JP2023508048A - Polymer, photosensitive resin composition containing the same, and photosensitive resin film, color filter and display device using the same - Google Patents

Abstract

A polymer containing a structural unit represented by a specific chemical formula, a photosensitive resin composition containing the polymer, a photosensitive resin film containing the photosensitive resin composition, a color filter containing the photosensitive resin film, and the color filter A display device is provided comprising:
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Description

The present description relates to a polymer, a photosensitive resin composition containing the same, a photosensitive resin film prepared using the photosensitive resin composition, a color filter containing the photosensitive resin film, and a display device containing the color filter. It is.

A liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption drive, and excellent bonding with integrated circuits. Its range of use has been expanded for Such a liquid crystal display device includes a lower substrate on which a light shielding layer, a color filter and ITO pixel electrodes are formed, and an upper substrate on which an active circuit section composed of a liquid crystal layer, a thin film transistor and a storage capacitor layer and an ITO pixel electrode are formed. Consists of Color filters are composed of a light-shielding layer formed in a predetermined pattern on a transparent substrate to shield the boundaries between pixels and a plurality of colors (usually red (R), green) to form each pixel. It has a structure in which pixel portions in which the three primary colors (G) and blue (B)) are arranged in a predetermined order are sequentially stacked.

The color filters are widely used in imaging devices, liquid crystal displays (LCDs), field emission displays (FEDs), light emitting displays (LEDs), and the like, and their application range is rapidly expanding. In particular, recently, applications for liquid crystal display devices, which have advantages such as light weight, low power consumption, and low driving voltage, are becoming more diversified, and color filters are one of the most important parts in reproducing the color tone of liquid crystal display devices. recognized as.

Due to the characteristics of the display industry, a high color reproduction rate, a high resolution, a clear contrast ratio, etc. are required, and the importance of color filters among the core components of the liquid crystal display device is emphasized. Pigments currently used in color filters have excellent properties such as heat resistance, light resistance, and chemical resistance. There is a disadvantage that the color of the display is not good because it is not clear. These shortcomings drive the need to use dyes instead of pigments. Dyes have better solubility than pigments and are advantageous for high color reproduction.

On the other hand, for dyes to be used in color filters, conditions such as wavelength, absorbance, transmittance, heat resistance, light resistance, and chemical resistance must be suitable. Among red dyes, xanthene-based compounds are often used as red dyes because they have a large absorption coefficient, are advantageous for coloring, and have excellent durability.

However, even if a xanthene-based compound is used as a red dye, it has not reached a level that satisfies the characteristics of high brightness and high durability compared to other dyes. Attempts to achieve superior brightness and durability continue.

One embodiment is for providing 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 produced using the photosensitive resin composition.

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

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

One embodiment provides a polymer comprising a structural unit represented by Formula 1 below.

In the above chemical formula 1,
R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted a substituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, 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 aryl group having 6 to 20 carbon atoms.

Each of R ¹ and R ² may be independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

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

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

In the above chemical formula 2,
X ¹ and X ² are each independently hydrogen, SO ₃ ⁻ A ⁺ , or SO ₂ NHR ³ ;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A ⁺ is a monovalent metal cation or a compound represented by the following chemical formula 3;
n1 is an integer from 1 to 10;

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The polymer may include a functional group represented by Chemical Formula 4 below at its terminal.

In the above chemical formula 4,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer of 1-10.

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

In the above chemical 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 chemical formula 3;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer from 1 to 10,

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The polymer may be represented by any one of Formulas 2A to 2D below.

In the above chemical formulas 2A-2D,
R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms 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 , but 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 alkyl group having 1 to 20 carbon atoms.

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

In the above chemical formulas 2-1 to 2-6,
B ⁺ is [ _CH3 ( _CH2 ) ₁₁ ] _2N ⁺ ( _CH3 ) 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 from 1,000 g/mol to 15,000 g/mol.

The polymer can have an absorbance maximum in the wavelength range of 500 nm to 600 nm.

Another embodiment provides a photosensitive resin composition comprising a colorant containing a red dye, said red dye comprising said polymer.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, 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 coloring agent.

The photosensitive resin composition contains 1% by weight to 50% by weight of the coloring agent, 1% by weight to 30% by weight of the binder resin, and 1% by weight of the photopolymerizable monomer, relative to the total amount of the photosensitive resin composition. ~15% by weight, 0.01% to 10% by weight of said photoinitiator and the balance of said solvent.

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

Yet another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

Yet another embodiment provides a color filter comprising the photosensitive resin composition.

Yet another embodiment provides a display device including the color filter.

Specifics of other aspects of the invention are contained in the detailed description below.

The polymer according to one embodiment has excellent solubility in an organic solvent, excellent fluorescence controllability and spectral matching, and exhibits brightness, heat resistance, A color filter having excellent chemical resistance and the like can be manufactured.

Hereinafter, embodiments of the present invention will be described in detail. However, this is given by way of example and is not intended to limit the invention, which is defined solely by the scope of the following claims.

Unless otherwise specified herein, "substituted" or "substituted" means that one or more hydrogen atoms in the functional groups of the present invention are halogen atoms (F, Br, Cl or I), hydroxy a nitro group, a cyano group, an amino group ( _NH2 , NH( ^R200 ) or N( ^R201 ) ( ^R202 ), wherein ^R200 , ^R201 and ^R202 are the same or different; each independently an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group. do.

Unless otherwise specified herein, the term "alkyl group" means an alkyl group having 1 to 20 carbon atoms, specifically an alkyl group having 1 to 15 carbon atoms, and a "cycloalkyl group". means a cycloalkyl group having 3 to 20 carbon atoms, specifically means a cycloalkyl group having 3 to 18 carbon atoms, and "alkoxy group" means an alkoxy group having 1 to 20 carbon atoms, Specifically, it means an alkoxy group having 1 to 18 carbon atoms, "aryl group" means an aryl group having 6 to 20 carbon atoms, specifically means an aryl group having 6 to 18 carbon atoms, "Alkenyl group" means an alkenyl group having 2 to 20 carbon atoms, specifically means an alkenyl group having 2 to 18 carbon atoms, and "alkylene group" means an alkylene group having 1 to 20 carbon atoms. Specifically, it means an alkylene group having 1 to 18 carbon atoms, and the term "arylene group" means an arylene group having 6 to 20 carbon atoms, and specifically means an arylene group having 6 to 16 carbon atoms. .

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

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

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

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

One embodiment provides a polymer comprising a structural unit represented by Formula 1 below.

In the above chemical formula 1,
R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted a substituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, or a combination thereof;
n1 is an integer from 1 to 10;

The * means a point connected to another atom.

A color filter made of a pigment-based photosensitive resin composition has limitations in brightness and contrast ratio starting from the size of the pigment particles. Also, in the case of a color imaging device for an image sensor, a finer pattern is required to have a smaller dispersion particle size. In order to meet these demands, dyes that do not form particles are introduced instead of pigments, and a photosensitive resin composition suitable for dyes is produced to realize a color filter with improved brightness and contrast ratio. Attempts continue.

In general, xanthene-based compounds are charge-separated, and photosensitive resin compositions containing them have low solubility in organic solvents such as PGMEA and poor durability such as heat resistance and chemical resistance. There was a limit to use as an internal colorant.

However, the compound according to one embodiment, i.e., the polymer including the structural unit represented by Formula 1, can improve the solubility in an organic solvent, and the structural unit has a polymer structure in which the structural unit is polymerized. It is possible to manufacture a color filter having superior fluorescence controllability and spectral matching compared to the monomeric compound, and further improved luminance and contrast ratio using the photosensitive resin composition containing the compound.

R ¹ and R ² may be substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, such as aryl groups having 6 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, aryl groups having 6 to 14 carbon atoms, There may be ten aryl groups. When R ¹ and R ² are aryl groups such as phenyl groups, the durability of the dye can be improved, and the color filter produced from the photosensitive resin composition containing the same has higher brightness and a higher contrast ratio. can be done.

At least one of R ¹ and R ² may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. For example, at least one of R ¹ and R ² may be a substituent represented by Formula A below.

In the above chemical formula A,
Y ¹ to Y ⁴ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
X is SO ₃ ⁻ A ⁺ , or SO ₂ NHR ³ ;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A ⁺ is a monovalent metal cation or a compound represented by the following chemical formula 3;
n1 is an integer from 1 to 10;

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

Here, R ¹ and R ² may each independently be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, for example, both R ¹ and R ² are represented by the chemical formula A It may be a substituent.

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

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

In the above chemical formula 2,
X ¹ and X ² are each independently hydrogen, SO ₃ ⁻ A ⁺ , or SO ₂ NHR ³ ;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A ⁺ is a monovalent metal cation or a compound represented by the following chemical formula 3;
n1 is an integer from 1 to 10;

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The monovalent metal cation may be, for example, a monovalent metal cation such as Na ⁺ or K ⁺ , and is not particularly limited as long as it can form a salt with the SO ₃ ^- .

R ⁴ to R ⁷ are, for example, each independently methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group.

The polymer may include a functional group represented by Chemical Formula 4 below at its terminal.

In the above chemical formula 4,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer of 1-10.

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

The substituted or unsubstituted acrylate group can be represented, for example, by Formula E below.

In the above chemical formula E, R ^a is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
R ^b is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

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, a hexyl (meth) acrylate group, a ) acrylate groups, heptyl (meth)acrylate groups, octyl (meth)acrylate groups, and the like.

By including the functional group represented by Formula 4 at the end of the polymer, the light absorbing property of the photosensitive resin composition containing the polymer can be improved. For example, when the terminal of the polymer is an alkyl group such as an ethyl group, the light absorption properties can be greatly improved.

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

In the above chemical 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 chemical formula 3;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer of 1-10.

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The monovalent metal cation may be, for example, a monovalent metal cation such as Na ⁺ or K ⁺ , and is not particularly limited as long as it can form a salt with the SO ₃ ^- .

R ⁴ to R ⁷ are, for example, each independently methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group.

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

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, a heptyl (meth)acrylate group, an octyl It may be an acrylate group such as a (meth)acrylate group.

The polymer may be represented by any one of Formulas 2A to 2D below.

In the above chemical formulas 2A-2D,
R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms 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 , but 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 alkyl group having 1 to 20 carbon atoms.

That is, the polymer can contain two or more different monomers by X ⁵ and X ⁶ being different substituents.

The polymer may be a polymer represented by any one of Chemical Formulas 2-1 to 2-9 below, but is not limited thereto.

In the above chemical formulas 2-1 to 2-9,
B ⁺ is [ _CH3 ( _CH2 ) ₁₁ ] _2N ⁺ ( _CH3 ) 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 said polymer is from 1,000 g/mol to 15,000 g/mol, such as from 1,000 g/mol to 14,000 g/mol, such as from 1,000 g/mol to 13,000 g/mol; For example from 1,000 g/mol to 12,000 g/mol, such as from 1,000 g/mol to 11,000 g/mol, such as from 1,000 g/mol to 10,000 g/mol, such as from 1,000 g/mol 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, such as from 4,000 g/mol to 15,000 g/mol, such as from 5,000 g/mol to 6,000 g/mol, such as from 7,000 g/mol to 15,000 g/mol, such as 8, 000 g/mol to 15,000 g/mol, but not limited thereto. If the weight-average molecular weight of the polymer is out of the range, the solubility in solvents may be low. In addition, when the polymer has a weight average molecular weight (Mw) value within the above range, the brightness of a color filter manufactured using the photosensitive resin composition containing the polymer can 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 the peak at 580 nm wavelength increases in relation to the red luminance, further improving the luminance. can be done.

Since the polymer according to one embodiment contains the structural unit represented by Formula 1, it is possible to express clearer colors even in a small amount, and when used as a colorant, a display having excellent color characteristics such as brightness and contrast ratio. Devices can be manufactured. For example, the dye compound represented by Formula 1 may have a maximum absorbance (λmax) in the wavelength range of 500 nm to 600 nm.

Generally, dyes are the most expensive components used in color filters. Therefore, in order to achieve desired effects, such as high brightness and high contrast ratio, more expensive dyes must be used, which inevitably increases the unit production cost. However, when the polymer according to the embodiment is used as a dye in a color filter, it is possible to achieve excellent color characteristics such as high brightness and high contrast ratio even in a small amount, thereby reducing the production cost.

According to another embodiment, there is provided a photosensitive resin composition comprising a colorant containing a red dye, said red dye comprising a polymer according to one embodiment.

The polymer according to one 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 photopolymerization initiator, and a solvent. That is, the photosensitive resin composition may include the polymer according to one embodiment as a colorant, and may also include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The components will be specifically described below.

Colorant The photosensitive resin composition may further contain a pigment as a colorant in addition to containing the polymer as a red dye.

The coloring agent 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 1 wt% to the total amount of the photosensitive resin composition. 35 wt%, such as 1 wt% to 30 wt%, such as 1 wt% to 25 wt%, such as 1 wt% to 20 wt%, such as 1 wt% to 15 wt%, such as 1 wt% to 10 wt% % and is not limited to these. When the colorant according to one embodiment is included within the above range, the color reproduction rate and the contrast ratio are excellent.

The pigments can include blue pigments, violet pigments, red pigments, green pigments, yellow pigments, and the like.

Examples of the blue pigment include C.I. I. blue pigment 15:6, C.I. I. Blue Pigment 15, C.I. I. blue pigment 15:1, C.I. I. blue pigment 15:2, C.I. I. blue pigment 15:3, C.I. I. blue pigment 15:4, C.I. I. blue pigment 15:5, C.I. I. Blue Pigment 16, C.I. I. blue pigment 22, C.I. I. Blue Pigment 60, C.I. I. Blue Pigment 64, C.I. I. blue pigment 80 or combinations thereof.

Examples of the violet pigment include C.I. I. Violet Pigment 1, C.I. I. Violet Pigment 19, C.I. I. Violet Pigment 23, C.I. I. Violet Pigment 27, C.I. I. Violet Pigment 28, C.I. I. Violet Pigment 29, C.I. I. Violet Pigment 30, C.I. I. Violet Pigment 32, C.I. I. Violet Pigment 37, C.I. I. Violet Pigment 40, C.I. I. Violet Pigment 42, C.I. I. Violet pigment 50 or combinations 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 pigments, quinacridone pigments, naphthol AS, shikomine pigments, anthraquinones (sudan I, II, III, R), visazo, and benzopyran. etc.

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

Examples of the yellow pigment include C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150 and the like can be mentioned, and these can be used alone or in combination of two or more.

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

The pigment dispersion may comprise a solid pigment, a solvent, and a dispersing agent for uniformly dispersing the pigment within 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, based on the total weight of the pigment dispersion. It may be included at 10% to 15% by weight.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like can be used. Specific examples of the dispersant include polyalkylene glycol and its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylic acid Acid salts, alkylamide alkylene oxide adducts, alkylamines and the like can be mentioned, and these can be used alone or in combination of two or more.

Commercially available products of the dispersant include BYK 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.; １００、ＥＦＫＡ－４００、ＥＦＫＡ－４５０など；Ｚｅｎｅｋａ社のＳｏｌｓｐｅｒｓｅ ５０００、Ｓｏｌｓｐｅｒｓｅ １２０００、Ｓｏｌｓｐｅｒｓｅ １３２４０、Ｓｏｌｓｐｅｒｓｅ １３９４０、Ｓｏｌｓｐｅｒｓｅ １７０００、Ｓｏｌｓｐｅｒｓｅ ２００００、Ｓｏｌｓｐｅｒｓｅ２４０００ＧＲ、Ｓｏｌｓｐｅｒｓｅ ２７０００、Ｓｏｌｓｐｅｒｓｅ ２８０００など；またはＡｊｉｎｏｍｏｔｏ社のＰＢ７１１、ＰＢ８２１などがbe.

The dispersant may be included in an amount of 1 wt % to 20 wt % with respect to the total weight of the pigment dispersion. When the dispersant is within the above range, it can maintain an appropriate viscosity and have excellent dispersibility of the photosensitive resin composition, thereby maintaining optical, physical and chemical qualities when applied to the product. can be done.

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. can be used.

Binder Resin The binder resin may comprise 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 includes at least one acrylic repeating unit. is.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, 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 wt % to 50 wt %, for example 10 wt % to 40 wt %, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate. , 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, unsaturated carboxylic acid ester compounds such as phenyl (meth) acrylate; 2-aminoethyl ( Unsaturated carboxylic acid aminoalkyl ester compounds such as meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl compounds such as glycidyl (meth)acrylate ester compounds; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide;

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2- Hydroxyethyl methacrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, etc., but not limited to these, these may be used alone or in combination of two or more. can also be used as

The acrylic binder resin has 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. may 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, suitable viscosity, and 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 Formula 6 below.

In the above chemical 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 alkyl group having 1 to 20 carbon atoms,
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 C 1-20 is an alkyl group of) or any one of the linking groups represented by the following chemical formulas 6-1 to 6-11,

(In the above chemical formula 6-5,
R ^a is a hydrogen atom, _an ethyl group _{, C2H4Cl} , _C2H4OH , _CH2CH = _CH2 or a phenyl group. )

Z ² is a dianhydride residue,
p1 and p2 are each independently an integer of 0-4.

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

In the above chemical formula 7,
Z ³ can be represented by the following chemical formulas 7-1 to 7-7.

(In the above chemical formula 7-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an ester group or an ether group.)

(In the above chemical formula 7-5, R ^d is O, S, NH, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an alkylamine group having 1 to 20 carbon atoms or an alkenylamine group having 2 to 20 carbon atoms. is.)

The cardo-based binder resin is, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, tetrahydrophthalic anhydride, etc. Anhydride compounds; Glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Solvents 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, benzyltriethylammonium chloride, etc. can be manufactured.

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

The cardo-based binder resin may have a weight average molecular weight of 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, pattern formation can be performed satisfactorily without residue during color filter production, and a favorable pattern can be obtained without loss of film thickness during development. can.

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% to 15 wt%, relative to the total amount of the photosensitive resin composition. It may be included in weight percent, such as 1 weight percent to 10 weight percent, such as 1 weight percent to 7 weight percent, such as 1 weight percent to 5 weight percent, but is not limited thereto. When the binder resin is within the above range, it is possible to obtain excellent surface smoothness due to excellent developability and improved crosslinkability during the manufacture of a color filter.

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer forms a pattern having excellent heat resistance, light resistance and chemical resistance by sufficiently polymerizing during exposure in the pattern forming process. be able to.

Specific examples of photopolymerizable monomers 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. (meth)acrylates, 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 ) acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, etc. .

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

The photopolymerizable monomer may be used after being treated with an acid anhydride in order to impart 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% to 15 wt%, based on the total amount of the photosensitive resin composition. It may be included in weight % to 5 weight %, but is not limited to these. When the photopolymerizable monomer is within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability and excellent developability with an alkaline developer.

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

Examples of the acetophenone compounds include 2,2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt- Butyldichloroacetophenone, 4-chloroacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2 -dimethylamino-1-(4-morpholinophenyl)-butan-1-one and the like.

Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis (Diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

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

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

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3′,4′-dimethoxystyryl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4′-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine , bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl )-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxy styryl)-s-triazine and the like.

Examples of the oxime compounds include O-acyloxime 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. be able to. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)- Butan-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)-octan-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate and the like.

As the photopolymerization initiator, in addition to the above compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc. can be used.

The photoinitiator may be used together with a photosensitizer that absorbs light into an excited state and then undergoes a chemical reaction by transferring its energy.

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

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%, relative to the total amount of the photosensitive resin composition. , such as from 0.01% to 5% by weight, such as from 0.01% to 3% by weight, such as from 1% to 10% by weight, such as from 3% to 10% by weight. , but not limited to: When the photopolymerization initiator is included in the above range, sufficient curing occurs during exposure in the pattern forming process, so that excellent reliability can be obtained, and the pattern has excellent heat resistance, light resistance, and chemical resistance. The resolution and adhesion are also excellent, and a decrease in transmittance due to unreacted initiators can be prevented.

Solvent As the solvent, a substance compatible with but not reactive with the (dye) compound, the pigment, the binder resin, the photopolymerizable monomer and the photoinitiator according to one embodiment can be used. .

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; glycols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethers; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate; methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether carbitols; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Alkoxyacetic acid alkyl esters such as ethyl; 3-oxypropionate alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy 3-alkoxypropionic acid alkyl esters such as ethyl propionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate 2-alkoxypropionic acids such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; alkyl esters; 2-oxy-2-methylpropionate esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; methyl 2-methoxy-2-methylpropionate, Monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , ethyl hydroxyacetate, esters such as methyl 2-hydroxy-3-methylbutanoate; ketone acid esters such as ethyl pyruvate; and N-methylformamide, N,N-dimethylformamide, N-methylform anilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, High boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like.

Of these, 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; 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 the balance amount, for example, 40 wt % to 90 wt %, based on the total amount of the photosensitive resin composition. When the solvent is within the above range, the photosensitive resin composition has an appropriate viscosity, thereby improving processability in manufacturing a color filter.

Other Additives The photosensitive resin composition contains malonic acid; 3-amino- 1,2-propanediol; a carboxyl group, a methacryloyl group, an isocyanate group, a silane coupling agent having a reactive substituent such as an epoxy group; a leveling agent; a fluorine-based surfactant; can further include:

Examples of the silane-based coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyl. Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like can be mentioned, and these can be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 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, storage stability, etc. are excellent.

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

Examples of the epoxy compounds include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, such as 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the above range, adhesion, storage stability, etc. are excellent.

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

A fluorosurfactant can be used as the surfactant, and examples of the fluorosurfactant include F-482, F-484, F-478 and F-554 manufactured by DIC Corporation. , but not limited to.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is within the above range, coating uniformity is ensured, staining does not occur, and wettability to the 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 as long as the physical properties are not impaired.

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

According to another embodiment, there is provided a color filter including the photosensitive resin layer 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 a photosensitive resin composition film; developing the exposed photosensitive resin composition film with an alkaline aqueous solution to produce a photosensitive resin film; and heat-treating the photosensitive resin film. . Since the process conditions and the like are well known in the art, detailed description thereof will be omitted in this specification.

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

Preferred embodiments of the invention are described below. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Synthesis example: polymer synthesis
Synthesis Example 1: Synthesis of Polymer Represented by Chemical Formula 2-1

Acid red 289 (1 mol) and Dilauryldimethylammonium Bromide (1.5 mol) were added to H ₂ O, heated to 70° C., stirred for 24 hours, cooled to room temperature, and the organic layer was extracted with MC to remove the intermediate. Obtained. This intermediate (1 mol), 1,2-Diodoethane (1 mol), and K ₂ CO ₃ (10 mol) were added to NMP (N-methylpyrrolidone), heated at 100° C. and stirred for 24 hours. I put it in and quenched it. Methylene chloride was added to this solution, and the organic layer was extracted by washing with water twice. The extracted organic layer was distilled under reduced pressure, purified by column chromatography, and solidified with hexane to synthesize a polymer represented by Formula 2-1 below.

Synthesis Example 2: Synthesis of Polymer Represented by Chemical Formula 2-2

Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1 except that 1,4-Diiodobutane was used instead of 1,2-Diiodoethane in the reaction of Synthesis Example 1. A polymer (GPC MS: 5,003 m/z) was synthesized.

Synthesis Example 3: Synthesis of Polymer Represented by Chemical 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, and the organic layer was extracted by washing with water twice. The extracted organic layer was distilled under reduced pressure and solidified with hexane to obtain intermediate 1. Thereafter, a polymer represented by the following chemical formula 2-3 was synthesized in the same manner as in Synthesis Example 1 except that Acid red 289 was replaced with intermediate 1.

Synthesis Example 4: Synthesis of Polymer Represented by Formula 2-4 Except that the intermediate reaction was omitted in the reaction of Synthesis Example 1, and Ethyl Methylmethacrylate was used instead of Acid red 289 and iodoethane as a quenching material. A polymer represented by the following chemical formula 2-4 (GPC MS: 6,705 m/z) was synthesized in the same manner as in Synthesis Example 1.

Synthesis Example 5: Synthesis of Polymer Represented by Formula 2-5 Synthesis Example 3 was carried out in the same manner as in Synthesis Example 3, except that 2-iodobutane was used instead of iodoethane, which is a quenching material in the reaction of Synthesis Example 3. , synthesized a polymer represented by the following chemical formula 2-5.

Synthesis Example 6: Synthesis of Polymer Represented by Chemical Formula 2-6 Synthesis Example 2 was carried out in the same manner as in Synthesis Example 2 except that 1-Bromo-2-propanol was used instead of Dilauryldimethylammonium Bromide in the reaction of Synthesis Example 2. Thus, a polymer represented by the following chemical formula 2-6 was synthesized.

In the above chemical formula 2-6,
R ¹¹ is a 2-hydroxypropyl group

is.

Synthesis Example 7: Synthesis of Polymer Represented by Chemical Formula 2-7 Intermediate reaction is omitted in the reaction of Synthesis Example 2, and iodoethane, which is a quenching material, is prepared in a mixture state of Acid red 289 and intermediate of Chemical Formula 2-2. A polymer represented by Formula 2-7 (where n4 and n5 have a ratio of 1:1) was synthesized in the same manner as in Synthesis Example 2 except that 2-Iodobutane was used instead.

Maldi-tof MS: 8,264m/z
Synthesis Example 8: Synthesis of Polymer Represented by Chemical Formula 2-8
Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1 except that 1,6-Diiodohexane was used instead of 1,2-Diiodoethane in the reaction of Synthesis Example 1. polymer was synthesized.

Synthesis Example 9: Synthesis of Polymer Represented by Formula 2-9 Synthesis Example 1, except that 1,8-Diiodooctane was used instead of 1,2-Diiodoethane for the linker chain in the reaction of Synthesis Example 1. A polymer (Maldi-tof MS: 8,264 m/z) was synthesized in the same manner.

Comparative Synthesis Example 1: Synthesis of Compound X

10 g of compound A (CAS No. 77545-45-0) is 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 charged with 800 mL of water to form a precipitate. The precipitate obtained was suction filtered and additionally washed with water. The filtrate was dried to obtain 9.9 g of the compound X (84% yield).

Maldi-tof MS: 478.2 m/z.

Comparative Synthesis Example 2: Synthesis of Compound Y

Acid red 289 (1 mol) and Dilauryldimethylammonium Bromide (1.5 mol) were added to H ₂ O, heated at 70° C., stirred for 24 hours, cooled to room temperature, and the organic layer was extracted with MC to remove the intermediate. Obtained. This intermediate (1 mol), 1,12-Diiodododecane (1 mol), and K ₂ CO ₃ (10 mol) were added to NMP (N-methylpyrrolidone), heated at 100° C. and stirred for 24 hours, and then iodoethane was added to the mixture. I put it in and quenched it. Methylene chloride was added to this solution, and the organic layer was extracted by washing with water twice. The extracted organic layer is distilled under reduced pressure and subjected to column chromatography.
The polymer represented by compound Y was synthesized by purifying by chromatography and solidifying with hexane.

Examples: Synthesis of photosensitive resin compositions (Examples 1 to 9, Comparative Examples 1 and 2)
A photopolymerization initiator was added to a solvent with the composition shown in Table 1 below, and dissolved by stirring at room temperature for 1 hour. Next, a binder resin and a photopolymerizable monomer were added and stirred at room temperature for 1 hour. Other additives were added thereto 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 thereto, stirred at room temperature for 2 hours, and then added to the solution three times. Filtration was performed over the water to remove impurities, and photosensitive resin compositions according to Examples 1 to 9, Comparative Examples 1 and 2 were prepared. 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)
(B) a photopolymerizable monomer
(B-1) DPHA (Nippon KAYAKU)
(B-2) ABPE-20 (Shin-nakamura)
(C) photoinitiator
(C-1) SPI-03 (Sanyosha)
(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) According to Comparative Synthesis Example 1 Monomer (D-11) Monomer according to Comparative Synthesis Example 2 (D-12) C.I. I. Pigment red 254 (SANYO)
(E) solvent
Propylene glycol monomethyl ethyl acetate (PGMEA, sigma-aldrich)
(F) Other additives
Fluorinated surfactant (F-554, DIC)

Evaluation 1: Evaluation of color change before/after baking The color change before/after baking was measured using a spectrophotometer (Otsuka Electronics MCPD3000) by additionally baking for 20 minutes three times in a hot air circulation oven (convection oven) of The results are shown in Table 2 below.

Evaluation 2: Luminance characteristic evaluation The photosensitive resin compositions produced in Examples 1 to 9, Comparative Examples 1 and 2 were applied to a thickness of 1 μm to 3 μm on a degreased and washed glass substrate having a thickness of 1 mm. and dried on a hot plate at 90° C. for 2 minutes to obtain a coating film. Subsequently, the entire surface of the coated film was exposed under the condition of 50 mJ/cm ² using a high-pressure mercury lamp having a dominant wavelength of 365 nm. Then, it was dried for 20 minutes in a hot air circulating drying oven at 230° C. to obtain samples of the same thickness. The brightness of the pixel layer was measured using a spectrophotometer (MCPD3000, Otsuka electronic), and the results are shown in Table 2 below.

Evaluation 3: Evaluation of chemical resistance The patterns of the color filter specimens produced using the photosensitive resin compositions produced in Examples 1 to 9, Comparative Examples 1 and 2 were placed in an NMP solution at 90°C. The PI solution chemical resistance was evaluated after immersion for 10 minutes. The chemical resistance was evaluated by the color change of the color filter pattern before and after immersion in the NMP solution and the presence or absence of peeling of the color filter pattern after immersion in the stripping solution. A change in color characteristics of the color filter pattern was measured using a spectrophotometer (MCPD3000 from Otsuka Electronics), and the presence or absence of peeling of the color filter pattern was evaluated with an optical microscope. The evaluation results are shown in Table 2 below.

Evaluation 4: Evaluation of heat resistance The dyes dissolved in the photosensitive resin compositions produced in Examples 1 to 9, Comparative Examples 1 and 2 were measured for heat resistance using a TGA (Discovery) heat resistance measuring instrument. evaluated the sex. The experiment was conducted by setting the temperature range from 30°C to 400°C under the air condition with a temperature increase rate of 5°C/min. The evaluation results are shown in Table 2 below.

Evaluation 5: Fluorescence Control Evaluation The dyes of Examples 1 to 9 and Comparative Examples 1 and 2 were diluted in a solvent. At this time, the concentration was 0.02A. less than U. Fluorescence properties were then evaluated using an integrating hemisphere measurement set-up for solutions.

Evaluation items are QY (Quantum Yield), FWHM (Full Width
at Half Maximum), Fluorescence intensity, λ_emission, other surface anomalies and process-specific appearance issues. QY is an index indicating the ratio of emitted light to incident light, and indicates how much fluorescence is emitted. FWHM is an item for reading the width indicated by two wavelength values of the portion corresponding to the half maximum intensity on the emission spectrum of light, and is also called the half width, and the narrower the better. Fluorescence intensity is a value corresponding to the y-axis of the emission spectrum and indicates the intensity of fluorescence, and is determined by taking into consideration the thickness correction value obtained by multiplying QY by Abs (absorbance).

As shown in Table 2 above, the photosensitive resin compositions of Examples 1 to 9 containing the polymer (red dye) according to one embodiment are compared with Comparative Examples 1 and 2, which do not contain the polymer, in terms of luminance, etc. It can be confirmed that not only the color properties of , but also heat resistance, chemical resistance, and fluorescence control properties are excellent.

Although specific embodiments of the invention have been described and illustrated above, the invention is not limited to the described embodiments, but can be variously modified and varied without departing from the spirit and scope of the invention. are self-evident to those of ordinary skill in the art. Therefore, such modifications or variations should not be understood separately from the technical spirit and viewpoint of the present invention, and it should be said that the modified embodiments belong to the scope of the claims of the present invention. It should not.

Claims (20)

A polymer containing a structural unit represented by the following chemical formula 1:

In the above chemical formula 1,
R ¹ and R ² are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted a substituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, or a combination thereof;
n1 is an integer from 1 to 10; The polymer of claim 1, wherein at least one of R ¹ and R ² is a substituted or unsubstituted 6-20 carbon aryl group. 2. The polymer of claim 1, wherein each of said R ¹ and R ² is independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. 2. The polymer according to claim 1, wherein the polymer comprises two or more structural units represented by Chemical Formula 1. The polymer according to claim 1, wherein the polymer comprises a structural unit represented by Formula 2 below:

In the above chemical formula 2,
X ¹ and X ² are each independently hydrogen, SO ₃ ⁻ A ⁺ , or SO ₂ NHR ³ ;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A ⁺ is a monovalent metal cation or a compound represented by the following chemical formula 3;
n1 is an integer from 1 to 10,

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The polymer according to claim 1, wherein the polymer comprises a functional group represented by the following chemical formula 4 at both ends:

In the above chemical formula 4,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer of 1-10. The polymer according to claim 1, wherein one of both ends of the polymer is represented by Formula 5 below:

In the above chemical 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 chemical formula 3;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
R ⁸ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted acrylate group;
n2 is an integer from 1 to 10,

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The polymer of claim 1, wherein the polymer is represented by any one of Formulas 2A to 2D below:

In the above chemical formulas 2A-2D,
R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms 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 , but X ⁵ and X ⁶ are different from each other;
A ⁺ is a monovalent metal cation or a compound represented by the following chemical formula 3;
R ³ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,

In the above chemical formula 3,
Each of R ⁴ to R ⁷ is independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The polymer according to claim 1, wherein the polymer is represented by any one of the following chemical formulas 2-1 to 2-6:

In the above chemical formulas 2-1 to 2-6,
B ⁺ is [ _CH3 ( _CH2 ) ₁₁ ] _2N ⁺ ( _CH3 ) 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 polymer of claim 1, wherein the weight average molecular weight (Mw) of said polymer is from 1,000 g/mol to 15,000 g/mol. The polymer of claim 1, wherein said polymer has a maximum absorbance in the wavelength range of 500nm to 600nm. a colorant containing a red dye,
A photosensitive resin composition, wherein the red dye comprises the polymer of any one of claims 1-11. 13. The photosensitive resin composition of claim 12, further comprising a binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent. 14. The photosensitive resin composition of claim 13, wherein the binder resin comprises an acrylic binder resin, a cardo-based binder resin, or a combination thereof. 13. The photosensitive resin composition according to claim 12, wherein said colorant further comprises a pigment. The photosensitive resin composition, with respect to the total amount of the photosensitive resin composition,
1% to 50% by weight of the coloring agent;
1% to 30% by weight of the binder resin;
1% to 15% by weight of the photopolymerizable monomer;
14. The photosensitive resin composition according to claim 13, comprising 0.01% to 10% by weight of the photoinitiator and the balance of the solvent. The photosensitive resin composition includes malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, and a radical polymerization initiator. Or the photosensitive resin composition of Claim 13 which further contains these combinations. A photosensitive resin film produced using the photosensitive resin composition according to claim 12 . A color filter comprising the photosensitive resin film of claim 18 . A display device comprising the color filter of claim 19.