA ® V-400 ® (Osaka Yuki Kayaku Kogyo Co. Ltd.), etc. These can be used alone or as a mixture of two or more.

[0122] Photopolymerizable compounds can be treated with acid anhydrides to give them better developability.

[0123] The desired range of photopolymerizable compounds is as described above. If the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure in the patterning process, resulting in excellent reliability and excellent developability in alkaline developers.

[0124] The photopolymerization initiator can be a photopolymerization initiator commonly used in photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, oxime compounds, etc.

[0125] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-but-1-one, etc.

[0126] Examples of benzophenone compounds include benzoyl benzoate, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0127] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0128] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0129] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-helianyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0130] Examples of oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone, O-ethoxycarbonyl-α-oxoamino-1-phenylprop-1-one, etc. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylhydrothiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylhydrothiophenyl)-but-1-one oxime-O-acetate.

[0131] In addition to the compounds mentioned above, photopolymerization initiators may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc.

[0132] Photopolymerization initiators can be used in conjunction with photosensitizers, which are capable of inducing a chemical reaction by absorbing light and subsequently transferring their energy.

[0133] Examples of photosensitizers include tetraethylene glycol bis(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and dipentaerythritol tetra(3-mercaptopropionate).

[0134] The desired range of photopolymerization initiators is as described above. If the photopolymerization initiator is included within the above range, excellent reliability can be ensured due to sufficient curing during exposure in the patterning process. The pattern can have excellent resolution and close contact characteristics, as well as excellent heat resistance, light resistance and chemical resistance, and transmittance degradation due to unreacted initiator can be prevented.

[0135] As a solvent, materials that are compatible with but do not react with a pigment dispersion comprising a compound, pigment, adhesive resin, photopolymerizable compound, and photopolymerization initiator according to one embodiment can be used.

[0136] Examples of solvents include alcohols, such as methanol and ethanol; ethers, such as dichloroethyl ether, n-butyl ether, diisopentyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; celecoxyl acetates, such as celecoxyl methyl acetate, celecoxyl ethyl acetate, and celecoxyl diethyl acetate; carbitols, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.; and propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate. Esters, such as 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-pentanone, 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; alkyl alkoxyacetic acid esters, such as methyl methoxyacetate and methyl methoxyacetate. Ethyl acetate, methoxyethyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; alkyl 3-oxypropionic acid esters, such as methyl 3-oxypropionic acid, ethyl 3-oxypropionic acid, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid, etc.; alkyl 2-oxypropionic acid esters, such as methyl 2-oxypropionic acid, ethyl 2-oxypropionic acid, propyl 2-oxypropionic acid, etc.; alkyl 2-alkoxypropionic acid esters, such as methyl 2-methoxypropionic acid, ethyl 2-methoxypropionic acid. Ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionates, such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, etc.; alkyl monooxycarboxylic acids of alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, etc.; keto esters, such as ethyl pyruvate, etc. In addition, high-boiling-point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caprylic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl acetate, etc. can also be used.

[0137] Among these, considering compatibility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates, such as ethyl celesu; esters, such as ethyl 2-hydroxypropionate; carbitol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and / or ketones, such as cyclohexanone.

[0138] To prevent stains or spots during coating, improve leveling properties, and prevent residues due to non-development, the photosensitive resin composition may also contain other additives such as malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorinated surfactants, free radical polymerization initiators, or combinations thereof.

[0139] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., which can be used alone or in mixtures of two or more.

[0140] Examples of fluorinated surfactants include BM-1000 from BM Chemie. ® BM-1100 ® etc.; Megafac F 142D from Dainippon Ink and Chemicals, Inc. ® F 172 ® F 173 ® F 183 ® etc.; Fluorad FC-135 from Sumitomo 3M Ltd. ® FC-170C ® FC-430 ® FC-431 ® etc.; Surflon S-112 from AsahiGlass Co., Ltd. ® S-113 ® S-131 ® S-141 ® S-145 ® And others; as well as commercially available products from ToraySilicone Co., Ltd., such as SH-28PA. ® SH-190 ® SH-193 ® SZ-6032 ® SF-8428® wait.

[0141] The amount of additives can be easily adjusted according to the desired physical properties.

[0142] Another embodiment provides a cured layer manufactured using the photosensitive resin composition.

[0143] Another embodiment provides a color filter that includes the cured layer.

[0144] The pattern formation process in the color filter is shown below.

[0145] The pattern forming process may include processes such as coating a photosensitive resin composition onto a support substrate by spin coating, slot coating, inkjet printing, etc.; drying the coated photosensitive resin composition to form a photosensitive resin composition film; exposing the photosensitive resin composition film; developing the exposed photosensitive resin composition film with an alkaline aqueous solution to manufacture a photosensitive resin film; and heat-treating the photosensitive resin film. Since the conditions in these processes are well known in the art, detailed descriptions thereof will be omitted in this specification.

[0146] Another embodiment provides a CMOS image sensor that includes the color filter.

[0147] Invention Model

[0148] The invention will be described in more detail below with reference to embodiments. However, the following embodiments are merely preferred embodiments of the invention, and the invention is not limited to these embodiments.

[0149] (Preparation of yellow pigment dispersion)

[0150] Prepare a yellow pigment dispersion with the composition shown in Tables 1 and 2 below.

[0151] dispersant

[0152] Tertiary amine dispersant Efka PX 4310 (amine value 19 mgKOH / g, BASF Co.)

[0153] Dispersion resin

[0154] Acrylic adhesive resin (molecular weight 6000 g / mol, acid value 70 mgKOH / g, double bond equivalent 370 g / mol, Showa Denko Co.)

[0155] solvent

[0156] Propylene glycol monomethyl ether acetate (PGMEA, Sigma-Aldrich Corporation)

[0157] [Table 1]

[0158] (Unit: wt%)

[0159] [Table 2]

[0160] (Unit: wt%)

[0161] [Chemical Formula 1-1]

[0162] [Chemical Formulas 1-3]

[0163] [Chemical Formulas 1-10]

[0164] [Chemical formula C-1]

[0165] [Chemical formula C-2]

[0166] (Preparation of photosensitive resin composition)

[0167] Photosensitive resin compositions having the compositions shown in Tables 3 and 4 below were prepared. In Table 3, the red pigment in the red pigment dispersion is R254, and in Table 4, the green pigment in the green pigment dispersion is G58. In Tables 3 and 4, the binder resin is an acrylic binder resin (molecular weight 6000 g / mol, acid value 70 mgKOH / g, double bond equivalent 370 g / mol, Showa Denko Co.), the photopolymerizable compound is DPHA (Nippon Kayaku Co., Ltd.), the photopolymerization initiator is SPI-03 (Samyang Corporation), and the solvent is propylene glycol monomethyl ether acetate (PGMEA, Sigma-Aldrich Corporation).

[0168] [Table 3]

[0169] (Unit: wt%)

[0170] [Table 4]

[0171] (Unit: wt%)

[0172] (evaluate)

[0173] Measuring viscosity

[0174] For each photosensitive resin composition of Examples 1 to 12 and Comparative Examples 1 to 10, the viscosity was measured immediately after preparation (25°C) and after storage at room temperature (25°C) for one week using a viscometer (ThermoFisher Scientific Inc. HAAKE MARS 40), and the results are shown in Table 5 below.

[0175] Spectrum measurement

[0176] Each photosensitive resin composition of Examples 1 to 12 and Comparative Examples 1 to 10 was spin-coated onto glass (118 mm × 118 mm, 0.7 mm thick) and heated at 100°C for 3 minutes using a hot plate to form a 0.6 μm coating. Then, an i-line step exposure apparatus (Nikon Co.) was used at 2500 J / m². 2 The sample was exposed to an energy level and heated on a hot plate at 200°C for 5 minutes to form a specimen. The transmittance of the obtained specimen was measured at a wavelength of 470 nm using an MCPD (Otsuka Electronics Co.), and the results are shown in Table 5 below.

[0177] Evaluation of residues (resolution)

[0178] On an 8-inch silicon wafer, each of the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 10 was spin-coated, and heated at 100°C for 3 minutes using a hot plate to form a 0.6 μm coating. Then, an i-line step-out exposure apparatus (Nikon Co.) was used at 2500 J / m². 2 The sample was exposed to high energy, then developed using a 0.38% tetramethylammonium hydroxide aqueous solution (ENF Co.) via a puddle method, followed by rinsing with pure water. Subsequently, the sample was heated at 200°C on a hot plate for 5 minutes to form a patterned specimen. For the formed specimen, a CD-SEM (Hitachi Co.) was used to locate patterns with a CD of 1.4 μm, and the residue between patterns was quantified according to the following criteria, with the results shown in Table 5 below. When the residue level was 1 to 2, the residue suppression effect was considered improved.

[0179] <Standards for Residue Evaluation>

[0180] No residue visible, but large amount of residue visible.

[0181] [Table 5]

[0182] (Unit: wt%)

[0183] As can be confirmed from Table 5 above, by using a yellow pigment dispersion containing a yellow pigment synergist with light-absorbing properties that also aids in pigment dispersion, the photosensitive resin composition according to one embodiment prevents aggregation between the pigments used, thereby significantly improving the dispersibility and dispersion stability of the pigment particles, and exhibiting excellent pattern residue suppression effects while possessing improved tinting strength. In other words, it can be readily anticipated that fine patterning and film formation can be achieved by using the photosensitive resin composition according to one embodiment.

[0184] This invention is not limited to the embodiments described above, but can be manufactured in various different forms, and those skilled in the art will understand that it can be implemented in other specific forms without changing the technical concept or essential characteristics of the invention. Therefore, it should be understood that the embodiments described above are exemplary and non-limiting in all respects.

Claims

1. A photosensitive resin composition comprising: A yellow pigment dispersion comprising a yellow pigment and a compound represented by chemical formula 1. pigment, Photopolymerizable compounds Photopolymerization initiators, and Solvent: [Chemical Formula 1] In chemical formula 1, X is a single bond, ether group ( -O- )or -N(R a )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (in, R a It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 aryl group, and R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group, provided that R 1 To R 4 One or more of them are acidic groups.

2. The photosensitive resin composition according to claim 1, wherein, The acidic group is -SO3 - Carboxyl, phosphate, or phosphonic acid groups.

3. The photosensitive resin composition according to claim 1, wherein, -N(R a )- Represented by the chemical formula N: [Chemical formula N] In the chemical formula N, L 5 It is a substituted or unsubstituted C1 to C10 alkylene group, and R 5 It is an acidic group.

4. The photosensitive resin composition according to claim 1, wherein, Chemical formula 1 is represented by chemical formula 1A or chemical formula 1B: [Chemical Formula 1A] [Chemical Formula 1B] In chemical formula 1A and chemical formula 1B, X is a single bond, ether group ( -O- )or -N(R a )- (where R) a (It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group). L 1 To L 4 Each is independently a single bond, substituted or unsubstituted C1 to C20 alkylene or ether group. -O- ), -N(R a )- (where R) a It is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof. L a It is a single-bonded or substituted or unsubstituted C6 to C20 aryl group, and R 1 To R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl or acidic group.

5. The photosensitive resin composition according to claim 1, wherein, R 1 To R 4 At least two or more of them are acidic groups.

6. The photosensitive resin composition according to claim 1, wherein, R 1 To R 4 At least three or more of them are acidic groups.

7. The photosensitive resin composition according to claim 6, wherein, The acidic groups are of the same type.

8. The photosensitive resin composition according to claim 1, wherein, The acidic groups are different from each other.

9. The photosensitive resin composition according to claim 1, wherein, The compound is represented by any one of chemical formulas 1-1 to 1-11: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formulas 1-3] [Chemical Formulas 1-4] [Chemical Formulas 1-5] [Chemical Formulas 1-6] [Chemical Formulas 1-7] [Chemical Formulas 1-8] [Chemical Formulas 1-9] [Chemical Formulas 1-10] [Chemical Formula 1-11] 。 10. The photosensitive resin composition according to claim 1, wherein, The pigment is a red pigment dispersion containing red pigment, and the photosensitive resin composition further contains a binder resin.

11. The photosensitive resin composition according to claim 10, wherein, Based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: The yellow pigment dispersion of 10 wt% to 30 wt%, The red pigment dispersion of 20 wt% to 50 wt%, The adhesive resin is 1 wt% to 10 wt%. 0.1 wt% to 5 wt% of the photopolymerizable compound, 0.01 wt% to 3 wt% of the photopolymerization initiator, and The remainder of the solvent.

12. The photosensitive resin composition according to claim 1, wherein, The pigment is a green pigment dispersion containing green pigment.

13. The photosensitive resin composition according to claim 12, wherein, Based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: The yellow pigment dispersion of 20 wt% to 40 wt%, The green pigment dispersion of 25 wt% to 55 wt%, 1 wt% to 10 wt% of the photopolymerizable compound, 0.1 wt% to 5 wt% of the photopolymerization initiator, and The remainder of the solvent.

14. A cured layer, manufactured using any one of the photosensitive resin compositions according to claims 1 to 13.

15. A color filter comprising the cured layer of claim 14.

16. A CMOS image sensor comprising the color filter of claim 15.

Images