TW201725448A - Photosensitive resin composition, photosensitive resin layer and color fliter - Google Patents

Abstract

Provided are a photosensitive resin composition including a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 as a colorant, a photosensitive organic layer manufactured using the same, and a color filter including the photosensitive organic layer. [Chemical Formula 1] [Chemical Formula 2] In Chemical Formula 1, each substituent is the same as defined in the detailed description.

Description

Photosensitive resin composition, photosensitive resin layer, and color filter

The present invention relates to a resin composition, and more particularly to a photosensitive resin composition, a photosensitive resin layer, and a color filter.

The color filter manufactured by using the pigment type photosensitive resin composition has limitations in brightness and contrast ratio due to the particle diameter of the pigment. Further, in the case of a color image forming apparatus which is an image sensor, it is required to have a small dispersed particle diameter to provide a fine pattern. In response to the above requirements, continuous attempts have been made to provide color filters having improved color characteristics such as brightness and contrast ratio by preparing a photosensitive resin composition containing a dye which does not form particles instead of a pigment.

However, dyes (especially dyes having a single molecular structure) have poor durability, and thus it is pointed out that the dyes are not suitable for use in the manufacturing process of color filters. For example, a photosensitive resin composition containing a single molecule dye may cause agglomeration and elution problems between dyes due to a high temperature heat history during the manufacturing process of the color filter, and it is processed together with other materials. When the dye is poor in durability. That is, a color filter containing a dye-type photosensitive resin composition may cause problems in color characteristics and reliability.

Therefore, studies have been continued on compounds (especially compounds having excellent color reproducibility) which are suitable as coloring agents for photosensitive resin compositions.

An embodiment of the present invention provides a photosensitive resin composition.

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

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

An embodiment of the present invention provides a photosensitive resin composition comprising a compound represented by Chemical Formula 1 as a colorant and a compound represented by Chemical Formula 2. [Chemical Formula 1] [Chemical Formula 2] In Chemical Formula 1 and Chemical Formula 2, R1 to R16 are independently a hydrogen atom, a chlorine atom, a bromine atom or a substituted or unsubstituted C1 to C20 alkyl group, and the limitation is that one to three of R1 to R16 are bromine Atom, and R17 to R21 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

R ¹ to R ¹⁶ may independently be a chlorine atom or a bromine atom.

R ¹⁷ to R ¹⁹ and R ²¹ may independently be a hydrogen atom and R ²⁰ may be a substituted or unsubstituted C1 to C20 alkyl group.

The compound represented by Chemical Formula 1 may be a green pigment and the compound represented by Chemical Formula 2 may be a yellow pigment.

The compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be contained in a weight ratio of 20:80 to 80:20.

The compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be contained in a weight ratio of 50:50 to 75:25.

The colorant may be contained in an amount of 10% by weight to 30% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further contain a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an antioxidant, and a solvent.

The binder resin may be an acrylic binder resin.

The photosensitive resin composition may further contain an epoxy-based binder resin.

The antioxidant can be represented by Chemical Formula 3. [Chemical Formula 3] In Chemical Formula 3, L1 to L8 are independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted a C6 to C20 arylene group, and R22 to R41 are independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted group. Or an unsubstituted C6 to C20 aryl group, at least one of R22 to R26, at least one of R27 to R31, at least one of R32 to R36, and at least one of R37 to R41 are a hydroxyl group, and R22 to R26 At least two of them, at least two of R27 to R31, at least two of R32 to R36, and at least two of R37 to R41 are a t-butyl group.

L ¹ to L ⁸ may independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant can be represented by Chemical Formula 4. [Chemical Formula 4]

The antioxidant can be represented by Chemical Formula 5. [Chemical Formula 5]

The photosensitive resin composition may contain 10 wt% to 30 wt% of the color former; 1 wt% to 30 wt% of the binder resin; 1 wt% to 20 wt% of the total amount of the photosensitive resin composition Photopolymerizable monomer; 0.1 wt% to 10 wt% of a photopolymerization initiator; 0.01 wt% to 1 wt% of an antioxidant; and a remaining amount of a solvent.

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

Another embodiment of the present invention provides a photosensitive resin layer produced using a photosensitive resin composition.

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

Other embodiments of the invention are included in the following embodiments.

The photosensitive resin composition according to an embodiment of the present invention can obtain a color coordinate having high color reproducibility even without using an excessive coloring agent, and can provide a color filter having improved brightness, heat resistance, and chemical resistance. .

Embodiments of the invention are set forth in detail below. However, the embodiments are exemplary, and the invention is not limited thereto and the invention is defined by the scope of the claims.

In the present specification, the term "substituted" means that at least one hydrogen of a functional group is substituted with at least one substituent selected from the group consisting of halogen (F, Br, Cl or I), a hydroxyl group, and a nitrate when a specific definition is not additionally provided. a cyano 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 and independently a C1 to C10 alkyl group , anthracenyl, fluorenyl, fluorenyl, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted An alkoxy group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

In the present specification, the term "alkyl" means a C1 to C20 alkyl group and especially a C1 to C15 alkyl group, and the term "cycloalkyl group" means a C3 to C20 cycloalkyl group and especially C3, when a specific definition is not additionally provided. To C18 cycloalkyl, the term "alkoxy" refers to a C1 to C20 alkoxy group and especially a C1 to C18 alkoxy group, and the term "aryl" refers to a C6 to C20 aryl group and especially a C6 to C18 aryl group, the term "Alkenyl" refers to C2 to C20 alkenyl and especially C2 to C18 alkenyl, the term "alkylene" refers to C1 to C20 alkylene and especially C1 to C18 alkylene, and the term "arylene" is Refers to C6 to C20 arylene and especially C6 to C16 arylene.

In the present specification, the term "aliphatic organic group" means a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkylene group, C2 to when a specific definition is not otherwise provided. C20 alkenylene or C2 to C20 alkynylene, and especially C1 to C15 alkyl, C2 to C15 alkenyl, C2 to C15 alkynyl, C1 to C15 alkylene, C2 to C15 alkenylene or C2 to C15 Alkynylene, the term "alicyclic organic group" means C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C3 to C20 cycloalkylene, C3 to C20 cycloalkylene Or a C3 to C20 cycloalkynylene group, and especially a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene group, a C3 to C15 cycloalkenylene group or C3 to C15 cycloalkynylene, the term "aromatic organic group" means C6 to C20 aryl or C6 to C20 arylene, and especially C6 to C16 aryl or C6 to C16 arylene, the term "hetero "Cycloalkyl" means C2 to C20 cycloalkyl, C2 to C20 cycloalkylene, C2 to C20 cycloalkenyl, C2 to C20 cycloalkenylene, C2 to C20 cycloalkynyl, C2 to C20 cycloalkynylene, a C2 to C20 heterocyclic ring containing 1 to 3 hetero atoms selected from O, S, N, P, Si, and combinations thereof in the ring Or a C2 to C20 heteroarylene group, and especially a C2 to C15 cycloalkyl group, a C2 to C15 cycloalkylene group, a C2 to C15 cycloalkenyl group, a C2 to C15 cycloalkenylene group, a C2 to C15 cycloalkynyl group, A C2 to C15 cycloalkynyl group, a C2 to C15 heteroaryl group or a C2 to C15 heteroarylene group containing 1 to 3 hetero atoms selected from O, S, N, P, Si, and combinations thereof in the ring.

In the present specification, the term "combination" means mixing or copolymerization when a definition is not otherwise provided. Further, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means a block copolymer to a random copolymer.

In the present specification, the term "hetero" means that at least one hetero atom selected from N, O, S and P is contained in the chemical formula when a specific definition is not additionally provided.

In the present specification, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" when a specific definition is not additionally provided. And "methacrylic acid".

In the chemical formula of the present specification, unless a specific definition is additionally provided, when a chemical bond is not drawn at a position to be given, hydrogen bonding is at the position.

In the present specification, "*" indicates a point connecting the same or different atoms or chemical formulas when a specific definition is not additionally provided.

In one embodiment, a photosensitive resin composition comprising a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 as a colorant is provided. [Chemical Formula 1] [Chemical Formula 2]

In Chemical Formula 1 and Chemical Formula 2, R ¹ to R ^{16 are} independently a hydrogen atom, a chlorine atom, a bromine atom or a substituted or unsubstituted C1 to C20 alkyl group, and the restriction is one of R ¹ to R ¹⁶ to Three are bromine atoms, and R ¹⁷ to R ^{21 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

Generally, the color filter is made of red (R), green (G), blue (B) dye or pigment, and the colorant converts the white light of the backlight unit into each corresponding color (red (R), The role of green (G) and blue (B)). Recently, according to the development of the display industry, it is more desirable to use Adobe or DCI color coordinates that can achieve higher color reproducibility than NTSC color coordinates, but only Adobe or DCI color coordinates with high color reproducibility are provided by conventional colorants. difficult. (Adobe or DCI color coordinates have a wider range of color reproducibility than NTSC color coordinates, thus facilitating high color reproducibility.) In addition, even by using an excess of conventional colorants to achieve desirable color reproducibility However, the processability is disadvantageously deteriorated due to an excessive amount of the coloring agent.

However, the photosensitive resin composition containing a colorant according to an embodiment can provide an Adobe or DCI color coordinate with high color reproducibility (even if a small amount of coloring agent is used) while ensuring workability and reliability ( Heat resistance, chemical resistance, etc.).

The photosensitive resin composition according to an embodiment may further contain a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an antioxidant, and a solvent, and a color former.

In the following, each component is explained in detail.

Colorant

A photosensitive resin composition according to an embodiment comprising a compound represented by Chemical Formula 1 as a colorant and a compound represented by Chemical Formula 2.

The compound represented by Chemical Formula 1 can be darkened due to 1 to 3 bromine atoms.

For example, R ¹ to R ¹⁶ may independently be a chlorine atom or a bromine atom.

For example, the compound represented by Chemical Formula 1 contains 1 to 3 bromine atoms and 13 to 15 chlorine atoms. In this case, it is easy to obtain a deeper and darker color.

A photosensitive resin composition according to an embodiment, which comprises, in addition to the compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2 as a colorant. In particular, when a color filter including a photosensitive resin layer obtained by using a green photosensitive resin composition is produced, it can be sufficiently ensured by using a smaller amount of a coloring agent than in the case of using only the compound represented by Chemical Formula 1. Color reproducibility, workability, reliability, etc.

For example, in Chemical Formula 2, R ¹⁷ to R ¹⁹ and R ²¹ may independently be a hydrogen atom, and R ²⁰ may be a substituted or unsubstituted C1 to C20 alkyl group.

For example, the compound represented by Chemical Formula 1 may be a green pigment and the compound represented by Chemical Formula 2 may be a yellow pigment.

In particular, the compound represented by Chemical Formula 1 can provide a darker and darker green than the conventional green pigment, and the compound represented by Chemical Formula 2 can provide a deeper and darker yellow than the conventional yellow pigment.

Further, as described above, by using the compound represented by Chemical Formula 1 as the green pigment and the yellow pigment represented by Chemical Formula 2, the amount of the colorant can be reduced to improve the workability, and at the same time, the color coordinates can have high color reproducibility.

For example, when the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are contained in a weight ratio of 20:80 to 80:20 (for example, 50:50 to 75:25, for example, 60:40 to 70:30) At the same time, color reproducibility can be more improved.

The coloring agent may be contained in an amount of 10% by weight to 30% by weight based on the total amount of the photosensitive resin composition. When the coloring agent in the range of the amount is contained, color reproducibility can be enhanced without deteriorating reliability (for example, heat resistance, chemical resistance, etc.). In particular, when less than 10% by weight of the coloring agent is contained based on the total amount of the photosensitive resin composition, the reliability is deteriorated too much to provide a color filter having excellent color characteristics such as brightness and contrast ratio. On the other hand, when more than 30% by weight of the coloring agent is contained based on the total amount of the photosensitive resin composition, it may have excellent color characteristics, but the workability may be deteriorated.

The colorant may be contained in the photosensitive resin composition in the form of a dispersion.

The primary particle diameter of the colorant can range from 10 nm to 80 nm, such as from 10 nm to 70 nm. When the primary particle diameter is in the range of the particle diameter, it is preferable because its stability is excellent and it is not necessary to worry about degradation of the pixel resolution.

The solvent used in the dispersion may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether or 3-methyl. Oxy-1-butanol, and wherein propylene glycol methyl ether acetate can be desirable. Herein, the amount of the solvent can be desirably controlled such that the solid content of the dispersion may be from 5 wt% to 30 wt%, but is not limited thereto.

The solvent may comprise the remaining amount of solvent, which may comprise, for example, from 30 wt% to 90 wt%, such as from 40 wt% to 90 wt%, such as from 50 wt% to 90 wt%, such as 60 wt%, based on 100 wt% of the dispersion. % to 90 wt%, for example 70 wt% to 90 wt%, for example 80 wt% to 90 wt% of the remaining amount of solvent.

The dispersion may also contain a dispersing agent. The dispersant may be a nonionic, anionic or cationic dispersant, such as a polyalkylene glycol and its esters, a polyoxyalkylene, a polyol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate a sulfonate, a carboxylic acid ester, a carboxylate, a alkylguanamine alkylene oxide addition product, an alkylamine, and the like. These dispersants may be used singly or in combination of two or more than two.

The dispersant may be contained in an amount of from 0.01% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant in the above range is contained, the photosensitive resin composition has excellent stability, developability, and pattern forming ability due to improved dispersion characteristics.

Binder resin

The photosensitive resin composition according to an embodiment may contain a binder resin such as 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 is a resin containing at least one acrylic repeating unit.

The acrylic binder resin may be a copolymer of a second ethylenically unsaturated monomer.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group. Examples of the monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

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

The diene unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylic acid ester compound such as (A) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, etc.; aminoalkyl ester compound of unsaturated carboxylic acid, such as 2-aminoethyl (meth)acrylate, 2-(meth)acrylic acid Dimethylaminoethyl ester or the like; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth)acrylate; an acrylonitrile compound For example, (meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth) acrylamide or the like; and the like. These may be used singly or in the form of a mixture of two or more than two.

Specific examples of the acrylic binder resin may be (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/ Benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, benzyl methacrylate An ester copolymer or the like, but is not limited thereto. These may be used singly or in the form of a mixture of two or more than two.

The acrylic binder resin may have a weight average molecular weight of from 3,000 g/mol to 150,000 g/mol, for example from 5,000 g/mol to 50,000 g/mol, for example from 6,000 g/mol to 10,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition can have excellent physical and chemical characteristics as well as appropriate viscosity, maintain appropriate developability and sensitivity, and be colored in color filter. During the manufacture of the light sheet, excellent characteristics of close contact with the substrate are exhibited.

The acrylic binder resin may have an acid value of from 15 mgKOH/g to 60 mgKOH/g, for example, from 20 mgKOH/g to 50 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the picture element has excellent resolution.

The binder resin in a solid form can be dissolved in a solvent to be described later. The binder resin in a solid form may be contained in an amount of 15% by weight to 40% by weight based on the total amount of the binder resin dissolved.

The binder resin may be contained in an amount of 0.5% by weight to 15% by weight, for example, 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin in the range is included, the developability can be improved, and excellent surface smoothness can be improved due to improved crosslinking during the manufacture of the color filter.

The photosensitive resin composition according to an embodiment may further contain an epoxy-based binder resin.

The epoxy-based binder resin is a resin containing an epoxy resin, and thus its heat resistance is improved. The epoxy resin may be, for example, a phenol novolac epoxy resin, a tetramethylbiphenyl epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is not limited thereto.

Further, the epoxy-based binder resin can contribute to formation of a picture having a desired resolution during development while ensuring dispersion stability of the colorant. In particular, the epoxy resin in the epoxy-based binder resin can improve the compatibility between the colorant and the binder resin.

The epoxy equivalent of the epoxy resin can range from 150 g/eq to 200 g/eq. When the epoxy resin having an epoxy equivalent within the above range is contained in the binder resin, the binder can improve the degree of curing of the pattern and promote the adhesion of the colorant in the patterned structure.

The binder resin may be contained in an amount of from 1 wt% to 30 wt%, for example from 1 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin in the range is present, developability and crosslinking are improved to provide excellent surface smoothness during the manufacture of the color filter.

Photopolymerizable monomer

The photopolymerizable monomer may be a (meth)acrylic monofunctional or polyfunctional ester containing at least one ethylenically unsaturated double bond.

The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during exposure of the pattern forming process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A (meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (methyl) Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol single Methyl ether (meth) acrylate, trimethylolpropane tri(meth) acrylate, tris(meth) propylene methoxyethyl phosphate, phenol aldehyde epoxy (meth) acrylate, and the like.

Commercially available examples of photopolymerizable monomers are as follows. The monofunctional (meth) acrylate may comprise Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); Kaya KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic Chemical Co., Ltd.) Ind., Ltd.)) and so on. Examples of the difunctional (meth) acrylate may include Aronix M-210 ^® , M-240 ^® , M-6200 ^® (East Asia Chemical Co., Ltd.), KAYARAD HDDA ^® , HX -220 ^® , R-604 ^® (Nippon Chemical Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth) acrylates may include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M- 8060 ^® (East Asia Chemical Co., Ltd.), KAYARAD TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Japan Chemicals Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Organic Chemical Co., Ltd.), etc. These may be used singly or in the form of a mixture of two or more than two.

The photopolymerizable monomer can be treated with an acid anhydride to improve developability.

The photopolymerizable monomer may be contained in an amount of from 1 wt% to 20 wt%, for example from 1 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer in the range is contained, the photopolymerizable monomer is sufficiently cured during exposure of the pattern forming process and has excellent reliability, and the developability of the alkaline developer can be improved.

Photopolymerization initiator

The photopolymerization initiator may be a photopolymerization initiator commonly used in the photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an anthraquinone-based compound, or the like.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl group. Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (methylthio)phenyl)-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4- Base-phenyl)-butan-1-one and the like.

Examples of the benzophenone-based compound may be benzophenone, benzhydryl benzoate, benzhydryl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobiphenyl Ketone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or the like.

Examples of the triazine-based compound may be 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(trichloro) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-double (trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s- Triazine, 2-(naphthoquinone-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthoquinone-1-yl)-4,6-double (trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperidinyl-s-triazine, 2-4-bis(trichloromethyl)-6- (4 -Methoxystyryl)-s-triazine and the like.

Examples of the lanthanoid compound may be an O-indenyl lanthanide compound, 2-(o-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1- (o-Ethyl hydrazide)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxygen Amino-1-phenylpropan-1-one and the like. A specific example of the O-mercapto lanthanide compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl) -Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-but-1,2-dione 2-indole-O-benzoate, 1-(4-phenylthio) Phenyl)-octane-1,2-dione 2-indole-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, 1- (4-phenylthiophenyl)-butan-1-one oxime-O-acetate or the like.

In addition to the above compounds, the photopolymerization initiator may further contain an oxazole compound, a diketone compound, a lanthanum borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator can be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and being excited and then transmitting its energy.

Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-mercaptopropionate, dipentaerythritol tetrakis-mercaptopropionate or the like.

The photopolymerization initiator may be contained in an amount of 0.1% by weight to 10% by weight, for example, 0.1% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator in the range is included, sufficient photopolymerization occurs during the exposure of the pattern forming process, excellent reliability can be obtained, and heat resistance, light resistance, chemical resistance, and resolution of the pattern can be improved. And close contact characteristics, and can prevent the transmittance from deteriorating due to the non-reactive starter.

Antioxidants

The photosensitive resin composition according to an embodiment further contains an antioxidant and the antioxidant can be represented by Chemical Formula 3. [Chemical Formula 3]

In Chemical Formula 3, L ¹ to L ^{8 are} independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted Substituted C6 to C20 arylene, R ²² to R ^{41 are} independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group a substituted or unsubstituted C6 to C20 aryl group, at least one of R ²² to R ²⁶ , at least one of R ²⁷ to R ³¹ , at least one of R ³² to R ³⁶ and R ³⁷ to R ⁴¹ At least one of the hydroxyl groups, and at least two of R ²² to R ²⁶ , at least two of R ²⁷ to R ³¹ , at least two of R ³² to R ³⁶ , and at least two of R ³⁷ to R ⁴¹ One is tert-butyl.

The antioxidant can have excellent heat resistance and chemical resistance due to the structure of Chemical Formula 3.

In general, the photosensitive resin composition generates radicals at a high temperature or the like in the post-treatment, and the radicals deteriorate the heat resistance and chemical resistance of the composition. However, the photosensitive resin composition according to an embodiment further contains an antioxidant to deactivate the radical, and thus excellent heat resistance and chemical resistance can be ensured.

In particular, free radicals generated at high temperatures are highly reactive and react with adjacent oxygen (see Reaction Scheme 1), and are then rapidly bonded to the hydroxyl groups of di-tert-butylphenol, ie, the substituents contained in the antioxidant. And inactivated (refer to Reaction Scheme 2).

[Reaction Scheme 1]

R ̇ + O ₂ → ROO ̇

[Reaction Scheme 2]

ROO ̇ + hydroxyl group of di-tert-butylphenol → ROOH

For example, L ¹ to L ⁸ may independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant can be represented by Chemical Formula 4. [Chemical Formula 4]

For example, the antioxidant can be represented by Chemical Formula 5. [Chemical Formula 5]

The antioxidant may be included in an amount of 0.01 wt% to 1 wt%, for example, 0.01 wt% to 0.5 wt%, for example, 0.01 wt% to 0.1 wt%, based on 100 wt% of the photosensitive resin composition. When the antioxidant is within the range, color change is minimized and heat resistance and chemical resistance are improved.

Solvent

The solvent is a material having compatibility with, but not reacting with, a coloring agent, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an antioxidant, and the like.

Examples of the solvent may include an alcohol such as methanol, ethanol, etc.; an ether such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran or the like; a glycol ether such as ethylene glycol monomethyl ether or ethylene Alcohol monoethyl ether, etc.; cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; carbitol, such as 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.; propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentyl Ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate Ester, isobutyl acetate, etc.; lactate, such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetate, such as methyl oxyacetate, ethyl oxyacetate, oxygen Butyl acetate and the like; alkyl alkoxyacetate, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. An alkyl 3-oxopropionate such as methyl 3-oxypropionate, ethyl 3-oxypropionate or the like; an alkyl 3-alkoxypropionate such as 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionate, such as 2-oxypropane Methyl ester, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionate, such as 2-oxy-2-methylpropane Methyl ester, ethyl 2-oxy-2-methylpropionate, etc.; alkyl monooxymonocarboxylate of alkyl 2-alkoxy-2-methylpropanoate, such as 2-methoxy Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , ethyl hydroxyacetate, 2-hydroxy-3-methyl Methyl butyrate or the like; a keto ester such as ethyl pyruvate. In addition, high boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di can also be used. Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, caproic acid, octanoic acid, 1-octanol, 1-indole Alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl acetate Cellulolytic agent, etc.

In view of miscibility and reactivity, a glycol ether such as ethylene glycol monoethyl ether or the like; ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; and the like; an ester such as 2-hydroxypropyl may be preferably used. Ethyl acetate or the like; carbitol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, and the like.

The solvent is used in the remaining amount, which is, for example, 20 wt% to 90 wt% based on the total amount of the photosensitive resin composition. When the solvent in the range is included, the photosensitive resin composition may have a suitable viscosity to improve the coating characteristics of the color filter.

Other additives

The photosensitive resin composition may further contain an epoxy compound, a decane coupling agent, a surfactant, or a combination thereof as an additive.

For example, the photosensitive resin composition may further contain an epoxy compound to improve characteristics in close contact with the substrate.

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

The epoxy compound may be contained in an amount of from 0.01 part by weight to 20 parts by weight and, for example, from 0.1 part by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound in the range is included, the close contact property, the storage property, and the like can be improved.

Further, the photosensitive resin composition may further contain a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl oxime group, an isocyanate group, an epoxy group or the like to improve adhesion to the substrate.

Examples of the decane coupling agent may include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate. Propyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These may be used singly or in the form of a mixture of two or more than two.

The decane coupling agent may be contained in an amount of from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a decane coupling agent in the above range is included, close contact characteristics, storage characteristics, and the like can be excellent.

Further, the photosensitive resin composition may further contain a surfactant to improve coating characteristics and prevent defects, if necessary.

Examples of surfactants are BM-1000 ^® and BM-1100 ^® (BM Chemie Inc.); MEGAFACE F 142D ^® , F 172 ^® , F 173 ^® and F 183 ^® (Daily Ink Chemical Industry) Ltd. (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135 ^® , FULORAD FC-170C ^® , FULORAD FC-430 ^® and FULORAD FC-431 ^® (Sumitomo 3M Co., Ltd) .)); SURFLON S-112 ^® , SURFLON S-113 ^® , SURFLON S-131 ^® , SURFLON S-141 ^® and SURFLON S-145 ^® (ASAHI Glass Co., Ltd.); -28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® and SF-8428 ^® (Toray Silicone Co., Ltd.); DIC Co., Ltd.) F-482, F-484, F-478, F-554, etc.

The surfactant may be included in an amount of from 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant in the above range is contained, coating uniformity is ensured, no dyeing is found, and the wettability to the glass substrate is excellent.

Further, unless the characteristics of the photosensitive resin composition are deteriorated, the photosensitive resin composition may further contain a predetermined amount of other additives such as an oxidation inhibitor, a stabilizer, and the like.

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

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

The pattern forming process of the color filter is as follows.

The process includes: coating a photosensitive resin composition according to an embodiment on a support substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied positive photosensitive resin composition to form a photosensitive resin composition film; exposing the positive photosensitive resin composition film; developing the exposed positive photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin layer; and performing the photosensitive resin layer Heat treatment. The conditions of the patterning process are well known in the relevant art and will not be described in detail in this specification.

In the following, the invention will be described in more detail with reference to examples, however, these examples should not be construed as limiting the scope of the invention in any way.

(Synthesis of photosensitive resin composition)

Instance 1 To instance 5 And comparative examples 1

According to the composition shown in Table 1, the following photopolymerization initiator was dissolved in the following solvent and then stirred at room temperature for 2 hours. A binder resin and a photopolymerizable monomer were added thereto and stirred at room temperature for 2 hours. A coloring agent was added thereto and stirred at room temperature for 1 hour, and an antioxidant and a surfactant were added and stirred at room temperature for 1 hour. The obtained solution was filtered 3 times to remove impurities, whereby the photosensitive resin compositions according to Examples 1 to 5 and Comparative Example 1 were obtained. Each component used to prepare the photosensitive resin composition is as follows:

Binder resin (A) epoxy-based binder resin (epoxy equivalent: 177 g/eq) (EHPE-3150, DIC Co., Ltd.) (B) Acrylic binder resin (SKY-095 or SKY-141) , Samsung SDI (Samsung SDI)

Photopolymerizable monomer Photopolymerizable monomer (dipentaerythritol hexaacrylate (DPHA)) (Nippon Chemical Co., Ltd.)

Photopolymerization initiator Lanthanide compound (IRGARCURE OXE01, manufactured by BASF)

The colorant (A) contains a pigment dispersion of G59 (DIC Co., Ltd.) (manufactured by ENF) (B) a pigment dispersion containing G58 (DIC Co., Ltd.) (manufactured by SKC) (C) contains Y185 (by YG Chemistry ( YG chem) manufactured pigment dispersion (manufactured by SKC) (D) contains Y138 (SANYO COLOR WORKS, Ltd.) pigment dispersion (manufactured by SKC)

Antioxidant Antioxidant of Chemical Formula 5 (IRGANOX 1010, manufactured by BASF) [Chemical Formula 5]

Solvent propylene glycol monomethyl ether acetate (PGMEA)

Other additives Surfactant (F-554, DIC Co., Ltd.)

[Table 1] (Unit: wt%)

Evaluation 1 : Color characteristics of photosensitive resin composition

Each of the photosensitive resin compositions according to Examples 1 to 5 and Comparative Example 1 was coated on a glass substrate with a coating apparatus (MIKASA Co., Ltd.) and at 90 ° C on a hot plate. Dry to obtain each film. The film was exposed to an exposure dose of 50 mJ/cm ² and baked in an oven condition of 230 ° C for 28 minutes. The film was further baked at 230 ° C for 1 hour, and before and after the post-baking (PSB), the color of the film was measured by using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD 3000). Coordinates and brightness, and the results are provided in Table 2. Color coordinates (Gx) and brightness (Y) are calculated based on the color coordinates (Gy).

[Table 2]

Evaluation 2 : heat resistance and chemical resistance of photosensitive resin composition

After measuring the color coordinates and brightness of Evaluation 1, the change values before and after the measurement were calculated to demonstrate heat resistance. Further, in order to obtain chemical resistance, the obtained film sample was immersed in N-methylpyrrolidone (NMP) at room temperature for 10 minutes, taken out and dried, and measured by a colorimeter similarly to the measurement of heat resistance. Next, the color difference before and after the measurement was calculated and compared in del(E*), and the results are shown in Table 3 below.

The references for evaluating heat resistance and chemical resistance are as follows: ○: The color del(E*) before and after baking is less than 2.5 Δ: The color del(E*) before and after baking is greater than or equal to 2.5 and less than 3.5 X: The color del(E*) before and after baking is greater than or equal to 3.5

[table 3]

Evaluation 3 : Patternability of photosensitive resin composition

Each of the photosensitive resin compositions according to Examples 1 to 5 and Comparative Example 1 was coated on a glass substrate with a coating apparatus (Sanken Co., Ltd.) and dried at 90 ° C on a hot plate to obtain each film. Each film obtained was exposed to an exposure dose of 50 mJ/cm ² and developed to obtain a pattern. The developer was prepared by diluting a KOH solution manufactured by Hoimyung, and then monitoring the time (seconds, BP) at which the pattern was displayed. In this case, BP can be at least less than or equal to 43 seconds. The developed pattern substrate was baked in an oven condition at 230 ° C for 30 minutes to complete patterning.

The obtained pattern was optically magnified 500 times by an optical microscope to measure the width of the found holes and patterns. The patternability was monitored by measuring the size by an optical microscope with reference to a width of 70 μm and a hole of 40 μm, and the results are shown in Table 4 below.

The reference for the evaluation of the pattern tear is as follows: ○: The pattern circumference and the close contact force are good when observed by the naked eye △: the pattern is torn when observed by the naked eye X: the pattern is layered when observed by the naked eye

[Table 4]

From Tables 2 to 4, it was confirmed that Examples 1 to 5 according to the present invention can provide high color reproducibility as well as excellent reliability and workability as compared with Comparative Example 1.

While the present invention has been described in connection with the embodiments of the present invention, it is understood that the invention is not intended to Equivalent configuration. Therefore, the above embodiments are to be considered as illustrative and not restrictive.

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Claims (18)

A photosensitive resin composition comprising a compound represented by Chemical Formula 1 as a colorant and a compound represented by Chemical Formula 2: [Chemical Formula 1] [Chemical Formula 2] Wherein, in Chemical Formula 1 and Chemical Formula 2, R ¹ to R ^{16 are} independently a hydrogen atom, a chlorine atom, a bromine atom or a substituted or unsubstituted C1 to C20 alkyl group, and the restrictions are in R ¹ to R ¹⁶ One to three are a bromine atom, and R ¹⁷ to R ^{21 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. The photosensitive resin composition as described in claim 1, wherein R ¹ to R ^{16 are} independently a chlorine atom or a bromine atom. The photosensitive resin composition according to claim 1, wherein R ¹⁷ to R ¹⁹ and R ^{21 are} independently a hydrogen atom, and R ²⁰ is a substituted or unsubstituted C1 to C20 alkyl group. The photosensitive resin composition as described in claim 1, wherein the compound represented by Chemical Formula 1 is a green pigment, and the compound represented by Chemical Formula 2 is a yellow pigment. The photosensitive resin composition as described in claim 1, wherein the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are contained in a weight ratio of from 20:80 to 80:20. The photosensitive resin composition according to claim 5, wherein the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are contained in a weight ratio of 50:50 to 75:25. The photosensitive resin composition according to claim 1, wherein the colorant is contained in an amount of 10% by weight to 30% by weight based on the total amount of the photosensitive resin composition. The photosensitive resin composition as described in claim 1, wherein the photosensitive resin composition further contains a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an antioxidant, and a solvent. The photosensitive resin composition as described in claim 8, wherein the binder resin is an acrylic binder resin. The photosensitive resin composition of the ninth aspect of the invention, wherein the photosensitive resin composition further contains an epoxy-based binder resin. The photosensitive resin composition according to claim 8, wherein the antioxidant is represented by Chemical Formula 3: [Chemical Formula 3] Wherein, in Chemical Formula 3, L ¹ to L ^{8 are} independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or Unsubstituted C6 to C20 arylene, R ²² to R ^{41 are} independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 An alkoxy group or a substituted or unsubstituted C6 to C20 aryl group, at least one of R ²² to R ²⁶ , at least one of R ²⁷ to R ³¹ , at least one of R ³² to R ³⁶ and R ³⁷ to At least one of R ⁴¹ is a hydroxyl group, and at least two of R ²² to R ²⁶ , at least two of R ²⁷ to R ³¹ , at least two of R ³² to R ³⁶ , and R ³⁷ to R ⁴¹ At least two are tert-butyl groups. The photosensitive resin composition according to claim 11, wherein L ¹ to L ^{8 are} independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group. The photosensitive resin composition according to claim 11, wherein the antioxidant is represented by Chemical Formula 4: [Chemical Formula 4] . The photosensitive resin composition according to claim 11, wherein the antioxidant is represented by Chemical Formula 5: [Chemical Formula 5] . The photosensitive resin composition according to claim 8, wherein the photosensitive resin composition contains: 10 wt% to 30 wt% of the coloring based on the total amount of the photosensitive resin composition 1 wt% to 30 wt% of the binder resin; 1 wt% to 20 wt% of the photopolymerizable monomer; 0.1 wt% to 10 wt% of the photopolymerization initiator; 0.01 From wt% to 1 wt% of the antioxidant; and the remaining amount of the solvent. The photosensitive resin composition as described in claim 1, wherein the photosensitive resin composition further contains an epoxy compound, a decane coupling agent, a surfactant, or a combination thereof. A photosensitive organic layer produced by using the photosensitive resin composition as described in any one of Claims. A color filter comprising the photosensitive organic layer according to claim 17 of the patent application.