KR20230024934A - Photosensitive resin composition, photosensitive resin layer including the same and color filter - Google Patents

Abstract

A photosensitive resin composition, a photosensitive resin film prepared by using the same, and a color filter comprising the photosensitive resin film are provided. The photosensitive resin composition comprises: (A) a colorant comprising a dye with a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein a shell is represented by formula 1. (In the formula 1, each substituent is as the same as defined in the specification.) The photosensitive resin composition according to one embodiment can implement the color filter with excellent brightness and durability by using a core-shell dye consisting of the shell of a specific structure surrounding a squarylium-based core.

Description

Photosensitive resin composition, photosensitive resin film and color filter using the same

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

A liquid crystal display device, which is one of display devices, has advantages such as light weight, thinness, low cost, low power consumption drive, and excellent bonding with integrated circuits, and its use range is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit unit composed of a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate on which an ITO pixel electrode is formed. The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels and a plurality of colors, typically red (R), green (G), and blue (B), to form each pixel. ) has a structure in which the pixel units in which the three primary colors are arranged in a predetermined order are sequentially stacked.

In the pigment dispersion method, which is one of the methods for realizing a color filter, a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, a pattern to be formed is exposed, and then the unexposed area is removed with a solvent. This is a method in which a colored thin film is formed by repeating a series of thermal curing processes. The colored photosensitive resin composition used in the manufacture of color filters according to the pigment dispersion method is generally composed of an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method is actively applied to manufacturing LCDs such as mobile phones, laptop computers, monitors, and TVs. However, in recent years, even in the photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also further improved performance is required. In particular, characteristics of high luminance and high contrast ratio along with high color gamut are urgently required.

An image sensor refers to a part of an imaging device that generates an image from a mobile phone camera or a digital still camera (DSC), and is largely complementary to a charge coupled device (CCD) image sensor depending on its manufacturing process and application method. It can be classified as a complementary metal oxide semiconductor (CMOS) image sensor. A color image sensor used for a solid-state image sensor or a complementary metal oxide semiconductor includes a color filter having filter segments of additive and mixed primary colors of red, green, and blue on a light-receiving element ( It is common to install each color filter and perform color separation. Recently, the pattern size of a color filter mounted on such a color imaging device is 2 μm or less, which is 1/100 to 1/200 times that of a color filter pattern for an existing LCD. Accordingly, an increase in resolution and a decrease in residue are important items that determine the performance of a device.

In a color filter made of a pigment-type photosensitive resin composition, there are limitations in luminance and contrast ratio due to the size of pigment particles. In addition, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required to form a fine pattern. In order to meet these demands, there is an attempt to implement a color filter with improved luminance and contrast ratio by preparing a photosensitive resin composition suitable for the dye by introducing a dye that does not form particles instead of a pigment. However, in the case of dyes, there is a concern about a decrease in luminance due to poor durability such as light resistance and heat resistance compared to pigments.

One embodiment is to provide a photosensitive resin composition having excellent brightness and durability.

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

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

One embodiment is (A) a colorant comprising a dye of a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the core is a squarylium-based compound, and the shell provides a photosensitive resin composition represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

However, R ¹ to R ⁵ are not hydrogen atoms at the same time,

m is an integer from 1 to 10;

n is an integer from 0 to 3;

L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The shell may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

However, R ¹ to R ⁵ are not hydrogen atoms at the same time,

n is an integer from 0 to 3;

The shell may be represented by any one of Chemical Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formula 2-1 to Formula 2-3,

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

R ⁷ and R ⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group).

The shell may have a cage width of 6.5 Å to 7.5 Å.

The shell may be represented by any one of the following Chemical Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The squarylium-based compound may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The length of the core may be 1 nm to 3 nm.

The core may have a maximum absorption peak at a wavelength of 530 nm to 680 nm.

The squarylium-based compound may be represented by any one of the following Chemical Formulas 4-1 to 4-6.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

The core-shell structured dye may include the core and the shell in a molar ratio of 1:1.

The dye of the core-shell structure may be a green dye.

The colorant may further include a pigment.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, 0.5% to 20% by weight of the colorant; 0.1% to 30% by weight of the binder resin; 0.1% to 30% by weight of the photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator; And it may include the remaining amount of the solvent.

The photosensitive resin composition further contains 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. can include

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

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

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

In the photosensitive resin composition according to an embodiment, a color filter having excellent luminance and durability may be implemented by using a core-shell dye composed of a shell having a specific structure surrounding a squarylium-based core.

1 is a diagram showing the cage width of a shell represented by Formula 3-4.

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

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

Unless otherwise specified herein, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" mean cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl, respectively. It means that at least one N, O, S or P heteroatom exists in the ring compound of ene.

Unless otherwise specified herein, "(meth)acrylate" means both "acrylate" and "methacrylate".

In this specification, unless otherwise specified, "combination" means mixing or copolymerization.

Unless otherwise defined in the chemical formula within this specification, if 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.

In addition, unless otherwise specified in this specification, "*" means a portion connected to the same or different atoms or chemical formulas.

The photosensitive resin composition according to one embodiment includes (A) a colorant including a dye having a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, the core is a squarylium-based compound, and the shell is represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

However, R ¹ to R ⁵ are not hydrogen atoms at the same time,

m is an integer from 1 to 10;

n is an integer from 0 to 3;

L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

In Formula 1, L ¹ and L ² may each independently be a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is excellent, and it is easy to form a structure in which the shell surrounds the squarylium-based compound.

For example, the dye having a core-shell structure according to one embodiment includes a non-covalent bond, that is, a hydrogen bond between an oxygen atom of a squarylium-based compound and a hydrogen atom bonded to a nitrogen atom of the shell represented by Formula 1 above.

In general, squarylium-based compounds are often used as green dyes because they have excellent green spectral properties and a high molar extinction coefficient. However, there is a problem in that a decrease in luminance occurs during a baking process after manufacturing a color resist due to poor durability compared to pigment. The photosensitive resin composition according to one embodiment uses a compound in which the shell represented by Chemical Formula 1 forms a core-shell structure by using a squarylium-based compound as a core instead of a conventional squarylium-based compound as a colorant, so that the core-shell structure The compound of can improve the durability of a color filter applied as a colorant, and accordingly, a color filter with high brightness and high contrast ratio can be implemented.

Each component is specifically described below.

(A) colorant

The photosensitive resin composition according to one embodiment includes the dye having the core-shell structure.

As described above, in the color filter made of the pigment-type photosensitive resin composition, there are limitations in luminance and contrast ratio due to the size of the pigment particles. In addition, in order to be applied for image sensors, a resin composition composed of smaller particles is required to form fine patterns. To achieve this, an attempt has been made to implement a color filter with improved luminance and contrast ratio by introducing a dye that does not form particles instead of a pigment to prepare a photosensitive resin composition suitable for the dye, but in the case of the dye, the durability is weak compared to the pigment, so the luminance and contrast ratio are improved. there was a limit to

However, in the case of a dye used as a colorant in the photosensitive resin composition according to an embodiment, the center of a squarylium-based compound having excellent green spectral characteristics and a high molar absorption coefficient is wrapped with a macrocyclic compound represented by Formula 1, It is possible to realize a color filter having excellent durability and excellent luminance and contrast ratio compared to a pigment-type photosensitive resin composition and a dye-type photosensitive resin composition.

Specifically, the dye having a core-shell structure has a structure consisting of a squarylium-based core and a shell surrounding the core, and the shell is a macrocyclic compound represented by Formula 1, while surrounding the squarylium-based core. A coating layer may be formed. Due to this structure, that is, by having a structure in which a squarylium-based compound exists inside the ring represented by Formula 1, the durability of the dye having a core-shell structure can be improved, and accordingly, a color with high luminance and high contrast ratio can be obtained. Filters can be implemented.

For example, the shell may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

However, R ¹ to R ⁵ are not hydrogen atoms at the same time,

n is an integer from 0 to 3;

For example, in Formula 1 and Formula 2, R ¹ is a hydrogen atom, R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, but at least one of R ² to R ⁵ is substituted. Or it may be an unsubstituted C1 to C20 alkyl group.

For example, in Formulas 1 and 2, R ¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group), and , R ² to R ⁵ may each independently be a hydrogen atom.

For example, R ¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group), and at least one of R ² to R ⁵ One may be a substituted or unsubstituted C1 to C20 alkyl group.

For example, Chemical Formula 2 may be represented by Chemical Formula 2A below.

[Formula 2A]

In Formula 2A,

R ¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the shell may be represented by any one of Chemical Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formula 2-1 to Formula 2-3,

R ² to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

R ⁷ and R ⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group).

For example, the cage width of the shell may be 6.5 Å to 7.5 Å, and the volume of the shell may be 10 Å to 16 Å. As used herein, the term "cage width" refers to the distance inside the shell, for example, the distance between two different phenylene groups having methylene groups connected to both sides in the shell represented by Formula 2 above (see FIG. 1). When the shell has a cage width within the above range, a core-shell dye having a structure surrounding a squarylium-based compound can be obtained, and thus durability by using the core-shell dye as a colorant constituting the photosensitive resin composition, This excellent color filter having high luminance can be implemented.

For example, the shell may be represented by any one of Chemical Formulas 3-1 to 3-4, but is not necessarily limited thereto.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

For example, in the core-shell structured dye, the squarylium-based compound constituting the core may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

For example, in Formula 4, R ⁹ and R ¹¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ¹⁰ and R ¹² are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group. It may be an unsubstituted C6 to C20 aryl group.

For example, R ⁹ and R ¹¹ may each independently be a 'C1 to C20 alkyl group unsubstituted or substituted with a C1 to C10 alkoxy group' or 'a C3 to C20 cycloalkyl group unsubstituted or substituted with a C1 to C10 alkoxy group'.

For example, the C1 to C10 alkoxy group may be an unsubstituted C1 to C10 alkoxy group or a C1 to C6 alkoxy group substituted with a C1 to C4 alkyl group.

As shown in the diagram below, the compound represented by Formula 4 has three resonance structures, but in this specification, only one resonance structure is shown for convenience. That is, the compound represented by Chemical Formula 4 may be represented by any one of the three resonance structures.

[scheme]

For example, the core, that is, the squarylium-based compound, may be represented by any one of Chemical Formulas 4-1 to 4-6, but is not necessarily limited thereto.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

For example, when the compound represented by Chemical Formulas 4-1 to 4-6, specifically, the compound represented by Chemical Formula 4-6 is used in a photosensitive resin composition (eg, as a dye), the solubility in a solvent described below is 5 It may be more than 5 to 10, for example. The solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent. When the solubility of the compound (eg, dye) is within the above range, compatibility and coloring strength with other components in the photosensitive resin composition, that is, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator described later, may be secured, and precipitation of the dye may be prevented. can be prevented

For example, the compounds represented by Chemical Formulas 4-1 to 4-6 may have excellent heat resistance. That is, when measured by a thermogravimetric analyzer (TGA), the thermal decomposition temperature may be 200° C. or higher, for example, 200° C. to 300° C.

For example, the length of the compound represented by Chemical Formula 4 included in or constituting the core may be 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the compound represented by Chemical Formula 4 has a length within the above range, a core-shell structure can be easily formed. In other words, as the compound represented by Chemical Formula 4 has a length within the above range, a structure in which a shell, which is a macrocyclic compound represented by Chemical Formula 1, surrounds the compound represented by Chemical Formula 4 can be easily formed. . When using another compound that does not correspond to the length of the above range, it is difficult to expect improvement in durability as it is difficult to form a structure surrounding the compound that serves as the core of the shell.

For example, the core-shell structure compound may have a maximum absorption peak at a wavelength of 530 nm to 680 nm. A photosensitive resin composition for a color filter having high luminance and high contrast ratio can be obtained by using the dye having the core-shell structure having the spectral characteristics as a green dye.

For example, the core-shell compound may include the squarylium-based core and the shell in a molar ratio of 1:1. When the core and the shell are present in the molar ratio, a coating layer (shell) surrounding the squarylium-based core may be well formed.

For example, the dye of the core-shell structure may be represented by any one selected from the group consisting of compounds represented by Chemical Formulas 5-1 to 5-24, but is not necessarily limited thereto.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

[Formula 5-12]

[Formula 5-13]

[Formula 5-14]

[Formula 5-15]

[Formula 5-16]

[Formula 5-17]

[Formula 5-18]

[Formula 5-19]

[Formula 5-20]

[Formula 5-21]

[Formula 5-22]

[Formula 5-23]

[Formula 5-24]

The core-shell dye may be used alone as a green dye or may be used in combination with a toning dye.

Examples of the toning dye include triarylmethane-based dyes, anthraquinone-based dyes, benzylidene-based dyes, cyanine-based dyes, phthalocyanine-based dyes, azapophyrin-based dyes, indigo-based dyes, xanthene-based dyes, and pyridone-azo-based dyes. can

The core-shell dyes may also be used in admixture with pigments. That is, the colorant may further include a pigment.

As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like may be used.

Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89 etc. are mentioned. Examples of the green pigment include C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green Pigment 59 etc. are mentioned. 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. and copper phthalocyanine pigments such as blue pigment 16 and the like. Examples of the yellow pigment include C.I. isoindoline-based pigments such as yellow pigment 139, C.I. quinophthalone pigments such as yellow pigment 138, C.I. nickel complex pigments such as Yellow Pigment 150 and the like; and the like. Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. The pigments may be used alone or in combination of two or more, but are not limited to these examples.

The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion. The pigment dispersion may be composed of the pigment, a solvent, a dispersing agent, and a dispersing resin.

Ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. may be used as the solvent, and among these, propylene glycol methyl ether acetate is preferably used. can

The dispersant helps to uniformly disperse the pigment in the dispersion, and all nonionic, anionic or cationic dispersants may be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide adduct Water, alkyl amine, etc. may be used, and these may be used alone or in combination of two or more.

As the dispersion resin, an acrylic resin containing a carboxyl group may be used, which may improve stability of the pigment dispersion and also improve pixel patternability.

When the core-shell dye and the pigment are mixed and used, they may be mixed in a weight ratio of 1:9 to 9:1, specifically, 3:7 to 7:3. When mixed in the above weight ratio range, it is possible to have high luminance and contrast ratio while maintaining color characteristics.

The colorant may be included in an amount of 0.5 wt % to 20 wt %, for example, 1 wt % to 15 wt %, based on the total amount of the photosensitive resin composition. When the colorant is used within the above range, high luminance and contrast ratio can be expressed in a desired color coordinate.

(B) binder resin

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy 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%, for example, 10 wt% to 40 wt%, based on the total amount of the alkali-soluble 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-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds, such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the binder resin include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer , methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer and the like, but are not limited thereto, and may be used alone or in combination of two or more thereof.

The weight average molecular weight of the 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 binder resin is within the above range, adhesion to the substrate is excellent, physical and chemical properties are good, and the viscosity is appropriate.

The acid value of the 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 binder resin is within the above range, excellent pixel resolution may be obtained.

The binder resin may be included in an amount of 0.1 wt% to 30 wt%, for example, 5 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, it is possible to obtain excellent surface smoothness due to excellent developability and improved crosslinking property in manufacturing the color filter.

(C) photopolymerizable monomer

The photopolymerizable monomer may be a monofunctional or multifunctional 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 during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol. Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Acrylates, 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, novolac epoxy (meth)acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S ^® of Nippon Kayaku Co., Ltd., the same TC-120S ^® , etc.; Osaka Yuki Kagaku Kogyo Co., Ltd.'s V- ^158® , V- ^2311® , etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M- ^210® , M- ^240® , and M- ^6200® of Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA ^® from Nippon Kayaku Co., Ltd., HX-220 ^® , R-604 ^® , etc.; Examples include V- ^260® , V- ^312® , and V-335 ^HP® of Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronix M- ^309® , M- ^400® , M- ^405® , M- ^450® , and M from Toagosei Chemical Industry Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^® , etc.; KAYARAD TMPTA ^® from Nippon Kayaku Co., Ltd., Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® , etc.; V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® and the like of Osaka Yuki Kayaku Kogyo Co., Ltd. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used after being treated with an acid anhydride to impart better developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt % to 30 wt %, for example, 5 wt % to 20 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, pattern characteristics and developability are excellent when manufacturing a color filter.

(D) photopolymerization initiator

As the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound may be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 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(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-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 benzyldimethylketal.

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-(naphtho1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl (4'-methoxystyryl)-6-triazine, and the like.

Examples of the oxime-based compound include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone etc. are mentioned.

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

The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt %, for example, 1 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization sufficiently occurs during exposure in a pattern forming process for manufacturing a color filter, resulting in excellent sensitivity and improved transmittance.

(E) solvent

The solvent is not particularly limited, but specifically, for example, alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol 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 alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; or ketonic acid ester compounds such as ethyl pyruvate, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. may be used alone or in combination of two or more thereof.

Considering miscibility and reactivity in the solvent, preferably glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxyethyl propionate; diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate may be used.

The solvent may be included as the remainder with respect to the total amount of the photosensitive resin composition, and specifically may be included in 20% by weight to 90% by weight. When the solvent is included within the above range, the coating property of the photosensitive resin composition is excellent, and excellent flatness can be maintained in a film having a thickness of 3 μm or more.

(F) other additives

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; Additives such as a radical polymerization initiator may be further included.

In addition, the photosensitive resin composition may further include an additive such as an epoxy compound to improve adhesion to a substrate.

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

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

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

Another embodiment provides a color filter including the photosensitive resin film. A manufacturing method of the color filter is as follows.

On a glass substrate on which nothing is coated or on a glass substrate on which a protective film of SiN _x is coated with a thickness of 500 Å to 1500 Å, the above-described photosensitive resin composition for a color filter is applied by using an appropriate method such as spin coating or slit coating. , each applied at a thickness of 3.1 μm to 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After light is irradiated, when the coating layer is treated with an alkaline developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained.

In addition, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by irradiation with actinic rays or the like.

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.

(manufacture of monomolecular compounds)

(Preparation Example 1: Preparation of Intermediate A)

중간체 A

Intermediate A

Aniline (10 mol), 4-bromotoluene (10 mol), Pd ₂ (dba) ₃ (0.1 mol), and Xphos (0.1 mol) were added to toluene, heated to 100° C., and stirred for 24 hours. Ethyl acetate was added to this solution, and the organic layer was extracted by washing twice with water. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain Intermediate A.

(Preparation Example 2: Preparation of Intermediate B-1)

중간체 B-1

Intermediate B-1

2,4-dimethyldiphenylamine (10 mol), 1,2-epoxyhexane (12 mol), and sodium hydride (12 mol) were added to N,N-dimethylformamide (DMF) and heated to 90 °C for 24 hours. while stirring. Ethyl acetate was added to this solution, and the organic layer was extracted by washing twice with water. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate B-1.

(Preparation Example 3: Preparation of Intermediate B-2)

중간체 B-2

Intermediate B-2

Intermediate B-2 was obtained by synthesizing in the same manner as in Preparation Example 2, except that 1,2-butylene oxide was used instead of 1,2-epoxyhexane.

(Preparation Example 4: Preparation of Intermediate B-3)

중간체 B-3

Intermediate B-3

Intermediate B-3 was obtained by synthesizing in the same manner as in Preparation Example 2, except that Intermediate A was used instead of 2,4-dimethyldiphenylamine.

(Preparation Example 5: Preparation of Intermediate B-4)

중간체 B-4

Intermediate B-4

Intermediate B-4 was obtained by synthesizing in the same manner as in Preparation Example 2, except that 1,2-epoxycyclohexane was used instead of 1,2-epoxyhexane.

(Preparation Example 6: Preparation of Intermediate C-1)

중간체 C-1

Intermediate C-1

Intermediate B-1 (10 mmol), iodomethane (15 mmol), and sodium hydride (15 mmol) were added to N,N-dimethylformamide and stirred at room temperature for 24 hours. Ethyl acetate was added to this solution, and the organic layer was extracted by washing twice with water. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate C-1.

(Preparation Example 7: Preparation of Intermediate C-2)

중간체 C-2

Intermediate C-2

A compound represented by Intermediate C-2 was obtained by synthesizing in the same manner as in Preparation Example 6, except that 2-iodopropane was used instead of iodomethane.

(Preparation Example 8: Preparation of Intermediate C-3)

중간체 C-3

Intermediate C-3

A compound represented by Intermediate C-3 was obtained by synthesizing in the same manner as in Preparation Example 6, except that Intermediate B-2 was used instead of Intermediate B-1.

(Preparation Example 9: Preparation of Intermediate C-4)

중간체 C-4

Intermediate C-4

A compound represented by Intermediate C-4 was obtained by synthesizing in the same manner as in Preparation Example 8, except that iodoethane was used instead of iodomethane.

(Preparation Example 10: Preparation of Intermediate C-5)

중간체 C-5

Intermediate C-5

A compound represented by Intermediate C-5 was obtained by synthesizing in the same manner as in Preparation Example 6, except that Intermediate B-4 was used instead of Intermediate B-1.

(Preparation Example 11: Preparation of Intermediate C-6)

중간체 C-6

Intermediate C-6

A compound represented by Intermediate C-6 was obtained by synthesizing in the same manner as in Preparation Example 10, except that 1-iodo-2-ethylhexane was used instead of iodomethane.

(Preparation Example 12: Preparation of Chemical Formula 4-1)

Intermediate C-1 (60 mmol) and 3,4-dihydroxy-3-cyclobutyn-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL) and refluxed to obtain Water is removed with a Dean-stark distillation unit. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by Chemical Formula 4-1.

(Preparation Example 13: Preparation of Chemical Formula 4-2)

A compound represented by Formula 4-2 was obtained by synthesizing in the same manner as in Preparation Example 12, except that Intermediate C-2 was used instead of Intermediate C-1.

(Preparation Example 14: Preparation of Chemical Formula 4-3)

A compound represented by Formula 4-3 was obtained by synthesizing in the same manner as in Preparation Example 12, except that Intermediate C-3 was used instead of Intermediate C-1.

(Preparation Example 15: Preparation of Chemical Formula 4-4)

A compound represented by Formula 4-4 was obtained by synthesizing in the same manner as in Preparation Example 12, except that Intermediate C-4 was used instead of Intermediate C-1.

(Preparation Example 16: Preparation of Formula 4-5)

A compound represented by Formula 4-5 was obtained by synthesizing in the same manner as in Preparation Example 12, except that Intermediate C-5 was used instead of Intermediate C-1.

(Preparation Example 17: Preparation of Formula 4-6)

A compound represented by Formula 4-6 was obtained by synthesizing in the same manner as in Preparation Example 12, except that Intermediate C-6 was used instead of Intermediate C-1.

(manufacture of core-shell dyes)

(Synthesis Example 1: Synthesis of Chemical Formula 5-1)

After dissolving the compound (5 mmol) represented by Chemical Formula 4-1 in 600 mL of chloroform solvent, triethylamine (TEA) (50 mmol) was added. 2,6-Pyridinedicarbonyl dichloride (20 mmol) and (2,3,5,6-tetramethyl-1,4-phenylene)dimethanamine (20 mmol) were dissolved in 60mL chloroform and stirred at room temperature for 5 simultaneous loading over time. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula 5-1.

Maldi-tof MS: 1346.75 m/z

(Synthesis Example 2: Synthesis of Chemical Formula 5-2)

A compound represented by Chemical Formula 5-2 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1402.82 m/z

(Synthesis Example 3: Synthesis of Chemical Formula 5-3)

A compound represented by Chemical Formula 5-3 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1290.60 m/z

(Synthesis Example 4: Synthesis of Chemical Formula 5-4)

A compound represented by Chemical Formula 5-4 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1318.72 m/z

(Synthesis Example 5: Synthesis of Formula 5-5)

A compound represented by Chemical Formula 5-5 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1342.72 m/z

(Synthesis Example 6: Synthesis of Formula 5-6)

A compound represented by Chemical Formula 5-6 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1538.94 m/z

(Synthesis Example 7: Synthesis of Formula 5-7)

After dissolving the compound (5 mmol) represented by Chemical Formula 4-1 in 600 mL of chloroform solvent, triethylamine (50 mmol) was added. 2,6-Pyridinedicarbonyl dichloride (20 mmol) and (2-methyl-1,4-phenylene)dimethanamine (20 mmol) were dissolved in 60 mL of chloroform and added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 5-7.

Maldi-tof MS: 1262.66 m/z

(Synthesis Example 8: Synthesis of Formula 5-8)

A compound represented by Chemical Formula 5-8 was obtained by synthesizing in the same manner as in Synthesis Example 7, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1318.72 m/z

(Synthesis Example 9: Synthesis of Formula 5-9)

A compound represented by Chemical Formula 5-9 was obtained by synthesizing in the same manner as in Synthesis Example 7, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1206.59 m/z

(Synthesis Example 10: Synthesis of Chemical Formulas 5-10)

A compound represented by Chemical Formula 5-10 was obtained by synthesizing in the same manner as in Synthesis Example 7, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1234.63 m/z

(Synthesis Example 11: Synthesis of Formula 5-11)

A compound represented by Chemical Formula 5-11 was obtained by synthesizing in the same manner as in Synthesis Example 7, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1258.63 m/z

(Synthesis Example 12: Synthesis of Formula 5-12)

A compound represented by Chemical Formula 5-12 was obtained by synthesizing in the same manner as in Synthesis Example 7, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1454.84 m/z

(Synthesis Example 13: Synthesis of Formula 5-13)

After dissolving the compound (5 mmol) represented by Chemical Formula 4-1 in 600 mL of chloroform solvent, triethylamine (50 mmol) was added. 4-Trifluoromethyl pyridine-2,6-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform and dropped simultaneously at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 5-13.

Maldi-tof MS: 1370.60 m/z

(Synthesis Example 14: Synthesis of Formula 5-14)

A compound represented by Chemical Formula 5-14 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1426.66 m/z

(Synthesis Example 15: Synthesis of Formula 5-15)

A compound represented by Chemical Formula 5-15 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1314.54 m/z

(Synthesis Example 16: Synthesis of Chemical Formulas 5-16)

A compound represented by Chemical Formula 5-16 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1342.57 m/z

(Synthesis Example 17: Synthesis of Formula 5-17)

A compound represented by Chemical Formula 5-17 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1366.57 m/z

(Synthesis Example 18: Synthesis of Formula 5-18)

A compound represented by Chemical Formula 5-18 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1562.79 m/z

(Synthesis Example 19: Synthesis of Formula 5-19)

After dissolving the compound (5 mmol) represented by Chemical Formula 4-1 in 600 mL of chloroform solvent, triethylamine (50 mmol) was added. 2-Ethylhexyloxy pyridine-2,6-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform and dropped simultaneously at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 5-19.

Maldi-tof MS: 1490.87 m/z

(Synthesis Example 20: Synthesis of Formula 5-20)

A compound represented by Chemical Formula 5-20 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1546.93 m/z

(Synthesis Example 21: Synthesis of Formula 5-21)

A compound represented by Chemical Formula 5-21 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1434.80 m/z

(Synthesis Example 22: Synthesis of Chemical Formula 5-22)

A compound represented by Chemical Formula 5-22 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1462.83 m/z

(Synthesis Example 23: Synthesis of Formula 5-23)

A compound represented by Chemical Formula 5-23 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1486.83 m/z

(Synthesis Example 24: Synthesis of Formula 5-24)

A compound represented by Chemical Formula 5-24 was obtained by synthesizing in the same manner as in Synthesis Example 13, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1.

Maldi-tof MS: 1683.05 m/z

(Comparative Synthesis Example 1)

After dissolving the compound (5 mmol) represented by Chemical Formula 4-1 in 600 mL of chloroform solvent, triethylamine (50 mmol) was added. 2,6-Pyridinedicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform and dropped simultaneously at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound having a core-shell structure.

(Preparation of photosensitive resin composition)

The specifications of components used in the preparation of the photosensitive resin composition are as follows.

(A) colorant

(dyes)

(A-1) Core-shell dye prepared in Synthesis Example 1 (represented by Chemical Formula 5-1)

(A-2) Core-shell dye prepared in Synthesis Example 2 (represented by Chemical Formula 5-2)

(A-3) Core-shell dye prepared in Synthesis Example 3 (represented by Chemical Formula 5-3)

(A-4) Core-shell dye prepared in Synthesis Example 4 (represented by Chemical Formula 5-4)

(A-5) Core-shell dye prepared in Synthesis Example 5 (represented by Chemical Formula 5-5)

(A-6) Core-shell dye prepared in Synthesis Example 6 (represented by Chemical Formula 5-6)

(A-7) Core-shell dye prepared in Synthesis Example 7 (represented by Chemical Formula 5-7)

(A-8) Core-shell dye prepared in Synthesis Example 8 (represented by Chemical Formula 5-8)

(A-9) Core-shell dye prepared in Synthesis Example 9 (represented by Chemical Formula 5-9)

(A-10) Core-shell dye prepared in Synthesis Example 10 (represented by Chemical Formula 5-10)

(A-11) Core-shell dye prepared in Synthesis Example 11 (represented by Chemical Formula 5-11)

(A-12) Core-shell dye prepared in Synthesis Example 12 (represented by Chemical Formula 5-12)

(A-13) Core-shell dye prepared in Synthesis Example 13 (represented by Chemical Formula 5-13)

(A-14) Core-shell dye prepared in Synthesis Example 14 (represented by Chemical Formula 5-14)

(A-15) Core-shell dye prepared in Synthesis Example 15 (represented by Chemical Formula 5-15)

(A-16) Core-shell dye prepared in Synthesis Example 16 (represented by Chemical Formula 5-16)

(A-17) Core-shell dye prepared in Synthesis Example 17 (represented by Chemical Formula 5-17)

(A-18) Core-shell dye prepared in Synthesis Example 18 (represented by Chemical Formula 5-18)

(A-19) Core-shell dye prepared in Synthesis Example 19 (represented by Chemical Formula 5-19)

(A-20) Core-shell dye prepared in Synthesis Example 20 (represented by Chemical Formula 5-20)

(A-21) Core-shell dye prepared in Synthesis Example 21 (represented by Chemical Formula 5-21)

(A-22) Core-shell dye prepared in Synthesis Example 22 (represented by Chemical Formula 5-22)

(A-23) Core-shell dye prepared in Synthesis Example 23 (represented by Chemical Formula 5-23)

(A-24) Core-shell dye prepared in Synthesis Example 24 (represented by Chemical Formula 5-24)

(A-25) Core-shell dye prepared in Comparative Synthesis Example 1

(Pigment)

(A'-1) C.I. Green Pigment 58

(B) binder resin

Methacrylic acid/benzyl methacrylate copolymer with a weight average molecular weight of 22,000 g/mol (mixing weight ratio 15wt%/85wt%)

(C) photopolymerizable monomer

dipentaerythritol hexaacrylate

(D) photopolymerization initiator

(D-1) 1,2-octanedione

(D-2) 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

(E) solvent

(E-1) cyclohexanone

(E-2) Propylene glycol methyl ether acetate

Examples 1 to 24, Comparative Example 1 and Comparative Example 2

A photosensitive resin composition was prepared by mixing each component according to the compositions shown in Tables 1 and 2 below. Specifically, after dissolving the photopolymerization initiator in a solvent, stirring at room temperature for 2 hours, adding a colorant and stirring for 30 minutes, adding a binder resin and a photopolymerizable monomer, followed by stirring at room temperature for 2 hours. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: % by weight) Example One 2 3 4 5 6 7 8 9 10 11 12 13 (A) colorant
A-1 2 - - - - - - - - - - - - A-2 - 2 - - - - - - - - - - - A-3 - - 2 - - - - - - - - - - A-4 - - - 2 - - - - - - - - - A-5 - - - - 2 - - - - - - - - A-6 - - - - - 2 - - - - - - - A-7 - - - - - - 2 - - - - - - A-8 - - - - - - - 2 - - - - - A-9 - - - - - - - - 2 - - - - A-10 - - - - - - - - - 2 - - - A-11 - - - - - - - - - - 2 - - A-12 - - - - - - - - - - - 2 - A-13 - - - - - - - - - - - - 2 A'-1 - - - - - - - - - - - - - (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) photopolymerizable monomer 8 8 8 8 8 8 8 8 8 8 8 8 8 (D) photopolymerization initiator D-1 One One One One One One One One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) solvent E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 45 45 45 45 45 45

(Unit: % by weight) Example comparative example 14 15 16 17 18 19 20 21 22 23 24 One 2 (A) colorant A-14 2 - - - - - - - - - - - - A-15 - 2 - - - - - - - - - - - A-16 - - 2 - - - - - - - - - - A-17 - - - 2 - - - - - - - - - A-18 - - - - 2 - - - - - - - - A-19 - - - - - 2 - - - - - - - A-20 - - - - - - 2 - - - - - - A-21 - - - - - - - 2 - - - - - A-22 - - - - - - - - 2 - - - - A-23 - - - - - - - - - 2 - - - A-24 - - - - - - - - - - 2 - - A-25 - - - - - - - - - - - 2 - A'-1 - - - - - - - - - - - - 2 (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) photopolymerizable monomer 8 8 8 8 8 8 8 8 8 8 8 8 8 (D) photopolymerization initiator D-1 One One One One One One One One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) solvent E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 45 45 45 45 45 45

(evaluation)

Evaluation 1: Durability evaluation

The photosensitive resin composition prepared in Examples 1 to 24, Comparative Example 1 and Comparative Example 2 was applied to a thickness of 1 μm to 3 μm on a degreased and washed glass substrate having a thickness of 1 mm, and After drying for a minute, a coating was obtained. Subsequently, the coating film was exposed to light using a high-pressure mercury lamp with a dominant wavelength of 365 nm, dried in an oven at 200 ° C for 60 hours, and then the color coordinate change value was measured using a spectrophotometer (MCPD3000, Otsuka electronic Co.) Durability was confirmed, and the results are shown in Table 3 below.

Durability Evaluation Criteria

Very good: color coordinate change value is less than 0.003

Good: Color coordinate change value is 0.003 or more and 0.005 or less

Bad: Color coordinate change value exceeds 0.005

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 durability Good Good Good Good Good very good Good Good Good Good Good very
Good Good Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative Example 1 Comparative Example 2 durability Good Good Good Good very good Good Good Good Good Good very
Good error error

From Table 3, it can be seen that the photosensitive resin composition according to Examples 1 to 24 including the core-shell dye according to one embodiment has excellent durability.

Evaluation 2: Evaluation of luminance and contrast ratio

The photosensitive resin composition prepared in Examples 1 to 24, Comparative Example 1 and Comparative Example 2 was applied to a thickness of 1 μm to 3 μm on a degreased and washed glass substrate having a thickness of 1 mm, and After drying for a minute, a coating was obtained. Subsequently, the coating film was exposed to light using a high-pressure mercury lamp having a dominant wavelength of 365 nm, and then dried for 5 minutes in a hot air circulation drying furnace at 200°C. The luminance and contrast ratio of the pixel layer were measured using a spectrophotometer (MCPD3000, Otsuka electronic Co.), and the results are shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 luminance 67.1 67.3 67.2 67.4 67.2 67.5 67.3 67.2 67.4 67.1 67.3 67.2 67.3 contrast ratio 14700 14900 15100 15200 14900 15300 15200 15100 14900 15100 15200 15100 14900 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative Example 1 Comparative Example 2 luminance 67.4 67.3 67.5 67.2 67.4 67.3 67.3 67.2 67.3 67.4 67.5 65.9 63.5 contrast ratio 15200 15100 14800 15000 14900 15200 14800 14700 15100 14900 14800 14100 12500

From Table 4, in the case of Examples 1 to 24 including the core-shell dye according to one embodiment, compared to the cases of Comparative Examples 1 and 2 not including the core-shell dye, high brightness And it can be confirmed that a high contrast ratio can be obtained.

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

Claims (16)

(A) a colorant containing a dye with a core-shell structure;
(B) a binder resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator; and
(E) contains a solvent;
The core is a squarylium-based compound,
The shell is a photosensitive resin composition represented by Formula 1 or Formula 3-4:
[Formula 1]

[Formula 3-4]

In Formula 1,
R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);
R ² to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group;
m is an integer from 1 to 10;
n is an integer from 0 to 3;
L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
According to claim 1,
Formula 1 is a photosensitive resin composition represented by Formula 2 below:
[Formula 2]

In Formula 2,
R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group);
R ² to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group;
n is an integer from 0 to 3;
According to claim 1,
Formula 1 is a photosensitive resin composition represented by any one of Formula 2-1 or Formula 2-3:
[Formula 2-1]

[Formula 2-3]

In Formula 2-1 or Formula 2-3,
R ² to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group;
R ⁷ and R ⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ⁶ (R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group).
According to claim 1,
The photosensitive resin composition of claim 1, wherein the shell has a cage width of 6.5 Å to 7.5 Å.
According to claim 1,
Formula 1 is a photosensitive resin composition represented by Formula 3-1 below.
[Formula 3-1]

According to claim 1,
The squarylium-based compound is a photosensitive resin composition represented by Formula 4 below:
[Formula 4]

In Formula 4,
R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
According to claim 1,
The length of the core is 1nm to 3nm photosensitive resin composition.
According to claim 1,
The core is a photosensitive resin composition having a maximum absorption peak at a wavelength of 530 nm to 680 nm.
According to claim 1,
The squarylium-based compound is a photosensitive resin composition represented by any one of the following formulas 4-1 to 4-6.
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

According to claim 1,
The dye of the core-shell structure comprises the core and the shell in a molar ratio of 1: 1 photosensitive resin composition.
According to claim 1,
The dye of the core-shell structure is a green dye photosensitive resin composition.
According to claim 1,
The photosensitive resin composition further comprises a pigment.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
0.5% to 20% by weight of the colorant;
0.1% to 30% by weight of the binder resin;
0.1% to 30% by weight of the photopolymerizable monomer;
0.1% to 5% by weight of the photopolymerization initiator; and
The remaining amount of the solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition further contains 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 using the photosensitive resin composition of any one of claims 1 to 14.
A color filter comprising the photosensitive resin film of claim 15 .

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