KR20210081287A - Polymer, photosensitive resin composition including the same, photosensitive resin layer, color filter and display device - Google Patents

Abstract

Provided are a polymer including a structural unit represented by chemical formula 1, a photosensitive resin composition including the same, a photosensitive resin film manufactured by using the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter. In the chemical formula 1, the definition of each substituent is the same as defined in the specification.

Description

Polymer, photosensitive resin composition comprising same, and photosensitive resin film, color filter and display device using the same

The present disclosure relates to a polymer, a photosensitive resin composition including the same, a photosensitive resin film prepared using the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent adhesion to integrated circuits, and thus its range of use is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a light shielding layer, a color filter, and an ITO pixel electrode are formed, an active circuit portion consisting of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which the ITO pixel electrode is formed. A color filter includes a light blocking 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), blue (B)) to form each pixel. ), in which the three primary colors are arranged in a predetermined order, the pixel units are sequentially stacked.

The color filter is widely used in imaging devices, liquid crystal display devices (LCDs), field emission displays (FELs), and light emitting displays (LEDs), and its application range is rapidly expanding. In particular, in recent years, the use of liquid crystal display devices having advantages such as light weight, low power, and low driving voltage has become more diversified, and accordingly, a color filter is recognized as one of the most important parts in reproducing the color tone of the liquid crystal display device.

As the characteristics of the display industry require high color reproducibility, high resolution, and clear contrast ratio, the importance of color filters among the core components of liquid crystal display devices is being emphasized. Pigments currently used in color filters have excellent properties such as heat resistance, light resistance, and chemical resistance, but their solubility is not good, so the pigment is dispersed and used in the form of particles, so the color contrast is not good and the contrast is not clear. There is a downside to this. Due to these disadvantages, the necessity of using dyes instead of pigments is increasing. Dyes have better solubility than pigments and are advantageous for high color reproduction.

Meanwhile, in order for the dye to be used in a color filter, conditions such as wavelength, absorbance, transmittance, heat resistance, light resistance, and chemical resistance must be appropriate. Among red dyes, Xanthene-based compounds have a large extinction coefficient, so they are advantageous for coloring and have excellent durability, so they are well used as red dyes.

However, even when the xanthene-based compound is used as a red dye, the high-brightness and high-durability characteristics have not reached a satisfactory level compared to other dyes, so attempts to achieve better brightness and durability by modifying the xanthene-based compound are continuing. .

One embodiment is to provide a copolymer compound that can be used as a dye.

Another embodiment is to provide a photosensitive resin composition comprising the dye copolymer.

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 composition film.

Another embodiment is to provide a display device including the color filter.

One embodiment provides a polymer including a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

n1 is an integer from 1 to 10;

At least one of R ¹ and R ² may be a substituted or unsubstituted C6 to C20 aryl group.

Each of R ¹ and R ² may independently be a substituted or unsubstituted C6 to C20 aryl group.

The polymer may include two or more structural units represented by Formula 1 above.

The polymer may include a structural unit represented by the following formula (2).

[Formula 2]

In Formula 2,

X ¹ and X ² are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,

wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),

n1 is an integer from 1 to 10;

[Formula 3]

In Formula 3,

R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

The polymer may include a functional group represented by the following Chemical Formula 4 at the end.

[Formula 4]

In Formula 4,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n2 is an integer from 1 to 10;

One of both ends of the polymer may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

X ³ and X ⁴ are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,

A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),

wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n2 is an integer from 1 to 10;

[Formula 3]

In Formula 3,

R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

The polymer may be represented by any one of the following Chemical Formulas 2A to 2D.

[Formula 2A]

[Formula 2B]

[Formula 2C]

[Formula 2D]

In Formulas 2A to 2D,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n1 is an integer from 1 to 10,

n3 is an integer from 1 to 20,

n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20;

X ⁵ to X ⁷ are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ^{3 However} , X ⁵ and X ⁶ are different from each other,

A ⁺ is a monovalent metal cation or a compound represented by Formula 3,

R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

The polymer may be represented by any one of the following Chemical Formulas 2-1 to 2-6.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,

B ⁺ is [CH ₃ (CH ₂ ) ₁₁ ] ₂ N ⁺ (CH ₃ ) ₂ ,

R ¹¹ is a 2-hydroxypropyl group,

n3 is an integer from 1 to 20,

n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20.

The weight average molecular weight (Mw) of the polymer may be 1,000 g/mol to 15,000 g/mol.

The polymer may have a maximum absorbance in a wavelength range of 500 nm to 600 nm.

Another embodiment provides a photosensitive resin composition including a red dye-containing colorant, wherein the red dye includes the polymer.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent.

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

The photosensitive resin composition may further include a pigment as a colorant.

The photosensitive resin composition, with respect to the total amount of the photosensitive resin composition, the colorant 1% to 50% by weight, the binder resin 1% to 30% by weight, the photopolymerizable monomer 1% to 15% by weight, the photopolymerization initiator 0.01 % to 10% by weight and the remaining amount of the solvent.

The photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. may include

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

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

Another embodiment provides a display device including the color filter.

The specific details of other aspects of the invention are included in the detailed description below.

The polymer according to an embodiment has excellent solubility in organic solvents, excellent fluorescence control and spectral consistency, and uses a photosensitive resin composition including a colorant including the compound as a component, luminance, heat resistance, chemical resistance, etc. This excellent color filter can be manufactured.

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

Unless otherwise specified herein, "substituted" to "substituted" means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (F, Br, Cl or I), 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, and each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, And it means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified herein, "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, "aryl group" means a C6 to C20 aryl group, specifically C6 to refers to a C18 aryl group, “alkenyl group” refers to a C2 to C20 alkenyl group, specifically refers to a C2 to C18 alkenyl group, and “alkylene group” refers to a C1 to C20 alkylene group, specifically C1 to C18 alkylene group, and “arylene group” means a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

Unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" is "acrylic acid" and "methacrylic acid" It means both are possible.

Unless otherwise defined herein, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

Unless otherwise defined in the chemical formulas in the present 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 to the position.

Unless otherwise defined herein, "*" means a moiety connected to the same or different atoms or chemical formulas.

Unless otherwise defined herein, "Et" refers to an unsubstituted ethyl group.

One embodiment provides a polymer including a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

n1 is an integer from 1 to 10;

The * means a point connected to another atom.

In the color filter made of the pigment-type photosensitive resin composition, there is a limit to the luminance and contrast ratio caused by the size of the pigment particle. In addition, in the case of a color imaging device for an image sensor, a smaller dispersed particle size is required for fine pattern formation. In order to meet this demand, attempts to implement a color filter with improved luminance and contrast ratio by introducing a non-particle dye instead of a pigment to prepare a photosensitive resin composition suitable for the dye are continuing.

In general, the xanthene-based compound has a separate charge, and the photosensitive resin composition including the same has low solubility in organic solvents such as PGMEA, and has poor durability such as heat resistance and chemical resistance, so there is a limit to use as a colorant in the photosensitive resin composition. .

However, the compound according to an embodiment, that is, the polymer including the structural unit represented by Chemical Formula 1 may improve solubility in an organic solvent, and furthermore, the structural unit may have a polymer structure in a polymerized form to form a monomer. The fluorescence control and spectral compatibility may be superior to those of the compound of , and a color filter with further improved luminance and contrast may be manufactured by using the photosensitive resin composition including the compound.

R ¹ and R ² may be a substituted or unsubstituted C6 to C20 aryl group, for example, a C6 to C18 aryl group, a C6 to C14 aryl group, or a C6 to C10 aryl group. When R ¹ and R ² are an aryl group such as a phenyl group, the durability of the dye may be improved, and the color filter made of the photosensitive resin composition including the R 1 and R 2 may have higher brightness and higher contrast ratio.

At least one of R ¹ and R ² may be a substituted or unsubstituted C6 to C20 aryl group. For example, ^{at least one of R 1} and R ² may be a substituent represented by Formula A below.

[Formula A]

In the above formula (A),

Y ¹ to Y ⁴ are each independently hydrogen or a C1 to C10 alkyl group,

X is SO ₃ ^{-A +} , or SO ₂ NHR ³ ,

wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),

n1 is an integer from 1 to 10,

[Formula 3]

In Formula 3,

R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

Here, R ¹ and R ² may each independently be a substituted or unsubstituted C6 to C20 aryl group, for example, ^{both R 1} and R ² may be a substituent represented by Formula A.

The polymer may include two or more structural units represented by Formula 1 above. That is, the polymer may be formed from copolymerization between different structural units, as represented by Chemical Formula 1.

The polymer may be a polymer including a structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2,

X ¹ and X ² are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,

wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),

n1 is an integer from 1 to 10,

[Formula 3]

In Formula 3,

R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

The monovalent metal cation may be, for example, a monovalent metal cation such as Na ⁺ , K ⁺ , and is not particularly limited as long as it is a monovalent metal cation capable of forming a salt with the SO ₃ ^{− .}

The R ⁴ to R ⁷ are, for example, each independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, iso It may be a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The polymer may include a functional group represented by the following Chemical Formula 4 at the end.

[Formula 4]

In Formula 4,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n2 is an integer from 1 to 10;

R ⁸ may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The substituted or unsubstituted acrylate group may be, for example, represented by the following formula (E).

[Formula E]

In the above formula E

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

R ^b is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

When R ⁸ is a substituted or unsubstituted acrylate group, R ⁸ is a methyl (meth) acrylate group, an ethyl (meth) acrylate group, a butyl (meth) acrylate group, a propyl (meth) acrylate group, It may be an acrylate group such as a hexyl (meth) acrylate group, a heptyl (meth) acrylate group, or an octyl (meth) acrylate group.

As the polymer includes the functional group represented by Chemical Formula 4 at the terminal, light absorption characteristics of the photosensitive resin composition including the polymer may be improved. For example, when the end of the polymer is an alkyl group such as an ethyl group, light absorption characteristics can be greatly improved.

One of both ends of the polymer may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

X ³ and X ⁴ are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,

A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),

wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n2 is an integer from 1 to 10,

[Formula 3]

In Formula 3,

R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

The monovalent metal cation may be, for example, a monovalent metal cation such as Na ⁺ , K ⁺ , and is not particularly limited as long as it is a monovalent metal cation capable of forming a salt with the SO ₃ ^{− .}

The R ⁴ to R ⁷ are, for example, each independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, iso It may be a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

R ⁸ may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

R ⁸ is, for example, a methyl (meth) acrylate group, an ethyl (meth) acrylate group, a butyl (meth) acrylate group, a propyl (meth) acrylate group, a hexyl (meth) acrylate group, heptyl ( It may be an acrylate group such as a meth)acrylate group or an octyl (meth)acrylate group.

The polymer may be represented by any one of the following Chemical Formulas 2A to 2D.

[Formula 2A]

[Formula 2B]

[Formula 2C]

[Formula 2D]

In Formulas 2A to 2D,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

n1 is an integer from 1 to 10,

n3 is an integer from 1 to 20,

n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20;

X ⁵ to X ⁷ are each independently each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ^{3 However} , X ⁵ and X ⁶ are different from each other,

A ⁺ is a monovalent metal cation or a compound represented by Formula 3,

R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

That is, as X ⁵ and X ⁶ are different substituents, the polymer may include two or more different monomers.

The polymer may be a polymer represented by any one of Chemical Formulas 2-1 to 2-9, 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]

[Formula 2-9]

In Formulas 2-1 to 2-9,

B ⁺ is [CH ₃ (CH ₂ ) ₁₁ ] ₂ N ⁺ (CH ₃ ) ₂ ,

R ¹¹ is a 2-hydroxypropyl group,

n3 is an integer from 1 to 20,

n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20.

The weight average molecular weight (Mw) of the polymer is 1,000 g / mol to 15,000 g / mol, for example, 1,000 g / mol to 14,000 g / mol, for example, 1,000 g / mol to 13,000 g / mol, for example For example, 1,000 g/mol to 12,000 g/mol, such as 1,000 g/mol to 11,000 g/mol, such as 1,000 g/mol to 10,000 g/mol, such as 1,000 g/mol to 9,000 g/mol, such as 1,000 g/mol to 8,000 g/mol, such as 1,000 g/mol to 7,000 g/mol, such as 1,000 g/mol to 6,000 g/mol, such as 1,000 g/mol to 5,000 g/mol, such as 1,000 g/mol to 4,000 g/mol, such as 2,000 g/mol to 15,000 g/mol, such as 3,000 g/mol to 15,000 g/mol mol, such as 4,000 g/mol to 15,000 g/mol, such as 5,000 g/mol to 6,000 g/mol, such as 7,000 g/mol to 15,000 g/mol, such as 8,000 g /mol to 15,000 g/mol, but is not limited thereto. When the weight average molecular weight of the polymer is out of the above range, solubility in a solvent may be lowered. In addition, when the polymer has a weight average molecular weight (Mw) value within the above range, the luminance of a color filter manufactured using the photosensitive resin composition including the same may be improved. Furthermore, when the polymer has a weight average molecular weight value within the above range and at the same time has a butylene linking group, the intensity of a peak at a wavelength of 580 nm with respect to red luminance increases, thereby further improving luminance.

Since the polymer according to an embodiment includes the structural unit represented by Formula 1, it is possible to express a more vivid color even with a small amount, so that when used as a colorant, it is difficult to manufacture a display device having excellent color characteristics such as luminance and contrast ratio. It is possible. For example, the dye compound represented by Formula 1 may have a maximum absorbance (λmax) in a wavelength range of 500 nm to 600 nm.

In general, the dye is the most expensive component among the components used in the color filter. Therefore, in order to achieve a desired effect, for example, high luminance or high contrast ratio, more expensive dyes must be used, which inevitably increases the production cost. However, when the polymer according to the embodiment is used as a dye in the color filter, excellent color characteristics such as high brightness and high contrast ratio can be achieved even with a small amount, thereby reducing the production cost.

According to another embodiment, there is provided a photosensitive resin composition comprising a red dye-containing colorant, wherein the red dye includes the polymer according to the embodiment.

The polymer according to the exemplary embodiment may serve as a red dye (colorant) in the photosensitive resin composition, thereby exhibiting excellent color characteristics.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent. That is, the photosensitive resin composition may include the polymer according to the embodiment as a colorant, and other binder resins, photopolymerizable compounds, photoinitiators, and solvents.

Hereinafter, the components will be described in detail.

coloring agent

The photosensitive resin composition may further include a pigment as a colorant in addition to including the polymer as a red dye.

The colorant is 1 wt% to 50 wt%, for example, 1 wt% to 45 wt%, for example, 1 wt% to 40 wt%, for example, 1 wt% to the total amount of the photosensitive resin composition 35% by weight, such as 1% to 30% by weight, such as 1% to 25% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight , for example, may be included in 1 wt% to 10 wt%, but is not limited thereto. When the colorant according to an embodiment is included in the above range, the color reproducibility and contrast ratio are excellent.

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 include 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. Blue pigment 16, C.I. Blue pigment 22, C.I. Blue pigment 60, C.I. Blue pigment 64, C.I. blue pigment 80 or a combination thereof.

Examples of the violet pigment include C.I. Violet pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet pigment 27, C.I. Violet Pigment 28, 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 include perylene-based pigments, anthraquinone-based pigments, azo-based pigments, diazo-based pigments, quinacridone-based pigments, and anthracene-based pigments. Specific examples of the red pigment include perylene pigment, quinacridone pigment, naphthol AS, cycomine pigment, anthraquinone (sudan I, II, III, R), vis azo ), benzopyran, and the like.

Examples of the green pigment include C.I. Pigment Green 58, C.I. Halogenated phthalocyanine pigments, such as pigment green 59, etc. are mentioned.

Examples of the yellow pigment include C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may include a solid pigment, a solvent, and a dispersing agent for uniformly dispersing the pigment in the solvent.

The solid content of the pigment is 1% to 20% by weight, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% to 20% by weight, based on the total amount of the pigment dispersion. It may be included in 15 wt%.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, and the like may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyalcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid 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 dispersant include BYK's 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, etc. from EFKA Chemicals; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc. from Zeneka; or Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 1 wt% to 20 wt% based on the total amount of the pigment dispersion. When the dispersant is included within the above range, it is possible to maintain an appropriate viscosity and thus the photosensitive resin composition has excellent dispersibility, thereby maintaining optical, physical and chemical quality when applying the product.

As a solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono) methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. may be used.

binder resin

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

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including 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 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene or vinylbenzylmethyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (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 a 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 include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl meth acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

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, has an appropriate viscosity, and has excellent adhesion to a substrate when manufacturing a color filter.

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

The cardo-based binder resin may include a repeating unit represented by the following formula (6).

[Formula 6]

In Formula 6,

R ¹² and R ¹³ are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group,

R ¹⁴ and R ¹⁵ 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 ¹⁶ R ¹⁷ , SiR ¹⁸ R ¹⁹ (wherein, R ¹⁶ to R ¹⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or Any one of the linking groups represented by Formulas 6-1 to 6-11,

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

(In Formula 6-5,

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 6-6]

[Formula 6-7]

[Formula 6-8]

[Formula 6-9]

[Formula 6-10]

[Formula 6-11]

Z ² is an acid dianhydride residue,

p1 and p2 are each independently an integer of 0 to 4.

The cardo-based binder resin may include a functional group represented by the following Chemical Formula 7 at at least one of both ends.

[Formula 7]

In Formula 7,

Z ³ may be represented by the following Chemical Formulas 7-1 to 7-7.

[Formula 7-1]

(In Formula 7-1, 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 7-2]

[Formula 7-3]

[Formula 7-4]

[Formula 7-5]

(In Formula 7-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group, or C2 to C20 alkenylamine group.)

[Formula 7-6]

[Formula 7-7]

The cardo-based binder resin may include, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylic acid dianhydride anhydride compounds such as , tetrahydrofuran tetracarboxylic acid dianhydride 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 tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, it can be prepared by mixing two or more of an amine or ammonium salt compound such as benzyltriethylammonium chloride.

When the cardo-based binder resin is used together with the above-described acrylic binder resin, a photosensitive resin composition having excellent adhesion and high resolution and high luminance characteristics can be obtained.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 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, a pattern can be formed without a residue when manufacturing a color filter, 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 is 1 wt% to 30 wt%, for example, 1 wt% to 25 wt%, for example, 1 wt% to 20 wt%, for example, 1 wt% based on the total amount of the photosensitive resin composition to 15% by weight, such as 1% to 10% by weight, such as 1% to 7% by weight, such as 1% to 5% by weight, for example, but not limited thereto. . When the binder resin is included within the above range, excellent developability and improved crosslinking properties can be obtained when manufacturing a color filter, thereby obtaining excellent surface smoothness.

photopolymerizable monomer

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, it is possible to form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization upon 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, 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. Examples of the monofunctional ester of (meth)acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^® by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD TC-110S ^® , Copper TC-120S ^®, etc.; ^{V-158 ®} and V-2311 ^{® of} Osaka Yuki Chemical High School Co., Ltd. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid, Toagosei Chemical Co., Ltd. Aronix M-210 ^® , copper M-240 ^® , copper M-6200 ^® and the like; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , Copper HX-220 ^® , Copper R-604 ^®, etc.; ^{and V-260 ®} , V-312 ^® , V-335 HP ^{® of} Osaka Yuki Chemical High School Co., Ltd. and the like. Examples of the trifunctional ester of (meth)acrylic acid, Toagosei Chemical Co., Ltd. Aronix M-309 ^® , copper M-400 ^® , copper M-405 ^® , copper M-450 ^® , copper M -710 ^® , copper M-8030 ^® , copper M-8060 ^®, etc.; Nihon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® etc.; ^{V-295 ®} , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® etc. from Osaka Yuki Kayaku High School Co., Ltd. are mentioned. These products may be used alone or in combination of two or more.

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

The photopolymerizable monomer is 1 wt% to 15 wt%, for example, 1 wt% to 10 wt%, for example, 1 wt% to 7 wt%, for example, 1 wt% with respect to the total amount of the photosensitive resin composition % to 5% by weight, but is not limited thereto. When the photopolymerizable monomer is included within the above range, curing occurs sufficiently during exposure in the pattern forming process, thereby providing excellent reliability and excellent developability in an alkaline developer.

photopolymerization initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or a combination thereof. Can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -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. are mentioned.

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

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are 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 compound 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. are mentioned.

Examples of the oxime-based compound include an O-acyloxime-based compound, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(o-acetyloxime). )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compound 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)-octane-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O- Acetate etc. are mentioned.

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

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light to enter an excited state and then transferring the energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like. can be heard

The photopolymerization initiator is 0.01 wt% to 10 wt%, for example, 0.01 wt% to 9 wt%, for example, 0.01 wt% to 7 wt%, for example, 0.01 wt%, based on the total amount of the photosensitive resin composition to 5% by weight, such as 0.01% to 3% by weight, such as 1% to 10% by weight, such as 3% to 10% by weight, but not limited thereto. . When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, and the pattern has excellent heat resistance, light resistance and chemical resistance, and also has excellent resolution and adhesion. A decrease in transmittance can be prevented.

menstruum

As the solvent, materials having compatibility with the (dye) compound, the pigment, the binder resin, the photopolymerizable monomer, and the photopolymerization initiator but not reacting according to an embodiment 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 monomethyl ether and ethylene glycol monoethyl 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 methyl ethyl 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-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; oxyacetic acid alkyl 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 3-oxy methyl propionate and 3-oxy ethyl propionate; 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 propionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate; 2-methoxy-2-methyl methyl propionate; 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionate alkyls such as ethyl methyl propionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxyacetate, and 2-hydroxy-3-methyl methyl butanoate; Ketonic acid esters such as ethyl pyruvate, and the like, and 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 and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, preferably, in consideration of compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; 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 can be used.

The solvent may be included in a balance, for example, 40 wt% to 90 wt% based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, since the photosensitive resin composition has an appropriate viscosity, processability in manufacturing the color filter is excellent.

other additives

The photosensitive resin composition may include malonic acid to prevent stains or spots during application, to improve leveling performance, and to prevent generation of residues due to undeveloped products; 3-amino-1,2-propanediol; a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group and an epoxy group; leveling agent; fluorine-based surfactants; An additive such as a radical polymerization initiator may be further included.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycan Cydoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

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

The epoxy compound may be included in an amount of 0.01 parts by weight to 20 parts by weight, for example, 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defect formation, if necessary.

A fluorine-based surfactant may be used as the surfactant, and examples of the fluorine-based surfactant include DIC's F-482, F-484, F-478, F-554, and the like, but are not limited thereto.

The surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is secured, staining does not occur, and wettability to a glass substrate is excellent.

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

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

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

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

applying the photosensitive resin composition onto a support substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied photosensitive resin composition to form a photosensitive resin composition film; exposing the photosensitive resin composition film; developing the exposed photosensitive resin composition film with an aqueous alkali solution to prepare a photosensitive resin film; and heat-treating the photosensitive resin film. Since the process conditions and the like are well known in the art, detailed descriptions thereof will be omitted herein.

According to another embodiment, there is provided a display device including the color filter according to the embodiment. The display device may be, for example, a liquid crystal display (LCD).

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

Synthesis Example: Polymer Synthesis

Synthesis Example 1: Synthesis of a polymer represented by Formula 2-1

Acid red 289 (1 mol), Dilauryldimethylammonium Bromide (1.5 mol) _{was added to H 2} O, heated to 70° C., stirred for 24 hours, cooled at room temperature, and the organic layer was extracted with MC to obtain an intermediate. This intermediate and (1 mol) 1,2-Diiodoethane (1 mol), K ₂ CO ₃ (10 mol) were put in NMP (N-methylpyrrolidone), heated to 100° C. and stirred for 24 hours, and then iodoethane in a mixture state was added for quenching. Methylene chloride was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure, purified by column chromatography, and solidified with hexane to synthesize a polymer represented by the following Chemical Formula 2-1.

[Formula 2-1]

GPC MS: 5,003 m/z

Synthesis Example 2: Synthesis of the polymer represented by Formula 2-2

In the reaction of Synthesis Example 1, a polymer represented by the following Chemical Formula 2-2 was synthesized in the same manner as in Synthesis Example 1, except that 1,4-Diiodobutane was used instead of 1,2-Diiodoethane as the linker chain.

[Formula 2-2]

GPC MS: 5,003 m/z

Synthesis Example 3: Synthesis of a polymer represented by Formula 2-3

3',6'-Dichlorospiro[3H-2,1-benzoxathiol-3,9'-[9H]xanthene]-1,1-dioxide (1 mol), 2,6-dimethylaniline (2 mol), ZnCl ₂ ( 1.7 mol) was added to DMF and stirred at room temperature for 24 hours. Methylene chloride was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and solidified with Hexane to obtain Intermediate 1 (intermediate 1). Thereafter, in Synthesis Example 1, Acid red 289 was replaced with Intermediate 1, and the same process was performed to synthesize a polymer represented by the following Chemical Formula 2-3.

[Formula 2-3]

GPC MS: 6,705 m/z

Synthesis Example 4: Synthesis of a polymer represented by Formula 2-4

In the reaction of Synthesis Example 1, the intermediate reaction was omitted and Ethyl methacrylate was used instead of Acid red 289 and iodoethane as a quenching material. In the same manner as in Synthesis Example 1, a polymer represented by the following Chemical Formula 2-4 was synthesized. did.

[Formula 2-4]

GPC MS: 8,550 m/z

Synthesis Example 5: Synthesis of a polymer represented by Formula 2-5

In the reaction of Synthesis Example 3, a polymer represented by the following Chemical Formula 2-5 was synthesized in the same manner as in Synthesis Example 3, except that 2-Iodobutane was used instead of iodoethane, which is a quenching material.

[Formula 2-5]

GPC MS: 6,502 m/z

Synthesis Example 6: Synthesis of a polymer represented by Formula 2-6

In the reaction of Synthesis Example 2, a polymer represented by the following Chemical Formula 2-6 was synthesized in the same manner as in Synthesis Example 2, except that 1-Bromo-2-propanol was used instead of Dilauryldimethylammonium Bromide.

[Formula 2-6]

GPC MS: 7,782 m/z

In Formula 2-6,

)이다.R ¹¹ is a 2-hydroxypropyl group (

)to be.

Synthesis Example 7: Synthesis of a polymer represented by Formula 2-7

In the reaction of Synthesis Example 2, the intermediate reaction was omitted, and 2-Iodobutane was used instead of the quenching material iodoethane in the mixture of Acid red 289 and the intermediate of Formula 2-2. In the same manner as in Synthesis Example 2, A polymer represented by the following Chemical Formula 2-7 (n4 and n5 has a ratio of 1:1) was synthesized.

[Formula 2-7]

Maldi-tof MS: 8,264 m/z

Synthesis Example 8: Synthesis of a polymer represented by Formula 2-8

In the reaction of Synthesis Example 1, a polymer represented by the following Chemical Formula 2-8 was synthesized in the same manner as in Synthesis Example 1, except that 1,6-Diiodohexane was used instead of 1,2-Diiodoethane for the linker chain.

[Formula 2-8]

Maldi-tof MS: 8,264 m/z

Synthesis Example 9: Synthesis of a polymer represented by Formula 2-9

In the reaction of Synthesis Example 1, a polymer represented by the following Chemical Formula 2-9 was synthesized in the same manner as in Synthesis Example 1, except that 1,8-Diiodooctane was used instead of 1,2-Diiodoethane as the linker chain.

[Formula 2-9]

Maldi-tof MS: 8,264 m/z

Comparative Synthesis Example 1: Synthesis of Compound X

10 g of Compound A (CAS No. 77545-45-0) was put into a reactor and dissolved with 100 g of 2-propanol. After adding 7.2 g of diethylamine, 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 resulting precipitate was suction filtered and further washed with water. The filtrate was dried to obtain 9.9 g (84% yield) of the compound X.

Maldi-tof MS: 478.2 m/z

Comparative Synthesis Example 2: Synthesis of Compound Y

Acid red 289 (1 mol), Dilauryldimethylammonium Bromide (1.5 mol) _{was added to H 2} O, heated to 70° C., stirred for 24 hours, cooled at room temperature, and the organic layer was extracted with MC to obtain an intermediate. This intermediate and (1 mol) 1,12-Diiodododecane (1 mol), K ₂ CO ₃ (10 mol) were put in NMP (N-methylpyrrolidone), heated to 100° C. and stirred for 24 hours, and then iodoethane in a mixture state was added for quenching. Methylene chloride was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure, purified by column chromatography, and solidified with hexane to synthesize the polymer represented by the compound Y.

Example: Synthesis of photosensitive resin composition

(Examples 1 to 9, Comparative Examples 1 and 2)

In the composition shown in Table 1 below, a photopolymerization initiator was added to a solvent and dissolved by stirring at room temperature for 1 hour. Then, a binder resin and a photopolymerizable monomer were added, and the mixture was stirred at room temperature for 1 hour. Here, other additives were added and stirred at room temperature for 1 hour. Here, the compounds prepared in Synthesis Examples 1 to 9, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 (or together with a red pigment) were added and stirred at room temperature for 2 hours, followed by 3 times with respect to the solution Filtration was performed to remove impurities to prepare photosensitive resin compositions according to Examples 1 to 9, Comparative Examples 1 and 2, respectively. The components used in the preparation of 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 company)

(B) photopolymerizable monomer

(B-1) DPHA (Nippon KAYAKU)

(B-2) ABPE-20 (Shin-nakamura)

(C) photoinitiator

(C-1) SPI-03 (Samyang Corporation)

(C-2) OXE-01 (Basf)

(D) colorant

(D-1) Polymer according to Synthesis Example 1

(D-2) Polymer according to Synthesis Example 2

(D-3) Polymer according to Synthesis Example 3

(D-4) Polymer according to Synthesis Example 4

(D-5) Polymer according to Synthesis Example 5

(D-6) Polymer according to Synthesis Example 6

(D-7) Polymer according to Synthesis Example 7

(D-8) Polymer according to Synthesis Example 8

(D-9) Polymer according to Synthesis Example 9

(D-10) Monomer according to Comparative Synthesis Example 1

(D-11) Monomer according to Comparative Synthesis Example 2

(D-12) C.I. pigment red 254 (SANYO company)

(E) solvent

Propylene glycol monomethyl ethyl acetate (PGMEA, sigma-aldrich)

(F) other additives

Fluorine-based surfactant (F-554, DIC)

(Unit: % by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 binder resin A-1 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 A-2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 photopolymerizable monomer B-1 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 B-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 photopolymerization initiator C-1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 C-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 coloring agent D-1 10.1 - - - - - - - - - - D-2 - 10.1 - - - - - - - - - D-3 - - 10.1 - - - - - - - - D-4 - - - 10.1 - - - - - - - D-5 - - - - 10.1 - - - - - - D-6 - - - - - 10.1 - - - - - D-7 - - - - - - 10.1 - - - - D-8 - - - - - - - 10.1 - - - D-9 - - - - - - - - 10.1 - - D-10 - - - - - - - - - 10.1 - D-11 - - - - - - - - - - 10.1 D-12 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 menstruum 41.7 41.7 41.7 41.7 41.7 41.7 41.7 41.7 41.7 41.7 41.7 other additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Evaluation 1: Evaluation of color change before/after baking

The color characteristics of the color filter specimens prepared using the photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 were measured three times for 20 minutes in a hot air circulation oven at 230°C. The color change before and after baking was measured using a spectrophotometer (MCPD3000 manufactured by Otsuka Electronics) by additional baking over a period of time, and the results are shown in Table 2 below.

Evaluation 2: Luminance characteristic evaluation

The photosensitive resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were applied to a thickness of 1 μm to 3 μm on a glass substrate having a thickness of 1 mm after degreasing, and on a hot plate at 90° C. A coating film is obtained by drying for 2 minutes. Then, using a high-pressure mercury lamp with a dominant wavelength of 365 nm on the coating film, the entire surface is exposed under the condition of ^{50 mJ/cm 2 .} Thereafter, the sample was dried for 20 minutes in a hot air circulation drying furnace at 230° C. to obtain a sample of the same thickness. The luminance of the pixel layer was measured using a spectrophotometer (MCPD3000, Otsuka electronic), and the results are shown in Table 2 below.

Evaluation 3: Chemical resistance evaluation

The color filter specimens prepared by using the photosensitive resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were immersed in an NMP solution at 90° C. for 10 minutes to evaluate the chemical resistance of the PI solution. . Chemical resistance was evaluated by the color change of the color filter pattern before and after immersion in the NMP solution and whether the color filter pattern was peeled off after immersion in the stripper. The change in color characteristics of the color filter pattern was measured using a spectrophotometer (MCPD3000 manufactured by Otsuka Electronics), and whether the color filter pattern was peeled off was evaluated with an optical microscope. The evaluation results are shown in Table 2 below.

Evaluation 4: Heat resistance evaluation

The dyes dissolved in the photosensitive resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were evaluated for heat resistance using a TGA (Discovery Co.) heat resistance measuring instrument. In the air condition, the temperature increase rate was 5 °C/min, and the experiment was carried out by setting the temperature range from 30 °C to 400 °C. The evaluation results are shown in Table 2 below.

Evaluation 5: Fluorescence control evaluation

The dyes of Examples 1 to 9, Comparative Examples 1 and 2 were diluted in a solvent. At this time, the concentration should be less than 0.02 A.U in UV-vis. After that, the fluorescence properties are evaluated using an integrating hemisphere measuring device for solution.

_emission, 기타 표면 이상 및 process별 외관상 issue 등 이다. QY는 입사된 빛 대비 방출된 빛의 비율을 나타내는 지표로, 형광이 얼마나 나오는지 알려주는 지표이다. FWHM은 빛의 방출 스펙트럼 상 최대 세기의 절반값에 해당하는 부분의 두 파장값이 나타내는 폭을 읽는 항목이며 반치폭이라고 하고 좁을수록 좋다. Fluorescence intensity는 방출 스펙트럼에서 y축에 해당하는 값으로 형광의 세기를 나타내며 QY에 Abs(흡광도)를 곱한 두께보정치를 감안한 값으로 판단한다. Evaluation items are QY (Quantum Yield), FWHM (Full Width at Half Maximum), Fluorescence intensity,

_emission, other surface abnormalities, and appearance issues by process. QY is an index indicating the ratio of emitted light to incident light, and is an index indicating how much fluorescence is emitted. FWHM is an item that reads the width indicated by the two wavelength values in the part corresponding to the half value of the maximum intensity on the emission spectrum of light. It is called the half maximum width, and the narrower it is, the better. Fluorescence intensity is a value corresponding to the y-axis in the emission spectrum, indicating the intensity of fluorescence, and is judged as a value considering the thickness correction value obtained by multiplying QY by Abs (absorbance).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Color difference after post-baking
(Δ Eab*) 2.2 2.2 2.3 2.0 2.4 2.2 2.3 2.3 2.4 3.6 3.2 Corrected luminance after post-baking (%) 103 102.9 102.9 103.1 103.5 103.6 103.6 102.5 101.5 100 100 chemical resistance
(Δ Eab*) 1.3 1.4 1.1 1.3 1.5 1.3 1.1 1.2 1.5 5.5 4.0 Heat resistance (℃) 300 301 336 314 333 311 300 299 301 283 279 Fluorescence control
QY*Abs
(%) 9.1 9.5 12 8.2 10.5 11.9 12.2 13.4 15 29.04 20.78

Referring to Table 2, the photosensitive resin compositions of Examples 1 to 9 including the polymer (red dye) according to one embodiment were compared with Comparative Examples 1 and 2 not including the polymer, luminance, etc. It can be confirmed that not only the color characteristics of the , but also the heat resistance, chemical resistance and fluorescence control characteristics are excellent.

In the foregoing, specific embodiments of the present invention have been described and shown, but it is common knowledge in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those who have Accordingly, such modifications or variations should not be individually understood from the technical spirit or point of view of the present invention, and modified embodiments should be said to belong to the claims of the present invention.

Claims (20)

A polymer comprising a structural unit represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,
n1 is an integer from 1 to 10;
According to claim 1,
At least one of R ¹ and R ² is a substituted or unsubstituted C6 to C20 aryl group.
According to claim 1,
wherein R ¹ and R ² are each independently a substituted or unsubstituted C6 to C20 aryl group.
According to claim 1,
The polymer is a polymer comprising two or more structural units represented by the formula (1).
According to claim 1,
The polymer is a polymer comprising a structural unit represented by the following formula 2:
[Formula 2]

In Formula 2,
X ¹ and X ² are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,
wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),
n1 is an integer from 1 to 10,
[Formula 3]

In Formula 3,
R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The polymer is a polymer comprising a functional group represented by the following formula (4) at both ends:
[Formula 4]

In Formula 4,
R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,
n2 is an integer from 1 to 10;
According to claim 1,
One of both ends of the polymer is a polymer represented by the following formula (5):
[Formula 5]

In Formula 5,
X ³ and X ⁴ are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ³ ,
A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),
wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,
n2 is an integer from 1 to 10,
[Formula 3]

In Formula 3,
R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The polymer is a polymer represented by any one of the following Chemical Formulas 2A to 2D:
[Formula 2A]

[Formula 2B]

[Formula 2C]

[Formula 2D]

In Formulas 2A to 2D,
R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,
n1 is an integer from 1 to 10,
n3 is an integer from 1 to 20,
n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20;
X ⁵ to X ⁷ are each independently hydrogen, SO ₃ ^- A ⁺ , or SO ₂ NHR ^{3 However} , X ⁵ and X ⁶ are different from each other,
A ⁺ is a monovalent metal cation or a compound represented by the following formula (3),
wherein R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
[Formula 3]

In Formula 3,
R ⁴ to R ⁷ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The polymer is a polymer represented by any one of the following Chemical Formulas 2-1 to 2-6:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,
B ⁺ is [CH ₃ (CH ₂ ) ₁₁ ] ₂ N ⁺ (CH ₃ ) ₂ ,
R ¹¹ is a 2-hydroxypropyl group,
n3 is an integer from 1 to 20,
n4 and n5 are each independently an integer from 1 to 10, provided that 2 ≤ n4+n5 ≤ 20.
According to claim 1,
The polymer has a weight average molecular weight (Mw) of 1,000 g/mol to 15,000 g/mol.
According to claim 1,
The polymer is a polymer having a maximum absorbance in a wavelength range of 500 nm to 600 nm.
a colorant containing a red dye;
The red dye is a photosensitive resin composition comprising the polymer of any one of claims 1 to 11.
13. The method of claim 12,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent.
14. The method of claim 13,
The binder resin is an acrylic binder resin, a cardo-based binder resin, or a photosensitive resin composition comprising a combination thereof.
13. The method of claim 12,
The colorant is a photosensitive resin composition further comprising a pigment.
14. The method of claim 13,
The photosensitive resin composition, with respect to the total amount of the photosensitive resin composition,
1% to 50% by weight of the colorant;
1 wt% to 30 wt% of the binder resin;
1 wt% to 15 wt% of the photopolymerizable monomer;
0.01 wt% to 10 wt% of the photopolymerization initiator, and
the remaining amount of the solvent
A photosensitive resin composition comprising a.
14. The method of claim 13,
The photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. A photosensitive resin composition comprising.
A photosensitive resin film prepared by using the photosensitive resin composition of claim 12 .
A color filter comprising the photosensitive resin film of claim 18 .
A display device comprising the color filter of claim 19 .