KR102624673B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) Resin containing an acrylic binder resin and an epoxy binder resin; (B) a colorant containing a phthalocyanine-based dye; (C) photopolymerizable compound; A photosensitive resin composition comprising (D) a photopolymerization initiator and (E) a solvent, wherein the phthalocyanine dye includes a hydroxy group at at least one terminal, a photosensitive resin film manufactured using the photosensitive resin composition, and a color filter containing the same. is provided.

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

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

Liquid crystal display devices, one of the display devices, have advantages such as light weight, thinness, low cost, low power consumption, and excellent adhesion to integrated circuits, so their range of use is expanding to laptop computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, an active circuit section consisting of a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate on which ITO pixel electrodes are formed.

The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels, and a plurality of colors (typically red (R), green (G), and blue (B) to form each pixel. ) has a structure in which pixel parts with three primary colors arranged in a certain order are stacked sequentially. The pigment dispersion method, which is one of the methods of implementing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. This is a method of forming a colored thin film by repeating a series of processes of exposing the pattern of the shape to be formed, removing the non-exposed area with a solvent and heat curing. Colored photosensitive resin used in the production of color filters according to the pigment dispersion method. The composition generally consists of alkali-soluble resin, photopolymerization monomer, photopolymerization initiator, epoxy resin, solvent and other additives, etc. The pigment dispersion method with the above characteristics is actively used in manufacturing LCDs for mobile phones, laptops, monitors, TVs, etc. However, in recent years, photosensitive resin compositions for color filters using pigment dispersion methods, which have various advantages, are required to have not only excellent pattern characteristics but also further improved performance. In particular, high color reproduction rate, high brightness and high contrast ratio are required. Characteristics are urgently needed.

In color filters manufactured from pigment-type photosensitive resin compositions, there are limitations in luminance and contrast ratio resulting from the size of pigment particles. Additionally, in the case of color imaging devices for image sensors, smaller dispersed particles are required to form fine patterns. In order to meet such demands, attempts are being made to implement color filters with improved color characteristics such as brightness and contrast ratio by manufacturing photosensitive resin compositions incorporating dyes that do not form particles instead of pigments.

However, dyes have the problem of poor reliability compared to pigments, and research is continuing on colorants that can improve both color characteristics and reliability.

One embodiment is to provide a photosensitive resin composition that is excellent in both developability and chemical resistance.

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

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

One embodiment of the present invention includes (A) a resin containing an acrylic binder resin and an epoxy-based binder resin; (B) a colorant containing a phthalocyanine-based dye; (C) photopolymerizable compound; A photosensitive resin composition is provided, including (D) a photopolymerization initiator and (E) a solvent, wherein the phthalocyanine-based dye includes a hydroxy group at at least one terminal.

The phthalocyanine-based dye may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy 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, or a substituted Or an unsubstituted C6 to C20 aryloxy group,

However, R ³ , R ⁷ , R ¹¹ and R ¹⁴ are each independently a hydroxy group, a C1 to C20 alkyl group substituted with one or more hydroxy groups, a C1 to C20 alkoxy group substituted with one or more hydroxy groups, or a C6 to C20 alkyl group substituted with one or more hydroxy groups. It is a C20 aryl group or a C6 to C20 aryloxy group substituted with one or more hydroxy groups.

R ¹ , R ² , R ⁴ to R ⁶ , R ⁸ to R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ may each independently be a hydrogen atom or a halogen atom.

The phthalocyanine-based dye may be included in an amount of 20% by weight to 30% by weight based on the total amount of the photosensitive resin composition.

The epoxy-based binder resin may have an epoxy equivalent weight of 500 g/eq to 150 g/eq.

The epoxy-based binder resin may have a weight average molecular weight of 500 g/mol to 20,000 g/mol.

The epoxy-based binder resin may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ to L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n is an integer from 3 to 6.

The epoxy-based binder resin may include a structural unit represented by the following Chemical Formula 3-1.

[Formula 3-1]

In Formula 3-1,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

R ²¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The epoxy-based binder resin containing the structural unit represented by Formula 3-1 may further include a structural unit represented by the following Formula 3-2.

[Formula 3-2]

In Formula 3-2,

R ²² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ²³ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a fused ring thereof.

The epoxy-based binder resin containing the structural unit represented by Formula 3-1 and the structural unit represented by Formula 3-2 may further include a structural unit represented by Formula 3-3 below.

[Formula 3-3]

In Formula 3-3,

R ²⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ²⁵ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

In an epoxy-based binder resin containing a structural unit represented by Formula 3-1 and a structural unit represented by Formula 3-2, the structural unit represented by Formula 3-1 has a structure represented by Formula 3-2. It may be included in amounts greater than the unit.

In the epoxy-based binder resin containing the structural unit represented by Formula 3-1, the structural unit represented by Formula 3-2, and the structural unit represented by Formula 3-3, the structure represented by Formula 3-1 The unit may be included in an amount greater than the structural unit represented by Chemical Formula 3-2.

The epoxy-based binder resin containing the structural unit represented by Formula 3-1 and the structural unit represented by Formula 3-2 is a structural unit-derived monomer represented by Formula 3-1 and the structural unit represented by Formula 3-2. It is formed by reacting a structural unit-derived monomer with an initiator, and during the reaction, the content of the structural unit-derived monomer represented by Formula 3-1 may be three times or more than the content of the structural unit-derived monomer represented by Formula 3-2.

An epoxy-based binder resin containing a structural unit represented by Formula 3-1, a structural unit represented by Formula 3-2, and a structural unit represented by Formula 3-3 is a structural unit represented by Formula 3-1. A derived monomer, a structural unit represented by Formula 3-2 is formed by reacting a derived monomer and a structural unit derived monomer represented by Formula 3-3 with an initiator, and during the reaction, a structural unit represented by Formula 3-1 The derived monomer content may be three times or more than the content of the structural unit derived monomer represented by Chemical Formula 3-2.

The acrylic binder resin may be included in a larger amount than the epoxy binder resin.

The photosensitive resin composition includes 1% to 10% by weight of the (A) binder resin, based on the total amount of the photosensitive resin composition; 15% to 55% by weight of the (B) colorant; 0.1% to 7% by weight of the (C) photopolymerizable compound; (D) 0.1% to 5% by weight of photopolymerization initiator; And it may include the remaining amount of the solvent (E).

The photosensitive resin composition includes malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Fluorine-based surfactant; and at least one additive selected from radical polymerization initiators.

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

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

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

The photosensitive resin composition according to one embodiment may simultaneously have superior developability and chemical resistance properties compared to a photosensitive resin composition containing a general phthalocyanine-based dye.

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

Unless otherwise specified herein, “substitution” means that at least one hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, or already. No group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group. , C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, or a combination thereof.

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

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

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

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

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

One embodiment includes (A) a resin containing an acrylic binder resin and an epoxy-based binder resin; (B) a colorant containing a phthalocyanine-based dye; (C) photopolymerizable compound; A photosensitive resin composition is provided, including (D) a photopolymerization initiator and (E) a solvent, wherein the phthalocyanine-based dye includes a hydroxy group at at least one terminal.

Phthalocyanine-based compounds have been studied structurally, and many green and blue dyes using them have been developed. However, color filters manufactured with a photosensitive resin composition containing the dye have limitations in the solvents that can be used due to the dye's lack of solubility. If the solubility in the developing solution is insufficient, it may not be developed in the LCD or CIS development process, or even if developed, there will be a residue. There is a problem that occurs.

In order to improve this, an attempt was made to increase the solubility of the dye in organic solvents by introducing a substituent with excellent solubility in organic solvents to the phthalocyanine dye. However, as the solubility of the dye improved, the chemical resistance properties became weaker. .

In the photosensitive resin composition according to one embodiment, a hydroxy group with excellent solubility in a developer is substituted at a specific position of the phthalocyanine dye so as to simultaneously improve the developability and chemical resistance properties of a conventional photosensitive resin composition containing a phthalocyanine dye. Furthermore, an epoxy-based binder resin was used together with an acrylic-based binder resin to enable a direct thermal curing reaction with the hydroxy group.

Below, each component is described in detail.

(B) Colorant

The photosensitive resin composition according to one embodiment includes a colorant including a phthalocyanine-based dye including a hydroxy group at at least one terminal.

For example, the phthalocyanine-based dye may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy 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, or a substituted Or an unsubstituted C6 to C20 aryloxy group,

However, R ³ , R ⁷ , R ¹¹ and R ¹⁴ are each independently a hydroxy group, a C1 to C20 alkyl group substituted with one or more hydroxy groups, a C1 to C20 alkoxy group substituted with one or more hydroxy groups, or a C6 to C20 alkyl group substituted with one or more hydroxy groups. It is a C20 aryl group or a C6 to C20 aryloxy group substituted with one or more hydroxy groups.

For example, in Formula 1, R ¹ , R ² , R ⁴ to R ⁶ , R ⁸ to R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ may each independently be a hydrogen atom or a halogen atom.

When the phthalocyanine-based dye has the above-described structure, its solubility in a developer is very excellent, compatibility and coloring power with the binder resin, photopolymerizable monomer, and photopolymerization initiator described later can be secured, and precipitation of the dye is prevented. At the same time, the hydroxyl group at the end of the phthalocyanine dye undergoes a direct thermal curing reaction with the epoxy binder resin, thereby greatly improving the chemical resistance of the composition.

The phthalocyanine-based dye may be included in an amount of 20% to 30% by weight based on the total amount of the photosensitive resin composition. In general, dyes are less durable than pigments, so compositions containing a high amount of dye (more than 20% by weight relative to the total amount of the composition) have a problem of lower reliability compared to compositions containing a small amount of dye or compositions containing only pigments. . However, since the composition according to one embodiment includes a phthalocyanine-based dye having the above-mentioned composition, reliability is maintained even when the phthalocyanine-based dye is included in a high content, for example, 20% by weight to 30% by weight based on the total amount of the photosensitive resin composition. This may not deteriorate.

For example, the colorant may further include a pigment in addition to the phthalocyanine-based dye.

For example, the pigment may include a yellow pigment, and the yellow pigment may be specifically included in the composition in the form of a yellow pigment dispersion.

When the colorant includes the phthalocyanine dye and the yellow pigment dispersion, the phthalocyanine dye may be included in a greater amount than the yellow pigment dispersion.

When the phthalocyanine-based dye and yellow pigment dispersion constitute a colorant in the above content range, coloring power can be improved, and by using this, a color filter with excellent brightness and contrast ratio can be implemented.

The yellow pigment used in the yellow pigment dispersion is C.I. within the color index. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, etc. can be mentioned, and these can be used alone or in a mixture of two or more types.

As described above, a dispersant may be used to disperse the yellow pigment, thereby forming the composition according to one embodiment in the form of a yellow dispersion. Specifically, the pigment may be used by previously surface-treating the pigment with a dispersant, or the dispersant may be added together with the pigment when preparing the composition.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, and carboxylic acid salt. , alkyl amide, alkylene oxide adduct, alkyl amine, etc., and these can be used alone or in a mixture of two or more.

Examples of commercially available dispersants include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the composition has excellent dispersibility, resulting in excellent stability, developability, and patternability when manufacturing a color filter.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used after the above pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed through the steps of kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be performed at a temperature of 40°C to 100°C, and the filtration and washing may be performed by washing the inorganic salt with water or the like and then filtering.

Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed and the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. alkylene glycol monoalkyl ether; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyethylene glycol, etc. can be used alone or in a mixture of two or more.

The pigment that has gone through the kneading step may have an average particle diameter of 5 nm to 200 nm, for example, 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, stability in the pigment dispersion is excellent, and there is no concern about deterioration of pixel resolution.

Solvents for forming the pigment dispersion include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, and propylene glycol methyl ether.

Specifically, the pigment may be used in the form of a pigment dispersion containing the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be included in an amount of 5% to 20% by weight, for example, 8% to 15% by weight, based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 15% by weight to 55% by weight, for example, 20% by weight to 50% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the coloring effect and developability are excellent.

(A) Binder resin

The binder resin may include an acrylic binder resin and an epoxy-based binder resin.

The epoxy-based binder resin can significantly improve the chemical resistance of the composition by causing a thermal curing reaction with the hydroxy group contained in the terminal of the phthalocyanine-based dye described above.

For example, if the binder resin according to one embodiment does not include an epoxy-based binder resin, chemical resistance properties are greatly reduced, which is not desirable.

For example, the epoxy-based binder resin may have an epoxy equivalent weight of 500 g/eq to 150 g/eq. When an epoxy-based binder resin having an epoxy equivalent within the above range is included as a binder resin in the photosensitive resin composition, there is a beneficial effect in improving the curability of the formed pattern and fixing the colorant in the structure in which the pattern is formed.

The epoxy-based binder resin may have a weight average molecular weight of 500 g/mol to 20,000 g/mol. When the weight average molecular weight of the epoxy binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate when manufacturing a color filter.

For example, the epoxy-based binder resin may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ to L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n is an integer from 3 to 6.

For example, the epoxy-based binder resin may include a structural unit represented by the following Chemical Formula 3-1.

[Formula 3-1]

In Formula 3-1,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

R ²¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the epoxy-based binder resin containing the structural unit represented by Formula 3-1 may further include a structural unit represented by the following Formula 3-2.

[Formula 3-2]

In Formula 3-2,

R ²² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ²³ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a fused ring thereof.

For example, in Formula 3-2, R ²³ may be a dicyclopentanyl group.

For example, the epoxy-based binder resin containing the structural unit represented by Formula 3-1 and the structural unit represented by Formula 3-2 may further include a structural unit represented by Formula 3-3 below.

[Formula 3-3]

In Formula 3-3,

R ²⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ²⁵ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

For example, in Formula 3-3, R ²⁵ may be an ‘unsubstituted C1 to C20 alkyl group’, a ‘C1 to C20 alkyl group substituted with a hydroxy group’, or a ‘substituted or unsubstituted C6 to C20 aryl group’.

For example, in an epoxy-based binder resin containing a structural unit represented by Formula 3-1 and a structural unit represented by Formula 3-2, (the number of) structural units represented by Formula 3-1 is Formula 3- It may be included in an amount greater than (the number of) structural units indicated by 2.

For example, in an epoxy-based binder resin containing a structural unit represented by Formula 3-1, a structural unit represented by Formula 3-2, and a structural unit represented by Formula 3-3, the structure represented by Formula 3-1 The unit (number of units) may be included in an amount greater than the (number of units) of the structural unit represented by Chemical Formula 3-2.

Among the structural units constituting the epoxy-based binder resin, when the content (number) of structural units represented by Formula 3-1 is greater than the content (number) of structural units represented by Formula 3-2, the chemical resistance properties are You can become excellent.

More specifically, i) the epoxy-based binder resin is formed by reacting the structural unit-inducing monomer represented by Formula 3-1 and the structural unit-inducing monomer represented by Formula 3-2 with an initiator, and during the reaction, the The content of the structural unit-derived monomer represented by Formula 3-1 may be three times or more than the content of the structural unit-derived monomer represented by Formula 3-2, and ii) the epoxy-based binder resin has a structure represented by Formula 3-1. It is formed by reacting a unit-derived monomer, a structural unit-derived monomer represented by Formula 3-2, and a structural unit-derived monomer represented by Formula 3-3 with an initiator, and upon reaction, a structure represented by Formula 3-1 The unit-derived monomer content may be three times or more than the structural unit-derived monomer content represented by Chemical Formula 3-2.

The photosensitive resin composition according to one embodiment must include an acrylic binder resin (not containing an epoxy group) along with the epoxy binder resin.

When only the epoxy-based binder resin is used as a binder resin in the photosensitive resin composition according to one embodiment, without the acrylic-based binder resin (not containing an epoxy group), developability is greatly reduced, which is not preferable.

For example, the acrylic binder resin may be included in a larger amount than the epoxy binder resin. When the content of the acrylic binder resin is greater than that of the epoxy binder resin, it may be preferable in terms of developability.

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 one or more acrylic repeating units.

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

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

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

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Examples include, but are not limited to, acrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and these may be used alone or in combination of two or more types. there is.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 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 has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate when manufacturing a color filter.

The binder resin may be included in an amount of 1% to 10% by weight, for example, 3% to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability is excellent when manufacturing a color filter, crosslinking is improved, and excellent surface smoothness can be obtained.

(C) Photopolymerizable compound

The photopolymerizable compound may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern with excellent heat resistance, light resistance, and chemical resistance by sufficiently polymerizing the compound upon exposure to light in the pattern formation process.

Specific examples of photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 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 Rate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate ) acrylate, tris (meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, etc.

Examples of commercially available photopolymerizable compounds are as follows. Examples of the monofunctional ester of (meth)acrylic acid include Aronics M- ^101® , M- ^111® , and M- ^114® manufactured by Toagosei Chemical Co., Ltd.; Nippon Kayaku Co., Ltd.'s KAYARAD TC-110S ^® , KAYARAD TC-120S ^® , etc.; Examples include V-158 ^® and V-2311 ^® manufactured by Osaka Yuki Chemical Co., Ltd. Examples of the above-mentioned difunctional ester of (meth)acrylic acid include Aronics M-210 ^® , M-240 ^® , and M-6200 ^® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , HX-220 ^® , R-604 ^® , etc.; Examples include V-260 ^® , V-312 ^® , and V-335 HP ^® manufactured by Osaka Yuki Chemical Engineering Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronics M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , and M manufactured by Toagosei Chemical Co., Ltd. -710 ^® , M-8030 ^® , M-8060 ^® , etc.; Nippon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , DPCA-20 ^® , Dong-30 ^® , Dong-60 ^® , Dong-120 ^® , etc.; Examples include V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , and Dong-400 ^® manufactured by Osaka Yuki Kayaku Kogyo Co., Ltd. The above products can be used alone or in combination of two or more types.

The photopolymerizable compound may be used by treating it with an acid anhydride to provide better developability.

The photopolymerizable compound may be included in an amount of 0.1% to 7% by weight, for example, 0.1% to 5% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.

(D) Photopolymerization initiator

The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. You can use it.

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

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

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

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

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

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

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

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

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

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

(E) Solvent

The solvent may be a material that is compatible with, but does not react with, the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; Alkyl oxyacetic acid esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionate esters such as methyl 2-oxy-2-methyl propionate, ethyl 2-oxy-2-methyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as ethyl methyl propionate; esters such as ethyl 2-hydroxy propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxy acetate, and 2-hydroxy-3-methyl methyl butanoate; Keto acid esters such as ethyl pyruvate, and others include N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, considering compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone may be used.

The solvent may be included in the remaining amount, for example, 30% by weight to 70% by weight, for example, 35% by weight to 65% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has excellent applicability and a coating film with excellent flatness can be obtained.

(F) Other additives

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

The additives can be easily adjusted according to desired physical properties.

The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Examples include isocyanate propyl triethoxysilane, γ glycidoxy propyl trimethoxysilane, and β epoxycyclohexyl)ethyltrimethoxysilane, and these can be used alone or in a mixture of two or more types.

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

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

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

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

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

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

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

The manufacturing method of the color filter is as follows.

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

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

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

(Synthesis of phthalocyanine dyes)

Synthesis Example 1: Synthesis of dye represented by Formula 1-1

Add 3,4,5,6-tetrachlorophthalonitrile (8g), 4-Hydroxybenzyl Alcohol (3.85g), K ₂ CO ₃ (6.24g), and Acetone (50ml) to a 100ml flask and stir while heating to 55°C. . After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, it is purified by column chromatography. After purification and vacuum drying, intermediate 1 is obtained.

[Intermediate 1]

Maldi-tof MS: 356 m/z

Add intermediate 1 (4g), 1,8-Diazabicycloundec-7-ene (2.08g), and 1-pentanol (15g) to a 100mL flask and heat to 90°C to dissolve the solid. Then add zinc acetate (0.52g) and dissolve at 140°C. Stir while heating to ℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid obtained to dissolve the solid, and then methanol is added to crystallize the solid. The crystallized solid was filtered and vacuum dried to synthesize a dye represented by the following formula 1-1.

[Formula 1-1]

Maldi-tof MS: 1480 m/z

Synthesis Example 2: Synthesis of dye represented by Formula 1-2

Add 3,4,5,6-tetrachlorophthalonitrile (8g), 2-(4-Hydroxyphenyl)ethanol (4.28g), K ₂ CO ₃ (6.24g), and acetone (50ml) to a 100ml flask and heat to 55°C. Stir while heating. After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, it is purified by column chromatography. After purification and vacuum drying, intermediate 2 is obtained.

[Intermediate 2]

Maldi-tof MS: 370 m/z

Add intermediate 2 (4g), 1,8-Diazabicycloundec-7-ene (2.08g), and 1-pentanol (15g) to a 100mL flask, heat to 90°C to dissolve the solid, add zinc acetate (0.50g), and dissolve at 140°C. Stir while heating to ℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid obtained to dissolve the solid, and then methanol is added to crystallize the solid. The crystallized solid was filtered and vacuum dried to synthesize a dye represented by the following formula 1-2.

[Formula 1-2]

Maldi-tof MS: 1536 m/z

Synthesis Example 3: Synthesis of dye represented by Formula 1-3

Add 3,4,6-trichloro-5-hydroxy-1,2-Benzenedicarbonitrile (4g), 1,8-Diazabicycloundec-7-ene (2.08g), and 1-pentanol (15g) to a 100mL flask and heat to 90℃. After heating to dissolve the solid, add zinc acetate (0.74g) and stir while heating to 140°C. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid obtained to dissolve the solid, and then methanol is added to crystallize the solid. The crystallized solid was filtered and vacuum dried to synthesize a dye represented by the following formula 1-3.

[Formula 1-3]

Maldi-tof MS: 1055 m/z

Comparative Synthesis Example 1: Synthesis of dye represented by formula C-1

3,4,6-Trichloro-5-(2-cyclohexylphenoxy)-phthalonitrile (0.5g), 3,4,5,6-Tetrachlorophthalonitrile (0.1g), 1,8-Diazabicycloundec-7-ene (0.3g) in a 100mL flask. g), 1-pentanol (5g), and zinc acetate (0.08g) were added and stirred while heating to 140°C. After completion of the reaction, it was concentrated and purified by column chromatography. After purification, the obtained liquid was concentrated to obtain a solid. The crystallized solid was vacuum dried to synthesize a compound represented by the following formula C-1.

[Formula C-1]

Maldi-tof MS: 1548.39 m/z

(Synthesis of epoxy-based binder resin)

Synthesis Examples 4 to 7 and Comparative Synthesis Example 2

After adding 3.5% by weight of AIBN as an initiator (based on the total amount of polymerization monomers excluding AIBN (100% by weight)) to a 100ml beaker, the polymerization monomers were sequentially added at the weight% ratio specified in Table 1 below, and then 30% by weight. Stirred for minutes. Afterwards, to proceed with the polymerization reaction, 70 g of PGMEA was added to a 250 ml glass reactor equipped with a cooler, the temperature was raised to 85°C, and the prepared monomer solution was added dropwise to the reactor over 3 hours. After the reaction was continued at the same temperature for another 6 hours, the temperature was lowered to room temperature and the reaction was terminated, and the reaction was carried out under a nitrogen atmosphere.

(Unit: weight%) monomer type Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Comparative Synthesis Example 2 Glycidyl methacrylate 20 40 60 80 0 Dicyclopentanyl methacrylate 20 20 20 20 20 Methyl methacrylate 60 40 20 0 80 AIBN 3.5 3.5 3.5 3.5 3.5 Molecular weight (Mw, g/mol) 8200 8300 8200 8500 8200

(Synthesis of photosensitive resin composition)

Examples 1 to 15 and Comparative Examples 1 to 7

Photosensitive resin compositions according to Examples 1 to 15 and Comparative Examples 1 to 7 were prepared by mixing the components mentioned below in the compositions shown in Tables 2 to 4.

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

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Binder resin A-1 6.50 6.50 6.50 6.50 6.50 6.50 6.50 - A-2 3.50 - - - - - 3.50 10.00 A-3 - 3.50 - - - - - - A-4 - - 3.50 - - - - - A-5 - - - 3.50 - - - - A-6 - - - - 3.50 - - - A-7 - - - - - 3.50 - - (B) Colorant B-1 33.00 33.00 33.00 33.00 33.00 33.00 - 33.00 B-2 - - - - - - - - B-3 - - - - - - - - B-4 - - - - - - 33.00 - B-5 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 (C) Photopolymerizable compound C-1 4.05 4.05 4.05 4.05 4.05 4.05 4.05 4.05 C-2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 (D) Photopolymerization initiator D-1 1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05 D-2 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 (E) Solvent 36.29 36.29 36.29 36.29 36.29 36.29 36.29 36.29 (F) Other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02

(Unit: weight%) Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 4 Comparative Example 5 (A) Binder resin A-1 6.50 6.50 6.50 6.50 6.50 6.50 - A-2 3.50 - - - - - 10.00 A-3 - 3.50 - - - - - A-4 - - 3.50 - - - - A-5 - - - 3.50 - - - A-6 - - - - 3.50 - - A-7 - - - - - 3.50 - (B) Colorant B-1 - - - - - - - B-2 33.00 33.00 33.00 33.00 33.00 33.00 33.00 B-3 - - - - - - - B-4 - - - - - - - B-5 15.00 15.00 15.00 15.00 15.00 15.00 15.00 (C) Photopolymerizable compound C-1 4.05 4.05 4.05 4.05 4.05 4.05 4.05 C-2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 (D) Photopolymerization initiator D-1 1.05 1.05 1.05 1.05 1.05 1.05 1.05 D-2 0.14 0.14 0.14 0.14 0.14 0.14 0.14 (E) Solvent 36.29 36.29 36.29 36.29 36.29 36.29 36.29 (F) Other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02

(Unit: weight%) Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 6 Comparative Example 7 (A) Binder resin A-1 6.50 6.50 6.50 6.50 6.50 6.50 - A-2 3.50 - - - - - 10.00 A-3 - 3.50 - - - - - A-4 - - 3.50 - - - - A-5 - - - 3.50 - - - A-6 - - - - 3.50 - - A-7 - - - - - 3.50 - (B) Colorant B-1 - - - - - - - B-2 - - - - - - - B-3 33.00 33.00 33.00 33.00 33.00 33.00 33.00 B-4 - - - - - - - B-5 15.00 15.00 15.00 15.00 15.00 15.00 15.00 (C) Photopolymerizable compound C-1 4.05 4.05 4.05 4.05 4.05 4.05 4.05 C-2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 (D) Photopolymerization initiator D-1 1.05 1.05 1.05 1.05 1.05 1.05 1.05 D-2 0.14 0.14 0.14 0.14 0.14 0.14 0.14 (E) Solvent 36.29 36.29 36.29 36.29 36.29 36.29 36.29 (F) Other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02

(A) Binder resin

(A-1) Acrylic binder resin (RY-25, Showa Denko)

(A-2) Epoxy-based binder resin (DMS-E11, Gelest; represented by the following chemical formula E-1)

[Formula E-1]

(In Formula E-1, n is an integer of 3 to 6)

(A-3) Epoxy-based binder resin (Synthesis Example 4)

(A-4) Epoxy-based binder resin (Synthesis Example 5)

(A-5) Epoxy-based binder resin (Synthesis Example 6)

(A-6) Epoxy-based binder resin (Synthesis Example 7)

(A-7) Epoxy-based binder resin (Comparative Synthesis Example 2)

(B) Colorant

(B-1) Phthalocyanine dye (Synthesis Example 1)

(B-2) Phthalocyanine dye (Synthesis Example 2)

(B-3) Phthalocyanine dye (Synthesis Example 3)

(B-4) Phthalocyanine dye (Comparative Synthesis Example 1)

(B-5) Pigment Y138 pigment (SANYO, pigment solids 15%)

(C) Photopolymerizable monomer

(C-1) Dipentaerythritol hexaacrylate (DPHA, Japanese gunpowder)

(C-2) ABPE-20 (Public Works)

(D) Photopolymerization initiator

(D-1) SPI-03 (Samyang)

(D-2) PBG-305 (Tronly)

(E) Solvent

Propylene glycol monomethyl ether acetate (Sigma-Aldrich)

(F) Other additives

Fluorine-based surfactant (F-554, DIC)

(evaluation)

Evaluation 1: Development speed and residue characteristics

For residue evaluation, a patterned substrate was prepared on the lower _SiN After coating and developing, the development speed was measured, and then the residue on the SiNx substrate was observed with an optical microscope, and the results are shown in Tables 5 to 7 below.

Criteria for evaluating the characteristics of residues on organic membranes

O: No residue on the organic film is observed under an optical microscope.

X: Residue on the organic layer is observed under an optical microscope

Evaluation 2: Chemical resistance

The photosensitive resin composition prepared in Examples 1 to 15 and Comparative Examples 1 to 7 was applied to a thickness of 1 ㎛ to 3 ㎛ on a degreased and washed glass substrate with a thickness of 1 mm, and placed on a hot plate at 90°C. A coating film was obtained by drying on the surface for 2 minutes. Subsequently, the coated film was fully exposed under conditions of 60 mJ/cm ² using a lamp with a dominant wavelength of 365 nm. Afterwards, samples of the same thickness were obtained by drying in a hot air circulation drying furnace at 245°C for 20 minutes. After manufacturing the sample in a size of 2 × 2 cm and precipitating it in NMP (N-methylpyrrolidone) solution at 25°C/30 minutes, the color change before and after treatment was measured using MCPD (Otsuka) equipment using a C light source. Reference color characteristics were evaluated. Chemical resistance was measured by calculating the ΔEab* value, and the results are shown in Tables 5 to 7 below.

Evaluation items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 development speed
(candle) 28 30 30 32 38 35 70 87 residue O O O O O O X X chemical resistance 3.5 2.3 2.1 1.8 1.6 5.5 4.3 4.4

Evaluation items Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 4 Comparative Example 5 development speed
(candle) 29 31 32 32 39 37 85 residue O O O O O O X chemical resistance 3.5 2.4 2.1 1.7 1.6 5.6 4.3

Evaluation items Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 6 Comparative Example 7 development speed
(candle) 42 43 42 42 48 45 89 residue O O O O O O X chemical resistance 4.4 4.1 3.6 3.0 2.8 6.5 5.5

From Tables 5 to 7, it can be seen that the photosensitive resin composition according to one embodiment is superior to the photosensitive resin compositions of Comparative Examples 1 to 7 in both developability and chemical resistance. Furthermore, by comparing Examples 1 to 10 and Examples 11 to 15, it can be confirmed that the substitution position of the hydroxy group at the end of the phthalocyanine dye also has a significant impact on developability and chemical resistance under the same conditions.

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

Claims (18)

(A) Resin containing an acrylic binder resin and an epoxy binder resin;
(B) a colorant containing a phthalocyanine-based dye represented by the following formula (1);
(C) photopolymerizable compound;
(D) photopolymerization initiator and
(E) comprising a solvent,
A photosensitive resin composition in which the phthalocyanine-based dye includes a hydroxy group at at least one terminal:
[Formula 1]

In Formula 1,
R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy 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, or a substituted Or an unsubstituted C6 to C20 aryloxy group,
However, R ³ , R ⁷ , R ¹¹ and R ¹⁴ are each independently a hydroxy group, a C1 to C20 alkyl group substituted with one or more hydroxy groups, a C1 to C20 alkoxy group substituted with one or more hydroxy groups, or a C6 to C20 alkyl group substituted with one or more hydroxy groups. It is a C20 aryl group, a C6 to C20 aryloxy group substituted with one or more hydroxy groups, or an aryloxy group substituted with an alkyl group substituted with one or more hydroxy groups.
delete According to paragraph 1,
The photosensitive resin composition wherein R ¹ , R ² , R ⁴ to R ⁶ , R ⁸ to R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a halogen atom.
According to paragraph 1,
The photosensitive resin composition wherein the phthalocyanine-based dye is included in an amount of 20% by weight to 30% by weight based on the total amount of the photosensitive resin composition.
According to paragraph 1,
The epoxy-based binder resin is a photosensitive resin composition having an epoxy equivalent weight of 500 g/eq to 150 g/eq.
According to paragraph 1,
The epoxy-based binder resin is a photosensitive resin composition having a weight average molecular weight of 500 g/mol to 20,000 g/mol.
According to paragraph 1,
The epoxy-based binder resin is a photosensitive resin composition represented by the following formula (2):
[Formula 2]

In Formula 2,
R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ to L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
n is an integer from 3 to 6.
According to paragraph 1,
The epoxy-based binder resin is a photosensitive resin composition comprising a structural unit represented by the following Chemical Formula 3-1:
[Formula 3-1]

In Formula 3-1,
L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,
R ²¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
According to clause 8,
The epoxy-based binder resin is a photosensitive resin composition further comprising a structural unit represented by the following Chemical Formula 3-2:
[Formula 3-2]

In Formula 3-2,
R ²² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ²³ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a fused ring thereof.
According to clause 9,
The epoxy-based binder resin is a photosensitive resin composition further comprising a structural unit represented by the following formula 3-3:
[Formula 3-3]

In Formula 3-3,
R ²⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ²⁵ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
According to claim 9 or 10,
A photosensitive resin composition in which the structural unit represented by Formula 3-1 is contained in a greater amount than the structural unit represented by Formula 3-2.
According to clause 9,
The epoxy-based binder resin is formed by reacting the structural unit-derived monomer represented by Formula 3-1 and the structural unit-derived monomer represented by Formula 3-2 with an initiator, and during the reaction, represented by Formula 3-1 A photosensitive resin composition in which the structural unit-derived monomer content is three times or more than the structural unit-derived monomer content represented by Chemical Formula 3-2.
According to clause 10,
The epoxy-based binder resin is prepared by reacting a structural unit-derived monomer represented by Formula 3-1, a structural unit-derived monomer represented by Formula 3-2, and a structural unit-derived monomer represented by Formula 3-3 with an initiator. A photosensitive resin composition is formed, and during the reaction, the content of the structural unit-derived monomer represented by Formula 3-1 is at least 3 times the content of the structural unit-derived monomer represented by Formula 3-2.
According to paragraph 1,
A photosensitive resin composition in which the acrylic binder resin is contained in a greater amount than the epoxy-based binder resin.
According to paragraph 1,
The photosensitive resin composition is, with respect to the total amount of the photosensitive resin composition,
(A) 1% to 10% by weight of binder resin;
15% to 55% by weight of the (B) colorant;
0.1% to 7% by weight of the (C) photopolymerizable compound;
(D) 0.1% to 5% by weight of photopolymerization initiator; and
(E) Solvent remaining amount
A photosensitive resin composition containing a.
According to paragraph 1,
The photosensitive resin composition includes malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Fluorine-based surfactant; and a radical polymerization initiator.
A photosensitive resin film manufactured using the photosensitive resin composition of claim 1.
A color filter comprising the photosensitive resin film of claim 17.