JP2020086458A - Photosensitive resin composition, and photosensitive resin film and color filter that employ the same - Google Patents

Abstract

To provide: a photosensitive resin composition allowing high color reproduction while exhibiting excellent light fastness; a photosensitive resin film manufactured using the photosensitive resin composition; and a color filter including the photosensitive resin film.SOLUTION: A photosensitive resin composition comprises (A) a colorant containing a blue pigment and an azaporphyrin-based dye, the dye having a maximum absorption wavelength in the wavelength region from 350 nm to 450 nm, (B) a binder resin, (C) a photopolymerizable compound, (D) a photoinitiator, and (E) a solvent.SELECTED DRAWING: None

Description

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

A liquid crystal display device, which is one of the display devices, has advantages such as weight reduction, thinness, cost reduction, low power consumption drive, and excellent connectivity with integrated circuits. Its range of use has been expanded for monitors and TV images. In such a liquid crystal display device, a lower substrate on which a black matrix (light-shielding layer), a color filter and an ITO pixel electrode are formed, an active circuit unit including a liquid crystal layer, a thin film transistor and a storage capacitor layer and an ITO pixel electrode are formed. And an upper substrate that has been formed.

The color filter includes a black matrix (light-shielding layer) formed on a transparent substrate in a predetermined pattern to shield the boundary between pixels and a plurality of colors (usually red ( It has a structure in which pixel portions in which R), green (G), and blue (B) are arranged in a predetermined order are sequentially stacked.

The pigment dispersion method, which is one of the methods for realizing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix to form a pattern of a form to be formed. It is a method of forming a colored thin film by repeating a series of steps of removing the non-exposed region with a solvent and thermally curing after exposing. The colored photosensitive resin composition used for producing a color filter by the pigment dispersion method generally comprises an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives. The pigment dispersion method having the above characteristics is actively applied to manufacture LCDs for mobile phones, notebook computers, monitors, TVs and the like.

However, recently, even in a photosensitive resin composition for a color filter using a pigment dispersion method, which has various advantages, the dispersion state must be stable in the dispersion liquid even if the powder micronization process is difficult and is dispersed. Therefore, various additives are required, the process is very difficult, and the pigment dispersion has the disadvantages that storage and transportation conditions are difficult in order to maintain optimum quality.

In addition, in a color filter manufactured from a pigment-type photosensitive resin composition, there are limits on the brightness and the dark-to-dark ratio caused by the size of the pigment particles. Further, in the case of a color image pickup device for an image sensor, a smaller dispersed particle size is required for forming a fine pattern. In order to meet such a demand, instead of a pigment or together with a pigment, a photosensitive resin composition into which a dye that does not form particles is introduced is produced, and a color filter having improved color characteristics such as brightness and contrast ratio is provided. Although attempts have been made to realize it, there is a problem that the dye-type photosensitive resin composition has lower light resistance than the pigment-type photosensitive resin composition.

As a result, C.I. I. Pigment Blue 15:6 (ε type) pigment instead of C.I. I. Pigment Blue 15:3 (β type) or C.I. I. Pigment Blue 15:4 (β type) pigment was applied, but in this case, although the light resistance was excellent, the Bx color coordinate was increased by the high color blue resist, and the high color There is a problem that it is not suitable for the recent trend of increasing demand for reproduction.

Therefore, research on a photosensitive resin composition capable of high color reproduction (having a small Bx color coordinate in a high-color blue resist) at the same time without causing deterioration in light resistance is ongoing.

Korean Registered Patent No. 1344790

One embodiment is to provide a photosensitive resin composition which has excellent light resistance and is capable of high color reproduction.

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

Still another embodiment is to provide a color filter including the photosensitive resin film.

One embodiment of the present invention is (A) a colorant containing a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength region of 350 nm to 450 nm, (B) a binder resin, and (C) a photopolymerizable compound. And (D) a photopolymerization initiator, and (E) a solvent.

The central metal of the azaporphyrin dye may be Cu or V(=O).

The azaporphyrin dye may be represented by the following Chemical Formula 1.

In the above chemical formula 1,
M is Cu or V (=O),
R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted An aryl group having 6 to 20 carbon atoms, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted alkyl ester group having 1 to 20 carbon atoms,
However, at least one or more of R ^{1 to} R ⁵ , at least one or more of R ^{6 to} R ¹⁰ , at least one or more of R ^{11 to} R ¹⁵ , and at least one of R ^{16 to} R ^20. One or more is not independently a hydrogen atom.

One of R ^{1 to} R ⁵ , one of R ^{6 to} R ¹⁰ , one of R ^{11 to} R ¹⁵ and one of R ^{16 to} R ²⁰ are each independently. It may be represented by the following chemical formula 2.

In the above chemical formula 2,
R ²¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The above R ³ , R ⁸ , R ¹³ and R ¹⁸ may be independently represented by the following chemical formula 3.

In the above chemical formula 3,
L ¹ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,
R ²² and R ²³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The azaporphyrin dye may be represented by the following chemical formula 1-1 or chemical formula 1-2.

The azaporphyrin dye may be included in an amount of 0.1 wt% to 5 wt% based on the total solid content of the photosensitive resin composition.

The colorant may further include a violet pigment.

The blue pigment is C.I. I. Pigment Blue 15:6.

The photosensitive resin composition contains 2% to 40% by weight of the colorant, 3% to 20% by weight of the binder resin, and 1% by weight of the photopolymerizable compound based on the total amount of the photosensitive resin composition. ˜20 wt %, 0.1 wt% to 5 wt% of the photopolymerization initiator, and the residual amount of the solvent may be included.

The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

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

Yet another embodiment of the present invention provides a color filter including the photosensitive resin film.

Other specific aspects of the invention are included in the detailed description below.

The photosensitive resin composition according to an embodiment of the present invention includes a compound that blocks a wavelength of 350 nm to 450 nm in order to improve the color reproducibility of a color filter that constitutes a panel of an optical display device such as a liquid crystal display device. Even at high color coordinates, relatively high light resistance can be maintained. In particular, since the compound has a property of strongly absorbing light in a very narrow region, it is possible to realize a high color (blue) by blocking the spectrum of the region even with a very small amount.

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

Unless otherwise specified herein, “substituted” to “substituted” means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (F, Br, Cl or I), hydroxy. A group, a nitro group, a cyano group, an amino group (NH ₂ , NH(R ²⁰⁰ ), or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ^201, and R ²⁰² are the same or different from each other. , Each independently an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted Those substituted with one or more substituents selected from the group consisting of an alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group means.

Unless otherwise specified in this specification, the “alkyl group” means an alkyl group having 1 to 20 carbon atoms, specifically an alkyl group having 1 to 15 carbon atoms, and a “cycloalkyl group”. Means a cycloalkyl group having 3 to 20 carbon atoms, specifically a cycloalkyl group having 3 to 18 carbon atoms, an "alkoxy group" means an alkoxy group having 1 to 20 carbon atoms, Specifically, it means an alkoxy group having 1 to 18 carbon atoms, "aryl group" means an aryl group having 6 to 20 carbon atoms, specifically an aryl group having 6 to 18 carbon atoms, The "alkenyl group" means an alkenyl group having 2 to 20 carbon atoms, specifically an alkenyl group having 2 to 18 carbon atoms, and the "alkylene group" means an alkylene group having 1 to 20 carbon atoms. , Specifically, means an alkylene group having 1 to 18 carbon atoms, "arylene group" means an arylene group having 6 to 20 carbon atoms, and specifically means an arylene group having 6 to 16 carbon atoms. To do.

Unless stated otherwise specifically in the specification, “(meth)acrylate” means both “acrylate” and “methacrylate”, “(meth)acrylic acid” means “acrylic acid” and “acrylic acid”. Methacrylic acid" means both are possible.

As used herein, unless otherwise defined, "combination" means mixed or copolymerized. Further, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymers.

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

Unless otherwise defined herein, “*” means the same or different atoms or moieties linked to chemical formulas.

Also, as used herein, a member is said to be "on" another member, not only when one member is in contact with another member, but also between two members. It also includes the case where members exist.

In addition, in the present specification, when a certain part includes “a component”, it does not exclude other component, and includes another component unless there is a contrary description. It means that you can do it.

One embodiment of the present invention includes (A) a colorant containing a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength range of 350 nm to 450 nm; (B) a binder resin; (C) a photopolymerizable compound; Provided is a photosensitive resin composition comprising D) a photopolymerization initiator; and (E) a solvent.

Hereinafter, each component will be specifically described.

(A) Colorant The photosensitive resin composition according to one embodiment includes a blue pigment and an azaporphyrin dye as a colorant.

The azaporphyrin dye has a maximum absorption wavelength in the wavelength range of 350 nm to 450 nm, for example, 400 nm to 440 nm.

In order to realize high color blue (realization of high color blue resist), it is essential to realize low Bx color coordinates, and the combination of colorants and the content thereof can minimize deterioration of light resistance and processability. is important. In order to realize a high color blue, a method of increasing the content of the colorant while blue-shifting the absorption of the blue colorant is generally used. However, the above method has a disadvantage in that durability characteristics such as light resistance are significantly deteriorated because the content of the colorant increases. Accordingly, a method of mixing and using other dyes in the blue colorant has been proposed, but when other dyes are applied to the blue colorant, the light resistance is greatly reduced by the other dyes, and thus the light resistance It was very difficult to achieve high color blue while maintaining excellent. For example, there has been an attempt to absorb a wavelength region of 380 nm to 420 nm using a conventional azo series yellow dye. In this case, a relatively large amount of the azo series yellow dye is added. In some cases, commercialization has failed because there is a problem that the process margin of the entire composition cannot be ensured because it has to be obtained. Further, when a conventional azo yellow dye is used together with an existing blue pigment (epsilon blue), the transmission and absorption spectra overlap each other, so that the blue (blue) transmission region is damaged and the luminance loss increases, resulting in a decrease in light resistance. There is a fear.

According to one embodiment, a blue pigment is mixed with an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength range of 350 nm to 450 nm to be used as a colorant to minimize the deterioration in light resistance, which is the above-mentioned problem. It is possible to realize high color blue at the same time.

For example, the central metal of the azaporphyrin dye may be Cu or V(═O). The type of the central metal of the azaporphyrin-based dye is very important because high color reproduction and light fastness may change depending on the central metal of the azaporphyrin-based dye. For example, when the central metal of the azaporphyrin dye is Zn, Co, Pt, or the like, it may be difficult to improve the light resistance even if it is mixed with the blue pigment and used as a colorant.

The azaporphyrin dye may be represented by the following Chemical Formula 1.

In the above chemical formula 1,
M is Cu or V (=O),
R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted An aryl group having 6 to 20 carbon atoms, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted alkyl ester group having 1 to 20 carbon atoms,
However, at least one or more of R ^{1 to} R ⁵ , at least one or more of R ^{6 to} R ¹⁰ , at least one or more of R ^{11 to} R ¹⁵ , and at least one of R ^{16 to} R ^20. One or more is not independently a hydrogen atom.

For example, in Formula 1, one of R ^{1 to} R ⁵ , one of R ^{6 to} R ¹⁰ , one of R ^{11 to} R ¹⁵ and one of R ^{16 to} R ^20. Can be independently represented by the following chemical formula 2.

In the above chemical formula 2,
R ²¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

For example, in Chemical Formula 1, R ³ , R ⁸ , R ¹³ and R ¹⁸ may be independently represented by the following Chemical Formula 3.

In the above chemical formula 3,
L ¹ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,
R ²² and R ²³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

For example, the azaporphyrin dye may be represented by the following chemical formula 1-1 or chemical formula 1-2.

The azaporphyrin dye may be included in a smaller amount than the blue pigment. The azaporphyrin-based dye is an auxiliary dye that plays a role of absorbing light in a wavelength range of 350 nm to 450 nm, and if it is contained in a smaller amount than the blue pigment, high color reproduction with a blue resist is possible. When the azaporphyrin-based dye is included in a content higher than that of the blue pigment, it may be difficult to reproduce a high color in the blue resist because the azaporphyrin-based dye is used in an excessive amount.

The azaporphyrin dye may be included in an amount of 0.1 wt% to 5 wt% based on the total solid content of the photosensitive resin composition. In the above content range, sufficiently high color reproduction is possible and an excellent process margin can be provided.

For example, the colorant may further include a violet pigment in addition to the blue pigment and the azaporphyrin dye.

For example, the blue pigment may be an epsilon blue pigment. The use of an epsilon blue pigment as a blue pigment used in the composition according to an embodiment may improve brightness (light fastness) rather than a beta blue pigment.

For example, the blue pigment may be C.I. I. Pigment Blue 15:6.

The colorant may be included in an amount of 2% by weight to 40% by weight based on the total solid content of the photosensitive resin composition according to an exemplary embodiment. When the colorant is included in the content range, excellent light resistance can be achieved at high color coordinates.

(B) Binder resin The binder resin may include an acrylic binder resin. For example, the binder resin may be an acrylic binder resin.

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer having one or more carboxy groups and/or hydroxy groups, and specific examples thereof include acrylic acid, methacrylic acid, and maleic acid. Acids, itaconic acid, fumaric acid or combinations thereof.

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

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether; methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate. , 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate and other unsaturated carboxylic acid ester compounds; 2-aminoethyl ( Unsaturated carboxylic acid aminoalkyl ester compounds such as (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl such as glycidyl (meth)acrylate Examples thereof include ester compounds; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and these can be used alone or in combination of two or more.

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2- Examples thereof include hydroxyethyl methacrylate copolymer and (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, but the invention is not limited thereto, and these may be used alone or in combination of two or more. It can also be used.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, for example 5,000 g/mol to 50,000 g/mol, for example 20,000 g/mol to 30,000 g/mol. .. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate during production of a color filter.

The acid value of the acrylic binder resin may be 15 mgKOH/g to 60 mgKOH/g, for example 20 mgKOH/g to 50 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the pixel pattern resolution is excellent.

The binder resin may be included in an amount of 3% by weight to 20% by weight, for example, 5% by weight to 15% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, the developability is excellent and the crosslinkability is improved during the production of the color filter, so that the excellent surface smoothness can be obtained.

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

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

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

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

The photopolymerizable compound may be used after being treated with an acid anhydride in order to impart more excellent developability.

The photopolymerizable compound may be included in an amount of 1% by weight to 20% by weight, for example, 3% by weight to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above range, curing is sufficiently performed during exposure in the pattern forming step, which is excellent in reliability and developability in an alkali developing solution.

(D) Photopolymerization Initiator The photopolymerization initiator is an initiator generally used in photosensitive resin compositions, and includes, for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds. , Oxime-based compounds or combinations thereof can be used.

Examples of the acetophenone compound 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, 2-benzyl-2. -Dimethylamino-1-(4-morpholinophenyl)-butan-1-one and the like can be mentioned.

Examples of the benzophenone 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, 3,3′-dimethyl-2-methoxybenzophenone and the like can be mentioned.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis(trichloromethyl)-s-triazine, and 2-(3',4'-dimethoxystyryl). -4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine , Bis(trichloromethyl)-6-styryl-s-triazine, 2-(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-methoxy) Styryl)-s-triazine and the like.

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(o-acetyloxime. )-1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one and the like are used. be able to. Specific examples of the O-acyl oxime compound 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- Examples include oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

The photopolymerization initiator may include an oxime-based initiator and an acetophenone-based initiator at the same time. In this case, curing efficiency can be increased and an excellent process margin can be secured as compared with the case where only one type of photopolymerization initiator is used. In this case, the oxime-based initiator may be included in a larger amount than the acetophenone-based initiator. When the oxime-based initiator is included in a larger amount than the acetophenone-based initiator, the sensitivity is low (sensitivity is excellent) and desired CD can be realized.

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

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

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionic acid, pentaerythritol tetrakis-3-mercaptopropionic acid, dipentaerythritol tetrakis-3-mercaptopropionic acid, and the like.

The photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, for example, 0.1% by weight to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, curing sufficiently occurs at the time of exposure in the pattern forming step, excellent reliability can be obtained, and heat resistance of the pattern, light resistance and chemical resistance are excellent, It has excellent resolution and adhesion, and can prevent a decrease in transmittance due to an unreacted initiator.

(E) Solvent As the solvent, a substance that is compatible with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator, but does not react can be used.
Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; glycols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethers; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate; methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc. Carbitols; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, acetic acid-n-butyl 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; methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Alkoxyacetic acid alkyl esters such as ethyl; methyl 3-oxypropionate, 3-oxypropionic acid alkyl esters such as ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy 3-Alkoxypropionic acid alkyl esters such as ethyl propionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate Alkyl ester; 2-oxy-2-methylpropionate such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; methyl 2-methoxy-2-methylpropionate, Monoalkyl monooxymonocarboxylates of alkyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate and the like; ketone acid esters such as ethyl pyruvate and the like, and 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, acetic acid High boiling point solvents such as benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate can be mentioned.

Of these, preferably in consideration of compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; 2-hydroxypropion Esters such as ethyl acid; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in the balance, for example, 20 wt% to 80 wt%, for example 25 wt% to 60 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included in the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability is excellent in manufacturing the color filter.

Other Additives The photosensitive resin composition according to one embodiment may further include an epoxy compound in order to improve adhesion with a substrate.

Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 to 20% by weight, for example, 0.1 to 10% by weight, based on the total amount of the photosensitive resin composition. When the epoxy compound is included in the above range, the adhesiveness, the storability, etc. are excellent.

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group in order to improve adhesiveness with a substrate. ..

Examples of the silane coupling agent, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γisocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyl Sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Examples thereof include propyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatepropyltriethoxysilane. These can be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 wt% to 10 wt% based on the total amount of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesiveness, storability, etc. are excellent.

In addition, the photosensitive resin composition may further include a surfactant for improving coating properties and preventing defect formation, if necessary.

Examples of the surfactant include BM-1000 (registered trademark) and BM-1100 (registered trademark) manufactured by BM Chemie; maker pack F142D (registered by Dainippon Ink and Chemicals, Inc.) (registered) Trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark), F554 (registered trademark) and the like; 3M Japan (former: Sumitomo 3M) Fluorad FC-135 (registered Trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark), etc.; AGC (former: Asahi Glass) Co., Ltd. Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark), etc.; SH-28PA (registered trademark) manufactured by Dow Toray Industries, Inc. ), the same -190 (registered trademark), the same -193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark) and the like. You can

The surfactant may be used in an amount of 0.001% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, unevenness does not occur, and wettability with respect to the glass substrate is excellent.

Further, the photosensitive resin composition may be added with a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

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

The pattern forming process in the photosensitive resin film is as follows.

Applying the photosensitive resin composition onto a supporting substrate by spin coating, slit coating, inkjet printing, etc.; drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film to light; developing the exposed photosensitive resin composition film with an alkaline aqueous solution to produce a photosensitive resin film; and heat treating the photosensitive resin film. .. Since the conditions in the above process and the like are widely known in the art, detailed description thereof will be omitted in this specification.

According to another embodiment, a color filter including the photosensitive resin film is provided.

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

(Synthesis of dye)
Synthesis Example 1: Synthesis of Dye Represented by Chemical Formula 1-1 A round bottom flask was charged with 30 g (0.2 mol) of terephthalaldehydic acid, and 600 g of propionic acid was added thereto and stirred. Let After adding 13.5 g (0.2 mol) of pyrrole to the reaction product, the reaction product was heated to 80° C. and stirred for 1 hour, then heated at 130° C. and stirred for 1.5 hours, and then terminated. It was The reaction product was cooled to room temperature (23° C.), 300 g of acetone was added thereto, and the mixture was stirred at room temperature for 1 hour and then filtered. Then, the solid compound existing on the filter was collected, washed with acetone, and then dried to synthesize 8.3 g (26%) of intermediate (A).

Then, 24.5 g (30.1 mmol) of the intermediate (A) synthesized above and 34.3 g (241 mmol) of K ₂ CO ₃ were placed in a round bottom flask, and 250 g of dimethylformamide (DMF) was added thereto. Allowed to stir. After adding 46.5 g (241 mmol) of 1-bromo-2-ethylhexane (1-bromo-2-ethylhexane) thereto, the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, DMF was removed through distillation, and then the mixture was extracted with methylene chloride (MC), washed with 10% NaCl and deionized water (DI water). Then, the solvent was removed through distillation, and MeCN (cyanomethane; acetonitile) was added thereto for washing, followed by drying to obtain 28.9 g (75%) of intermediate (B).

After that, 1.0 g (0.81 mmol) of the intermediate (B) synthesized above and 0.44 g (2.42 mmol) of Cu(OAc) ₂ H ₂ O (copper acetate hydrate) were placed in a round bottom flask, After adding DMF10g here, it stirred at 100 degreeC for 15 hours. After the reaction was completed, the temperature was lowered to room temperature, DMF was removed through distillation, and then the mixture was extracted with MC and washed with 10% NaCl and deionized water (DI water). Then, the solvent was removed through distillation, the reaction product was dissolved with a minimum amount of MC, and then gradually dropped into 100 g of MeCN to cause precipitation. The precipitate was filtered, washed with MeCN and then dried to obtain 0.9 g (86%) of a compound represented by the following chemical formula 1-1.

LC Mass (liquid chromatography mass spectrometry): 1299 m/z.

Synthesis Example 2: Synthesis of Dye Represented by Chemical Formula 1-2 With respect to 1.0 g (0.81 mmol) of the intermediate (B), vanadium oxide hydrate (instead of Cu(OAc) ₂ H ₂ O ( 0.84 g of a compound represented by the following chemical formula 1-2 was performed in the same manner as in Synthesis Example 1, except that the temperature was raised to 120° C. using Vanadium oxide sulfide hydrate (2.42 mmol). (80%) was obtained.

LC Mass: 1303 m/z.

Comparative Synthesis Example 1: Synthesis of Dye Represented by Chemical Formula 1-3 3.2 g (2.58 mmol) of the intermediate (B) was placed in one round bottom flask, 160 g of chloroform was added thereto, and the temperature was changed to 60°C. It was stirred at. 1.42 g (7.74 mmol) of Zn(OAc) ₂ was placed in another round-bottomed flask, 30 g of MeOH was placed therein, and the mixture was stirred at room temperature to dissolve Zn(OAc) ₂ (Zinc acetate). Then, the Zn(OAc) ₂ solution was added to the flask containing the intermediate (B), and the reaction was performed for 2 hours with stirring. When the reaction was completed, the temperature was lowered to room temperature, followed by extraction with MC and washing with 10% NaCl and deionized water (DI water). After removing the solvent through distillation, the reaction product was dissolved with a minimum amount of MC and then gradually dropped into 100 g of MeCN to cause precipitation. The precipitate was filtered, washed with MeCN, and dried to obtain 3.1 g (92%) of a compound represented by the following chemical formula 1-3.

LC Mass: 1300 m/z.

(Synthesis of photosensitive resin composition)
Example 1, Example 2, and Comparative Examples 1 to 3
The components mentioned below were mixed in the composition shown in Table 1 below to prepare photosensitive resin compositions according to Example 1, Example 2 and Comparative Examples 1 to 3.

Specifically, after dissolving the photopolymerization initiator in the solvent, the mixture was stirred at room temperature for 2 hours, the binder resin and the photopolymerizable compound were added thereto, and the mixture was stirred at room temperature for 2 hours. Next, a colorant and other additives were added to the obtained reaction product and stirred at room temperature for 1 hour. Then, the photosensitive resin composition was manufactured by filtering the product 3 times to remove impurities.

(A) Colorant (A-1) C.I. I. Pigment Blue 15:6 pigment dispersion liquid (GC1679, manufactured by SANYO; pigment solid content 10% by weight).
(A-2) C.I. I. Pigment Blue 15:6 pigment dispersion liquid (GC1207, manufactured by SANYO; pigment solid content 10% by weight).
(A-3) Compound of Comparative Synthesis Example 1 (dye represented by Chemical Formula 1-3)
(A-4) Compound of Synthesis Example 1 (dye represented by Chemical Formula 1-1)
(A-5) Compound of Synthesis Example 2 (dye represented by chemical formula 1-2)
(B) Binder resin Acrylic binder resin (CRB-400H, manufactured by SMS)
(C) Photopolymerizable compound dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku Co., Ltd.)
(D) Photopolymerization initiator Oxime compound (OXE01, manufactured by BASF)
(E) Solvent Propylene glycol methyl ether acetate (Kyowa Kako Co., Ltd.)
(F) Additive Fluorine-based surfactant (F-554, manufactured by DIC Corporation).

Evaluation: Bx color coordinates and light resistance A photosensitive resin composition prepared in Example 1 and Example 2 and Comparative Examples 1 to 3 with a thickness of 1 μm to 3 μm on a degreased and washed glass substrate having a thickness of 1 mm. Was applied under the condition of 250 rpm to 350 rpm and dried on a hot plate at 90° C. for 2 minutes to obtain a coating film. Then, the coating film is exposed on the whole surface under the condition of 50 mJ/cm ² by using a high pressure mercury lamp having a main wavelength of 365 nm, and then washed with KOH developer (111 times diluted solution) with a developing machine. Development was carried out for 60 seconds under the condition of liquid/developing solution=1/0.8 (mass ratio), followed by washing for 60 seconds again to give a development history. Then, it was dried in a hot air circulation type drying oven at 230° C. for 20 minutes to obtain a color sample.

After measuring the CIE color coordinates and luminance (Y) before and after light resistance using a spectrophotometer (MCPD3000, manufactured by Otsuka electronic Co., Ltd.) on the obtained color test piece, a change value by light resistance evaluation was calculated, The results are shown in Tables 2 and 3 below.

*Light fastness evaluation: A light fastness test was carried out by exposing the color test piece to a Xenon lamp (0.68 W) at 60° C. for 20 hours under the respective environmental conditions of Air and N ₂ gas.

From the above Tables 2 and 3, when the azaporphyrin dye represented by the chemical formula 1-1 or the chemical formula 1-2 is used together with a blue pigment, a small amount of the azaporphyrin dye can be used in a blue resist while maintaining excellent light resistance. It can be confirmed that high color can be realized.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention. Of course, this also belongs to the scope of the present invention.

In the present specification,
Bx: In the CIE color coordinates represented by (x, y), it is the Bx value of the color coordinates (Bx, By) of the blue area (B);
High color: Expressed as a higher color is realized as the Bx value of the color coordinates (Bx, By) of the blue area (B) is smaller (C light source reference);
Del(x): the amount of change in the Bx value of the color coordinates (Bx, By) of the blue area (B) (after processing Bx-before processing Bx);
Del(y): change amount of By value in the color coordinates (Bx, By) of the blue area (B) (after-processing By-before-processing By);
Del(Y): Amount of change in brightness (after processing Y-before processing Y);
Del(E ^* ): Color difference between the color sample before and after the treatment (the smaller the color difference, the better the light resistance). Del(E ^* ) can be represented by the following formula.

In the above formula, ΔL ^* =L ^* _t− L ^*
Δa ^* =a ^* _t− a ^*
Δb ^* =b ^* _t− b ^*
L ^* _t , a ^* _t , b ^* _t : L ^* a ^* b ^* value after processing
L ^* , a ^* , b ^* : L ^* a ^* b ^* values before processing.

Claims (13)

(A) a colorant containing a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in the wavelength region of 350 nm to 450 nm;
(B) a binder resin,
(C) a photopolymerizable compound,
(D) a photopolymerization initiator,
(E) a solvent,
A photosensitive resin composition comprising: The photosensitive resin composition according to claim 1, wherein the central metal of the azaporphyrin dye is Cu or V(=O). The photosensitive resin composition according to claim 1, wherein the azaporphyrin dye is represented by the following chemical formula 1.

In the above chemical formula 1,
M is Cu or V (=O),
R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted An aryl group having 6 to 20 carbon atoms, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted alkyl ester group having 1 to 20 carbon atoms,
However, at least one or more of R ^{1 to} R ⁵ , at least one or more of R ^{6 to} R ¹⁰ , at least one or more of R ^{11 to} R ¹⁵ , and at least one of R ^{16 to} R ^20. One or more is not independently a hydrogen atom. One of R ^{1 to} R ⁵ , one of R ^{6 to} R ¹⁰ , one of R ^{11 to} R ¹⁵ and one of R ^{16 to} R ²⁰ are each independently. The photosensitive resin composition according to claim 3, which is represented by the following chemical formula 2:

In the above chemical formula 2,
R ²¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition according to claim 4, wherein R ³ , R ⁸ , R ¹³ and R ¹⁸ are each independently represented by the following chemical formula 3:

In the above chemical formula 3,
L ¹ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,
R ²² and R ²³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition according to claim 1, wherein the azaporphyrin-based dye is represented by the following chemical formula 1-1 or chemical formula 1-2.
7. The photosensitive material according to claim 1, wherein the azaporphyrin-based dye is contained in an amount of 0.1% by weight to 5% by weight based on the total solid content of the photosensitive resin composition. Resin composition. The photosensitive resin composition according to claim 1, wherein the colorant further contains a violet pigment. The blue pigment is C.I. I. Pigment Blue 15:6, The photosensitive resin composition as described in any one of Claims 1-9. The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
2% to 40% by weight of the colorant,
3 wt% to 20 wt% of the binder resin,
1% by weight to 20% by weight of the photopolymerizable compound,
0.1% to 5% by weight of the photopolymerization initiator,
With the residual amount of the solvent,
The photosensitive resin composition according to any one of claims 1 to 9, which comprises: The photosensitive resin composition according to claim 1, further comprising an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof. A photosensitive resin film produced using the photosensitive resin composition according to claim 1. A color filter comprising the photosensitive resin film according to claim 12.