KR20200061793A - Photosensitive resin composition and photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided is a photosensitive resin composition comprising: (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant including a polymer dye; and (E) a solvent. Also, provided are a photosensitive resin film and a color filter produced using the same. According to the present invention, the photosensitive resin composition can implement high brightness by ensuring structural stability in patterns.

Description

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

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

Recently, as the spread of large-screen liquid crystal display devices has increased, the demand for new performance enhancements for liquid crystal display devices is increasing, and among the components of liquid crystal display devices, color filters are the most important for realizing color. Research is ongoing.

In addition, in the case of a large screen liquid crystal display device, the colorant concentration of the photosensitive resin composition is increasing when manufacturing a color filter in order to increase color purity, and a photosensitive resin composition having a low development speed and excellent sensitivity at a small exposure amount is required to increase productivity and yield in the manufacturing process. Is becoming.

The color filter using the photosensitive resin composition can be mainly produced by coating three or more colors on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, etc., and recently, a pigment dispersion method is widely used.

On the other hand, in a color filter made of a pigment-type photosensitive resin composition, there is a limit in that luminance and contrast ratios are lowered due to pigment particle size and aggregation of pigment particles. In order to improve these limitations, attempts are being made to use a dye-type photosensitive resin composition that does not form particles or introduces a dye having a very small primary particle size compared to a pigment dispersion. However, the dye-type photosensitive resin composition has difficulty in commercialization due to its weak heat resistance, light resistance, and chemical resistance.

One embodiment is to provide a photosensitive resin composition capable of achieving high luminance by securing structural stability in a pattern.

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

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

One embodiment is (A) a binder resin; (B) photopolymerizable monomer; (C) photopolymerization initiator; (D) a polymer dye comprising “a structural unit selected from the group consisting of structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2” and “structural units represented by Chemical Formulas 3 to 6” Coloring agent containing; And (E) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 1 to 6,

R ¹ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ is a substituted or unsubstituted C11 to C20 alkyl group,

R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

L ² is *-NH(C=O)O-*,

X is represented by the following formula (X-1) or formula (X-2).

[Formula X-1]

[Formula X-2]

The polymer dye may have a weight average molecular weight of 6,000 g/mol to 20,000 g/mol.

The polymer dye is 25% by weight to 35% by weight of the structural unit represented by Chemical Formula 1 or the structural unit represented by Chemical Formula 2, 10 to 20% by weight of the structural unit represented by Chemical Formula 3, based on the total amount of the polymer dye. 10 to 20% by weight of the structural unit represented by Chemical Formula 4, 15 to 25% by weight of the structural unit represented by Chemical Formula 5 and 15 to 25% by weight of the structural unit represented by Chemical Formula 6 .

The structural unit represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

The structural unit represented by Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2-1 to 2-8.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

The polymer dye may be included in an amount of 0.1 to 20% by weight based on solids based on the total amount of the photosensitive resin composition.

The colorant may further include a yellow dye.

The colorant may further include a pigment.

The photosensitive resin composition is (A) 1 to 20% by weight of the binder resin; (B) 1 to 20% by weight of the photopolymerizable monomer; (C) 0.1 to 5% by weight of the photopolymerization initiator; (D) 2 to 40% by weight of the colorant; And the residual amount of the solvent (E).

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or it may further include additives of these combinations.

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

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

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

The photosensitive resin composition according to one embodiment may include a colorant containing a polymer dye, thereby enabling stable pattern realization, and thus providing a color filter having excellent luminance.

1 is a scanning electron microscope photograph showing a pattern of a photosensitive resin film prepared using the photosensitive resin composition according to Example 1.
2 is a scanning electron microscope photograph showing a pattern of a photosensitive resin film prepared using the photosensitive resin composition according to Comparative Example 1.
FIG. 3 is a scanning electron microscope photograph of the photograph of FIG. 2 enlarged 6 times.
4 is a scanning electron microscope photograph of the photo of FIG. 2 magnified 15 times.

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 claims to be described later.

Unless otherwise specified in the present specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (F, Cl, Br or I), a hydroxyl group, a nitro group, a cyano group, an amino group ( NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, each independently being a C1 to C10 alkyl group), amidino group, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, And substituted or unsubstituted heterocyclic groups.

Unless otherwise specified in the present specification, "alkyl group" means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and "cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" means a C1 to C20 alkoxy group, specifically means a C1 to C18 alkoxy group, and "aryl group" means a C6 to C20 aryl group, specifically C6 to C18 aryl group means, "alkenyl group" means a C2 to C20 alkenyl group, specifically means C2 to C18 alkenyl group, "alkylene group" means a C1 to C20 alkylene group, specifically C1 To C18 alkylene group, and "arylene group" means a C6 to C20 arylene group, specifically, a C6 to C16 arylene group.

In addition, unless otherwise specified herein, "hetero" means that at least one hetero atom of at least one of N, O, S and P is included in the formula.

Also, unless otherwise specified herein, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid”. "It means both are possible.

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

In this specification, the cardo-based resin means a resin in which at least one functional group selected from the group consisting of the following Chemical Formulas 20-1 to 20-11 is included in the backbone in the resin.

Unless otherwise defined, the term “ethylenically unsaturated double bond” means “carbon-carbon double bond”, and the ethylenically unsaturated monomer means a monomer containing the ethylenically unsaturated double bond.

Also, unless otherwise specified in this specification, "*" refers to a part connected to the same or different atom or chemical formula.

The photosensitive resin composition according to one embodiment includes (A) a binder resin; (B) photopolymerizable monomer; (C) photopolymerization initiator;

(D) A polymer dye comprising “a structural unit selected from the group consisting of structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2” and “structural units represented by Chemical Formulas 3 to 6” Coloring agent containing; And (E) a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 1 to 6,

R ¹ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ is a substituted or unsubstituted C11 to C20 alkyl group,

R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

L ² is *-NH(C=O)O-*,

X is represented by the following formula (X-1) or formula (X-2).

[Formula X-1]

[Formula X-2]

As described above, in a color filter made of a pigment-type photosensitive resin composition, there are limitations in luminance and contrast ratio resulting from pigment particle size. In addition, in the case of a color imaging element for an image sensor, a smaller dispersion particle size is required to form a fine pattern. In order to meet these demands, attempts have been made to implement a color filter with improved brightness and contrast ratio by preparing a photosensitive resin composition suitable for dyes by introducing dyes that do not form particles instead of pigments.

However, in the case of dyes, there are advantages in terms of brightness and contrast compared to pigments, but durability is poor, and dye-type photosensitive resin compositions do not control pattern variation compared to pigment-type photosensitive resin compositions, resulting in poor pattern durability and securing high brightness characteristics. Having difficulty.

However, the photosensitive resin composition according to an embodiment includes a polymer dye comprising “a structural unit represented by Chemical Formula 1 or a structural unit represented by Chemical Formula 2” and “a structural unit represented by Chemical Formulas 2 to 6” as a colorant. By using it, it is possible to easily control the pattern shift and secure stable pattern durability and high brightness characteristics. Specifically, by forming the copolymer (polymer) by copolymerizing the structural unit represented by Chemical Formula 1 or Chemical Formula 2 with a structural unit derived from another monomer (the structural unit represented by Chemical Formulas 3 to 6), the conventional dye is The problem of reduced durability is improved, which leads to securing stability in the pattern, and ultimately, it is possible to realize high luminance characteristics.

Each component will be described in detail below.

(D) Coloring agent

In the present invention, the colorant includes a polymer dye comprising “a structural unit represented by Chemical Formula 1 or a structural unit represented by Chemical Formula 2” and “a structural unit represented by Chemical Formulas 3 to 6”.

The polymer dye may have a weight average molecular weight of 6,000 g/mol to 20,000 g/mol. When the polymer dye has a weight average molecular weight in the above range, pattern variation can be easily controlled.

For example, the polymer dye is 25 wt% to 35 wt% of the structural unit represented by Formula 1 or the structural unit represented by Formula 2, and 10 wt% to 20 of the structural unit represented by Formula 3 with respect to the total amount of the polymer dye. Weight%, 10% to 20% by weight of the structural unit represented by Formula 4, 15% to 25% by weight of the structural unit represented by Formula 5 and 15% to 25% by weight of the structural unit represented by Formula 6 It can be included as When the polymer dye includes each of the structural units in the content range, it may have excellent heat resistance and chemical resistance, which suppresses the formation of pattern foreign matter, and can produce a color filter that realizes high luminance.

For example, the structural unit represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-6, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

For example, the structural unit represented by Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2-1 to 2-8, but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

For example, the polymer dye may be red.

The polymer dye may be included in an amount of 0.1 to 20% by weight based on solids based on the total amount of the photosensitive resin composition. For example, the polymer dye may be included in 0.5% to 10% by weight relative to the total amount of the photosensitive resin composition. When the polymer dye is included within the above range, the color filter reproducibility, exposure sensitivity, and fine patterns are secured while the color filter pattern is manufactured while using the conventional color filter process as it is, and the heat resistance is also excellent. A color filter having luminance can be manufactured.

For example, the colorant may further include a yellow dye.

For example, the colorant may further include a pigment.

The pigment may include a blue pigment, a violet pigment, a red pigment, a green pigment, a yellow pigment, and the like.

Examples of the blue pigment is C.I. Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue Pigment 15:5, C.I. And copper phthalocyanine pigments such as blue pigment 16 and the like.

Examples of the violet pigment, C.I. Violet Pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet Pigment 27, C.I. Violet Pigment 29, C.I. Violet Pigment 30, C.I. Violet Pigment 32, C.I. Violet Pigment 37, C.I. Violet Pigment 40, C.I. Violet Pigment 42, C.I. Violet pigment 50 or a combination thereof.

Examples of the red pigment are C.I. Red pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. And red pigment 89.

Examples of the green pigment are C.I. Green Pigment 58, C.I. Green Pigment 59, C.I. Green Pigment 36, C.I. And halogen-substituted copper phthalocyanine pigments such as green pigment 7.

Examples of the yellow pigment is C.I. Isoindoline pigments such as yellow pigment 139, C.I. Quinophthalone-based pigments such as yellow pigment 138, C.I. And nickel complex pigments such as yellow pigment 150 and the like.

The pigment may be used alone or in combination of two or more, and is not limited to these examples.

Dispersants may be used together to disperse the pigment in the photosensitive resin composition. Specifically, the pigment may be surface-treated with a dispersant in advance, or may be used by adding a dispersant together with the pigment when preparing the photosensitive resin composition.

As the dispersant, a nonionic dispersant, anionic dispersant, or cationic dispersant may be used. Specific examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylenes, polyalcohol esters alkylene oxide adducts, alcoholalkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

Examples of commercially available products of the dispersing agent include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, 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 from EFKA Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc.; Or Ajinomoto's PB711 or 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, stability, developability, and patternability are excellent when manufacturing a light-shielding layer as the dispersibility of the photosensitive resin composition is excellent.

The pigment may also be used by pre-treatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used as the pretreatment, the primary particle size of the pigment can be refined.

The pre-treatment may be performed through a step 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 acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed and the pigment can be easily pulverized. Examples include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin polyethylene glycol. These may be used alone or in combination of two or more.

The pigment subjected to the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, a fine pattern can be effectively formed while being excellent in heat resistance and light resistance.

Specifically, the pigment may be used in the form of a pigment dispersion liquid containing the dispersing agent and the solvent described below, and the pigment dispersion liquid may include a solid pigment, a dispersant, and a solvent. The solid pigment may be included in an amount of 10% to 15% by weight based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 2 to 40% by weight based on solids based on the total amount of the photosensitive resin composition. For example, the colorant may be included in an amount of -3 wt% to 30 wt% based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, luminance, color reproduction rate, curability of the pattern, heat resistance and adhesion are excellent.

(A) Binder resin

The binder resin may include acrylic binder resin, cardo-based binder resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

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 combinations thereof.

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

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl 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; And the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic binder resin are (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmethacrylate Acrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

The acrylic binder resin may have a weight average molecular weight of 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, physical and chemical properties of the photosensitive resin composition are excellent, viscosity is appropriate, and adhesion to a substrate is excellent when producing a color filter.

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

The cardo-based binder resin may include a repeating unit represented by Chemical Formula 20 below.

[Formula 20]

In Chemical Formula 20,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ (where R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or Formula 20-1 to any one of the linking group represented by Formula 20-11,

[Formula 20-1]

[Formula 20-2]

[Formula 20-3]

[Formula 20-4]

[Formula 20-5]

(In the above formula 20-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.)

[Formula 20-6]

[Formula 20-7]

[Formula 20-8]

[Formula 20-9]

[Formula 20-10]

[Formula 20-11]

Z ² is an acid dianhydride residue,

m1 and m2 are each independently an integer of 0-4.

The cardo-based binder resin may include a functional group represented by the following Chemical Formula 21 on at least one of both ends.

[Formula 21]

In Chemical Formula 21,

Z ³ may be represented by the following formulas 21-1 to 21-7.

[Formula 21-1]

(In the formula 21-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 21-2]

[Formula 21-3]

[Formula 21-4]

[Formula 21-5]

(In the formula 21-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Formula 21-6]

[Formula 21-7]

The cardo-based binder resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid anhydride, pyromellitic dihydride, cyclobutanetetracarboxylic acid anhydride, perylenetetracarboxylic acid anhydride , Anhydride compounds such as tetrahydrofurantetracarboxylic acid anhydride and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; Solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the cardo-based binder resin is used together with the aforementioned acrylic-based binder resin, it is possible to obtain a photosensitive resin composition having excellent adhesion and high resolution and high brightness characteristics.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, such as 3,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, the pattern is well formed without residue when manufacturing the color filter, and there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may have an acid value of 100 mgKOH/g to 140 mgKOH/g.

The binder resin may be included in 1 to 20% by weight relative to the total amount of the photosensitive resin composition. When the binder resin is included in the above range, it is possible to further improve the pattern surface properties.

(B) Photopolymerizable monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, it is possible to form a pattern excellent in heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the 　 pattern forming process.

Specific examples of the photopolymerizable monomer 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)acrylic 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, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy (meth)acrylate　.

Examples of commercially available products of the photopolymerizable monomer are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® of Nihon Kayaku Co., Ltd., and TC-120S ^® of the same; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; Nippon Kayaku (Note)社of KAYARAD HDDA ^®, copper HX-220 ^®, copper R-604 ^®, and the like; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M ^® -710, Dong M-8030 ^®, same M-8060 ^®, and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride to impart better developability.

The photopolymerizable monomer may be included in 1% by weight to 20% by weight relative to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, curing is sufficiently performed during exposure in the 형성 pattern forming process, and reliability is excellent, and developability to an alkali developer is excellent.

(C) Photopolymerization initiator

The photopolymerization initiator may use acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and the like.

Examples of the acetophenone-based compound, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

Examples of the benzophenone-based compound, benzophenone, benzoylbenzoate, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylate benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 And'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

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

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

Examples of the triazine-based compound, 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 And bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like. .

Examples of the oxime-based compound are 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 As a specific example of the O-acyloxime-based compound, 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane -1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanylphenyl)-octane-1,2- Dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butane-1-one oxime -O-acetate　 can be used.

In addition to the above compound, the photopolymerization initiator may use a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, or the like.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and transmitting its energy.

Examples of the photosensitizer, tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritoltetrakis-3-mercaptopropionate, etc. Can be heard.

The photopolymerization initiator may be included in an amount of 0.1 to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently during exposure in a pattern forming process, and a decrease in transmittance due to an unreacted initiator can be prevented.

(E) solvent

As the solvent, materials having compatibility with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant, but not reacting may be used.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butylkenone, 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 alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; Acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, γ butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. These may be used alone or in combination of two or more.

When considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether are preferred; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in a residual amount, such as 20% by weight to 80% by weight, such as 25% by weight to 60% by weight relative to the total amount of the photosensitive resin composition. When the solvent is included in the above range, a coating film having excellent coating properties and excellent flatness can be obtained.

(F) antioxidant

The photosensitive resin composition according to an embodiment may further include an antioxidant, and the antioxidant may be represented by Formula 7 below.

[Formula 7]

In Chemical Formula 7,

L ⁴ to L ¹¹ are each 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 group,

R ⁴¹ to R ⁶⁰ are each 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 or unsubstituted C6 to C20 aryl group,

At least one of R ⁴¹ to R ⁴⁵ , at least one of R ⁴⁶ to R ⁵⁰ , at least one of R ⁵¹ to R ⁵⁵ and at least one of R ⁵⁶ to R ⁶⁰ is a hydroxy group,

At least one of R ⁴¹ to R ⁴⁵ , at least one of R ⁴⁶ to R ⁵⁰ , at least one of R ⁵¹ to R ⁵⁵ and at least two of R ⁵⁶ to R ⁶⁰ are t-butyl groups.

The antioxidant may have excellent heat resistance and chemical resistance by having the structure of Chemical Formula 7.

In general, the photosensitive resin composition generates free radicals in a post-processing step such as high temperature, and thus, the heat resistance and chemical resistance of the composition are deteriorated. However, the photosensitive resin composition according to one embodiment may further have excellent heat resistance and chemical resistance by inactivating the free radical by further including the antioxidant.

Specifically, free radicals generated at high temperature have good reactivity and react with surrounding oxygen (see Scheme 1), and free radicals reacted with oxygen have a rapid rate with the hydroxyl group of di-t-butylphenol, a substituent included in antioxidants. And inactivated (see Scheme 2).

[Scheme 1]

R˙ + O ₂ → ROO˙

[Scheme 2]

ROO˙ + hydroxy group of di-t-butylphenol → ROOH

For example, L ⁴ to L ¹¹ may be each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant may be represented by the following formula 8 or formula 9.

[Formula 8]

[Formula 9]

The content of the antioxidant may be 0.01% by weight to 5% by weight based on 100% by weight of the photosensitive resin composition, such as 0.01% by weight to 3% by weight, such as 0.01% by weight to 1% by weight. When the antioxidant is included in the above range, color resistance is minimized, and heat resistance and chemical resistance are excellent.

(G) Other additives

The photosensitive resin composition is to prevent stains or spots when applied, to improve the leveling performance, and also to prevent the generation of residues due to undeveloped, malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or it may further include other additives such as combinations thereof.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γmethacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γisocyanate propyl triethoxysilane, γglycidoxy Cypropyl trimethoxysilane, β-epoxycyclohexyl)ethyl trimethoxysilane, etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the fluorine-based surfactant, BM-1000 ^® , BM-1100 ^{® of} BM Chemie; Dai Nippon Inki Chemical Industry Co., Ltd. Mecca Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^®, etc.; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to the desired physical properties.

Another embodiment provides a photosensitive resin film prepared using the photosensitive resin composition described above.

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

The manufacturing method of the color filter is as follows.

A suitable method such as spin coating, roller coating, spray coating, or the like is applied onto the glass substrate to form the resin composition layer by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 μm to 10 μm.

Subsequently, light is irradiated to form a pattern required for the color filter on the substrate on which the resin composition layer is formed. UV, electron beam or X-ray may be used as a light source used for irradiation, and for example, UV in a region of 190 nm to 　 450 nm, specifically 200 nm to 400 nm may be irradiated. In the irradiation step, a photoresist mask may be further used. After performing the irradiation step as described above, the resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed portion of the resin composition layer is dissolved to form a pattern required for the color filter. By repeating this process according to the number of colors required, a color filter having a desired pattern can be obtained. In addition, cracking, solvent resistance, etc. can be improved by heating the image pattern obtained by developing in the above step again or curing it by actinic radiation or the like.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

(Preparation of compounds)

Preparation Example 1 Synthesis of Compound Represented by Formula 10-1

32 g of Compound A (CAS No. 77545-45-0) was introduced into the reactor and dissolved with 300 g of 2-propanol. After adding 28.2 g of 2-ethylamino ethanol, the mixture was stirred at 80°C for 8 hours. The reaction was cooled and 2 L of water was added to form a precipitate. The obtained precipitate was suction filtered and further washed with water. The filtrate was dried to obtain 32 g of compound B (80% yield).

10 g of Compound B was introduced into the reactor, 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane was added to the reaction mixture and washed with water. The obtained organic layer was distilled under reduced pressure after silica filtration. The distilled mixture was dissolved with 10 g of dichloromethane and then precipitated by dropwise addition to 100 g of normal hexane. The obtained precipitate was suction filtered and further washed. The filtrate was dried to obtain 12.8 g (80% yield) of the compound represented by Chemical Formula 10-1.

Maldi-tof MS: 820.3 m/z

Preparation Example 2: Synthesis of Compound Represented by Formula 10-2

[Formula 10-2]

4.0 g of dimethylformamide and 70 g of chloroform were added to the reactor, and the mixture was cooled and stirred at 0°C. 5.0 g of thionyl chloride was added dropwise so that the temperature of the liquid in the mixture did not exceed 12°C, and stirred at 0°C for 30 minutes. 10 g of a compound represented by Chemical Formula 10-1 of Synthesis Example 1-1 was slowly added at room temperature and stirred at 35° C. for 3 hours. And after adding 0.6 g of thionyl chloride, the reaction solution was stirred at 35° C. for 1.5 hours.

The reaction solution was cooled again, and 7.3 g of trifluoromethane sulfonamide was slowly added so as not to exceed 12°C, and 12.3 g of triethylamine was continuously added dropwise, followed by stirring at room temperature for 14 hours. Insolubles were removed by filtration and the reaction solvent was removed under reduced pressure. 100 g of water was added and a 15% aqueous sodium carbonate solution was added dropwise, and the suspension was stirred for 1 hour while maintaining a pH of 7.0 to 7.5. The compound represented by Chemical Formula 10-2 was extracted using 100 g of dichloromethane, and column purified using a dichloromethane/methanol (15/1) mixture. The organic solvent was removed and dried to obtain 7.1 g of a compound represented by Chemical Formula 10-2 (61% yield).

Maldi-tof MS: 951.3 m/z

Preparation Example 3: Synthesis of Compound Represented by Formula 11-1

10 g of Compound A (CAS No. 77545-45-0) was introduced into the reactor and dissolved with 100 g of 2-propanol. After adding 9.4 g of 2-butylamino ethanol, the mixture was stirred at 80°C for 8 hours. The reaction was cooled and 800 mL of water was added to form a precipitate. The obtained precipitate was suction filtered and further washed with water. The filtrate was dried to give compound C 10.9 g (78% yield). 10 g of Compound B was introduced into the reactor, 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane was added to the reaction mixture and washed with water. The obtained organic layer was distilled under reduced pressure after silica filtration. The distilled mixture was dissolved with 10 g of dichloromethane and then precipitated by dropwise addition to 100 g of normal hexane. The obtained precipitate was suction filtered and further washed. The filtrate was dried to obtain 11.6 g (75% yield) of the compound represented by Chemical Formula 11-1.

Maldi-tof MS: 876.4 m/z

Preparation Example 4 Synthesis of Compound Represented by Formula 11-2

[Formula 11-2]

A compound represented by Formula 11-2 was synthesized in the same manner as in Synthesis Example 1-2, except that a compound represented by Formula 11-1 was used instead of the compound represented by Formula 10-1.

Maldi-tof MS: 1007.3 m/z

Preparation Example 5 Synthesis of Compound Represented by Formula 14-1

10 g of Compound B was introduced into the reactor, 30 g of dimethylformamide and 6.4 g of acryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane was added to the reaction mixture and washed with water. The obtained organic layer was distilled under reduced pressure after silica filtration. The distilled mixture was dissolved with 10 g of dichloromethane and then precipitated by dropwise addition to 100 g of normal hexane. The obtained precipitate was suction filtered and further washed. The filtrate was dried to obtain 13.2 g (85% yield) of the compound represented by Chemical Formula 14-1.

[Formula 14-1]

Maldi-tof MS: 792.3 m/z

Preparation Example 6: Synthesis of Compound Represented by Formula 14-2

[Formula 14-2]

The compound represented by Formula 14-2 was synthesized in the same manner as in Synthesis Example 1-2, except that the compound represented by Formula 14-1 was used instead of the compound represented by Formula 10-1.

Maldi-tof MS: 923.2 m/z

(Red polymer dye production)

Synthesis Examples 1 to 6

After adding 2 g of AIBN as an initiator to a 100 ml beaker, the polymerization monomers listed in Table 1 below were sequentially added at a ratio of weight percent shown in Table 1 below, and then stirred for 30 minutes. Thereafter, in order to proceed with the polymerization reaction, 70 g of PGMEA was added to a 250 ml glass reactor with a cooler, and then heated to 85° C., and the prepared monomer solution was added dropwise to the reactor for 3 hours. After further reacting at the same temperature for 6 hours, the temperature was lowered to room temperature and the reaction was terminated, and the reaction was performed under a nitrogen atmosphere.

(Unit: weight%) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Compound of Formula 10-1 30 30 30 30 30 30 Acrylic acid 15 20 25 40 - - N-Phenyl maleimide 15 20 25 - 30 70 Lauryl acrylate 20 30 - - - - Methyl Methacrylic acid 20 - 20 30 40 - Weight average molecular weight (g/mol) 9,000 8,500 8,000 7,500 6,500 6,000

(Production of photosensitive resin composition)

Example 1, Example 2 and Comparative Examples 1 to 6

Photosensitive resin compositions according to Example 1, Example 2 and Comparative Examples 1 to 6 were prepared with the compositions shown in Table 2 below using the components mentioned below.

Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent was added, and the photopolymerization initiator was sufficiently stirred until all dissolved (30 minutes or more). Here, the acrylic binder resin and the photopolymerizable monomer were sequentially added, followed by stirring for another hour. Subsequently, a coloring agent was added, and after adding an antioxidant and other additives, the entire composition was finally stirred for 2 hours or more to prepare a photosensitive resin composition.

The specifications of each component used in manufacturing the photosensitive resin composition are as follows.

(A) Binder resin

(A-1) Acrylic binder resin (RY-25, Showadenko)

(A-2) Acrylic binder resin (CRG-1000S, SMS)

(B) Photopolymerizable monomer

DPHA (Nippon KAYAKU)

(C) Photopolymerization initiator

SPI-03 (Samyang Corporation)

(D) Coloring agent

(D-1) Red polymer dye according to Synthesis Example 1

(D-2) Red polymer dye according to Synthesis Example 2

(D-3) Red polymer dye according to Synthesis Example 3

(D-4) Red polymer dye according to Synthesis Example 4

(D-5) Red polymer dye according to Synthesis Example 5

(D-6) Red polymer dye according to Synthesis Example 6

(D-7) C.I. Pigment Red 254 pigment dispersion (AF1768, SANYO; pigment solids 12%)

(D-8) C.I. Pigment Red 177 pigment dispersion (EC960R, ENF; pigment solids 13%)

(D-9) Yellow dye solution (YDP-302, Gyeongin Yang; dye solids 15%)

(E) solvent

Propylene glycol methyl ether acetate (PGMEA, sigma-aldrich)

(F) antioxidants

Antioxidant of Formula 9 (IRGANOX 1010, BASF)

[Formula 9]

(G) Other additives

Fluorine surfactant (F-554, DIC)

(Unit: weight%) Kinds Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) Binder resin A-1 1.9 - 1.9 - 1.9 - 1.9 - A-2 - 2.4 - 2.4 - 2.4 - 2.4 (B) Photopolymerizable monomer 3.2 3.9 3.2 3.9 3.2 3.9 3.2 3.9 (C) Photopolymerization initiator 0.3 0.4 0.3 0.4 0.3 0.4 0.3 0.4 (D) Coloring agent D-1 1.5 1.7 - - - - - - D-2 - - 1.5 1.7 - - - - D-3 - - - - 1.5 - - - D-4 - - - - - 1.7 - - D-5 - - - - - - 1.5 - D-6 - - - - - - - 1.7 D-7 40 34 40 34 40 34 40 34 D-8 4.5 - 4.5 - 4.5 - 4.5 - D-9 - 6.5 - 6.5 - 6.5 - 6.5 (E) solvent 48.55 51.05 48.55 51.05 48.55 51.05 48.55 51.05 (F) antioxidant 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 (G) Other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Evaluation: color characteristics and pattern stability

After coating was performed at rpm that can exhibit a certain thickness for each photosensitive resin composition obtained in Examples 1, 2 and Comparative Examples 1 to 6 using a coating device (Mikasa, Opticoat MS-A150), 90 Pre-baking was carried out on a hot plate. Subsequently, front exposure was performed under an exposure condition of 50mj/cm ^{2 in} an exposure machine (Ushio, HB-50110AA), baking was performed at 230°C for 20 minutes under an oven condition, and specimen preparation was completed. Color characteristics (color coordinates, luminance (Y), contrast ratio (CR)) were measured before and after baking using MCPD 3000 equipment, and the results are shown in Table 3 below. Blooming (pattern foreign matter) measurement, the pattern was burned at 240°C for 40 minutes, analyzed through EDS, and photographed through a scanning electron microscope to check whether the pattern was foreign, and the results are shown in Table 3 and FIG. 1 to 4 are shown.

Pattern stability evaluation criteria

OK: Pattern blooming was not observed on the scanning electron microscope

NG: Pattern blooming observed on a scanning electron microscope

SPL Rx Ry Luminance (Y) Contrast Ratio (CR) Pattern Blooming Example 1 Before Bake 0.6638 0.3213 17.33 - - After Bake 0.6638 0.3212 17.32 10121 OK Example 2 Before Bake 0.6638 0.3210 17.24 - - After Bake 0.6638 0.3211 17.23 10113 OK Comparative Example 1 Before Bake 0.6638 0.3214 17.21 - - After Bake 0.6638 0.3213 17.15 10114 NG Comparative Example 2 Before Bake 0.6638 0.3211 17.08 - - After Bake 0.6637 0.3212 17.07 10115 NG Comparative Example 3 Before Bake 0.6635 0.3212 17.11 - - After Bake 0.6634 0.3211 17.10 10111 NG Comparative Example 4 Before Bake 0.6635 0.3214 17.07 - - After Bake 0.6633 0.3213 17.06 9984 NG Comparative Example 5 Before Bake 0.6635 0.3212 17.18 - - After Bake 0.6634 0.3215 17.19 10124 NG Comparative Example 6 Before Bake 0.6636 0.3214 17.02 - - After Bake 0.6637 0.3211 17.01 10024 NG

Through Table 3 and FIGS. 1 to 4, in the case of the photosensitive resin composition of Examples 1 and 2, compared with the photosensitive resin composition of Comparative Examples 1 to 6, there is no pattern blooming, that is, the structural structure of the pattern It is confirmed that it is possible to manufacture a curlie filter having excellent color characteristics (brightness and contrast ratio) due to its excellent stability.

The present invention is not limited to the above embodiments, but may be manufactured in various different forms, and those skilled in the art to which the present invention pertains have other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that can be implemented as. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (12)

(A) binder resin;
(B) photopolymerizable monomer;
(C) photopolymerization initiator;
(D) A polymer dye comprising “a structural unit selected from the group consisting of structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2” and “structural units represented by Chemical Formulas 3 to 6” Coloring agent containing; And
(E) solvent
Photosensitive resin composition comprising:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 1 to 6,
R ¹ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ² to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ⁷ is a substituted or unsubstituted C11 to C20 alkyl group,
R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
L ² is *-NH(C=O)O-*,
X is represented by the following formula (X-1) or formula (X-2).
[Formula X-1]

[Formula X-2]

According to claim 1,
The polymer dye is a photosensitive resin composition having a weight average molecular weight of 6,000 g / mol to 20,000 g / mol.
According to claim 1,
The polymer dye is relative to the total amount of polymer dye,
Structural unit represented by the formula (1) or 25 to 35% by weight of the structural unit represented by the formula (2),
10 to 20% by weight of the structural unit represented by Formula 3,
10 to 20% by weight of the structural unit represented by the formula (4),
15 to 25% by weight of the structural unit represented by the formula (5),
A photosensitive resin composition comprising 15 to 25% by weight of the structural unit represented by Formula 6.
According to claim 1,
The structural unit represented by Chemical Formula 1 is a photosensitive resin composition represented by any one of the following Chemical Formulas 1-1 to 1-6.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

According to claim 1,
The structural unit represented by Chemical Formula 2 is a photosensitive resin composition represented by any one of the following Chemical Formulas 2-1 to 2-8.
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

According to claim 1,
The polymer dye is a photosensitive resin composition containing 0.1 to 20% by weight relative to the total amount of the photosensitive resin composition.
According to claim 1,
The colorant is a photosensitive resin composition further comprising a yellow dye.
According to claim 1,
The colorant is a photosensitive resin composition further comprising a pigment.
According to claim 1,
The photosensitive resin composition
(A) 1 to 20% by weight of the binder resin;
(B) 1 to 20% by weight of the photopolymerizable monomer;
(C) 0.1 to 5% by weight of the photopolymerization initiator;
(D) 2 to 40% by weight of the colorant; And
(E) Residual amount of solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or a photosensitive resin composition further comprising an additive of a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-10.
A color filter comprising the photosensitive resin film of claim 11.

Images