KR20230006282A - Photosensitive resin composition, photosensitive resin layer including the same, color filter and electronic device - Google Patents

Abstract

Provided is a photosensitive resin composition which contains a colorant. The colorant contains a dye represented by chemical formula 1, a dye having a core-shell structure, and a phthalocyanine dye. Also, provided are a photosensitive resin film manufactured utilizing the composition, a color filter comprising the photosensitive resin film, and an electronic device comprising the color filter. In the chemical formula 1, each substituent is as defined in the specification. While the color purity is increased, the durability can be secured.

Description

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

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

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 capable of securing durability while increasing color purity by minimizing the content of a colorant.

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.

Another embodiment is to provide an electronic device including the color filter.

One embodiment is a photosensitive resin composition containing a colorant,

The colorant provides a photosensitive resin composition including a dye represented by Formula 1 below, a dye having a core-shell structure, and a phthalocyanine-based dye.

[Formula 1]

In Formula 1,

X is an oxygen atom or a sulfur atom,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;

R ¹ to R ⁴ are each independently a hydrogen atom, 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 L ¹ may be represented by Formula L-1 below.

[Formula L-1]

In the above formula L-1,

R ⁵ and R ⁶ are each independently a hydrogen atom or a C1 to C20 alkyl group unsubstituted or substituted with a halogen group.

The dye represented by Chemical Formula 1 may be represented by any one of Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The dye represented by Chemical Formula 1 may be included in an amount greater than that of the core-shell structured dye, and the dye represented by Chemical Formula 1 may be contained in an amount greater than that of the phthalocyanine-based dye.

The phthalocyanine-based dye may be included in an amount greater than that of the core-shell dye.

The dye represented by Chemical Formula 1 may be included in an amount greater than the content of the core-shell structured dye and the content of the phthalocyanine-based dye.

The dye of the core-shell structure may be composed of a core represented by Chemical Formula 2 and a shell represented by Chemical Formula 3 below.

[Formula 2]

In Formula 2,

R ⁷ to R ¹⁰ 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;

[Formula 3]

In Formula 3,

R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or 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 ² and L ³ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The length of the core represented by Chemical Formula 2 may be 1 nm to 3 nm.

The core represented by Chemical Formula 2 may have a maximum absorption peak at a wavelength of 530 nm to 680 nm.

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

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

The shell represented by Chemical Formula 3 may be represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

n is an integer from 0 to 3;

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

[Formula 3-1-1]

[Formula 3-1-2]

[Formula 3-1-3]

In Formula 3-1-1 to Formula 3-1-3,

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

R ¹⁷ and R ¹⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group).

The shell represented by Chemical Formula 3 may have a cage width of 6.5 Å to 7.5 Å.

The shell represented by Chemical Formula 3 may be represented by any one of Chemical Formulas 3-A to 3-E.

[Formula 3-A]

[Formula 3-B]

[Formula 3-C]

[Formula 3-D]

[Formula 3-E]

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

The phthalocyanine-based dye may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

R ¹⁰¹ to R ¹¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C3 to C20 aryl group. A cyclic C6 to C20 aryloxy group,

However, at least one of R ¹⁰¹ to R ¹⁰⁴ , at least one of R ¹⁰⁵ to R ¹⁰⁸ , and at least one of R ¹⁰⁹ to R ¹¹² are each independently represented by the following formula (5),

At least one of R ¹¹³ to R ¹¹⁶ is represented by a halogen atom or the following formula (5),

[Formula 5]

In Formula 5,

R ¹¹⁷ and R ¹¹⁸ are each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.

Chemical Formula 5 may be represented by any one of Chemical Formulas 5-1 to 5-4.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

The colorant may further include a pigment.

The colorant may be included in an amount of 1 wt% to 15 wt% based on the total amount of the photosensitive resin composition.

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

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, 1% to 15% by weight of the colorant; 1% to 20% by weight of the binder resin; 1% to 20% by weight of the photopolymerizable monomer; 0.1% to 10% 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.

Another embodiment provides an electronic device including the color filter.

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

The photosensitive resin composition according to an embodiment can increase the color purity of the green region by mixing and using three different kinds of dyes, and furthermore, durability, which is one of the representative problems of using dyes, can be additionally secured.

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

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 an embodiment includes a colorant, and the colorant includes a dye represented by Formula 1 below, a core-shell structured dye, and a phthalocyanine-based dye.

[Formula 1]

In Formula 1,

X is an oxygen atom or a sulfur atom,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;

R ¹ to R ⁴ are each independently a hydrogen atom, 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.

CMOS image sensor refers to a non-memory semiconductor that converts the image received by the camera into a digital signal, and is manufactured with the same CMOS semiconductor process as DRAM. The structure has an aggregate structure of pixels such as color filters, photodiodes, and amplifiers, and securing color filter technology is key to realizing high-definition and ultra-slim camera modules. Color filter technology requires a high-resolution and high-sensitivity material, and in order to satisfy the above two characteristics, it is necessary to be able to cut a specific wavelength capable of controlling the characteristics and sensitivity of the negative photoresist.

In order to cut a specific wavelength, conventionally, a technology of selecting a pigment most similar to the wavelength and increasing the ratio has been used to control the wavelength, but in this case, the content of the colorant in the photoresist increases, which deteriorates fairness and reliability. , in most cases, it was not applied to the actual process or the desired characteristics could not be matched.

The present invention relates to a photosensitive resin composition that improves the above problems and has desired cutting properties. Specifically, the photosensitive resin composition of the present invention is cut by adjusting the wavelength of the dye represented by the formula (1) in the blue-green region between blue and green (Green) and blue ( The yellow region between blue can be cut by applying the dye on the core-shell structure to increase the color purity of green. Furthermore, by applying a phthalocyanine-based dye together with the above two types of dyes, durability can be secured. And, due to the combination of the three types of dyes as described above, the amount of colorants used can be greatly reduced.

That is, the photosensitive resin composition according to one embodiment can secure processability and reliability in a thin thickness by using a small amount of colorant through a combination of specific dyes, so it is optimized for process materials for LCD and CIS, without deterioration in transmittance. Color gamut can be increased, and this part can be said to be highly differentiated from existing technologies.

For example, in Chemical Formula 1, L ¹ may be represented by the following Chemical Formula L-1.

[Formula L-1]

In the above formula L-1,

R ⁵ and R ⁶ are each independently a hydrogen atom or a C1 to C20 alkyl group unsubstituted or substituted with a halogen group.

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

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

For example, the dye represented by Chemical Formula 1 may be included in an amount greater than that of the core-shell structured dye, and the dye represented by Chemical Formula 1 may be contained in an amount greater than that of the phthalocyanine-based dye. In this case, it may be advantageous to simultaneously secure color purity and durability.

Furthermore, the phthalocyanine-based dye may be included in a larger amount than the core-shell dye. Specifically, the dye represented by Formula 1 may be included in an amount greater than that of the phthalocyanine-based dye, and the phthalocyanine-based dye may be included in an amount greater than that of the core-shell dye, and the dye represented by Formula 1 may be included in an amount greater than the mixed content of the core-shell structured dye and the phthalocyanine-based dye. In this case, it may be more advantageous to simultaneously secure color purity and durability.

For example, the dye having a core-shell structure may be composed of a core represented by Chemical Formula 2 and a shell represented by Chemical Formula 3 below.

[Formula 2]

In Formula 2,

R ⁷ to R ¹⁰ 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;

[Formula 3]

In Formula 3,

R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or 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 ² and L ³ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

For example, the dye having a core-shell structure may include a non-covalent bond between an oxygen atom of the compound represented by Formula 2 and a hydrogen atom bonded to a nitrogen atom of the shell represented by Formula 3, that is, a hydrogen bond. .

The compound represented by Formula 2 can be used as a green dye because it has excellent green spectral characteristics and a high molar extinction coefficient, but there is a problem in that luminance decreases during the baking process after manufacturing a color resist due to poor durability compared to pigments. there is. In one embodiment, the shell represented by Formula 3 has a core-shell structure using the compound represented by Formula 2 as a core, so that the compound of the core-shell structure is applied as a colorant. The durability of the color filter can be improved. Accordingly, it is possible to implement a color filter with high luminance and high contrast ratio.

Specifically, the dye of the core-shell structure has a structure consisting of a shell surrounding the core and the compound represented by Formula 2 as a core, and the shell is a macrocyclic compound represented by Formula 3, A coating layer may be formed while surrounding the core. Due to this structure, that is, by having a structure in which the compound represented by Chemical Formula 2 exists inside the ring represented by Chemical Formula 3, durability of a dye having a core-shell structure can be improved, and thus high brightness and high A color filter with a contrast ratio can be implemented.

For example, in Formula 3, L ² and L ³ 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 compound represented by Formula 2.

For example, in Formula 2, R ⁷ and R ⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ⁸ and R ¹⁰ 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 ⁷ and R ⁹ 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', The R ⁸ and R ¹⁰ may each independently be a 'C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl 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 2 has three resonance structures, but in this specification, only one resonance structure is shown for convenience. That is, the compound represented by Chemical Formula 2 may be represented by any one of the three resonance structures.

[scheme]

For example, the core may be represented by any one of Chemical Formulas 2-1 to 2-6, but is not necessarily limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

For example, when the compounds represented by Chemical Formulas 2-1 to 2-6 are used in a photosensitive resin composition (eg, as a dye), the solubility in a solvent described below may be 5 or more, such as 5 to 10. 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 2-1 to 2-6 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 2 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 2 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 2 has a length within the above range, a structure in which a shell, which is a macrocyclic compound represented by Chemical Formula 3, surrounds the compound represented by Chemical Formula 2 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 core and the shell in a molar ratio of 1:1. When the core and the shell are present in the above molar ratio, a coating layer (shell) surrounding the core may be well formed.

For example, the shell represented by Chemical Formula 3 may be represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

n is an integer from 0 to 3;

For example, in Formula 3-1, R ¹¹ is a hydrogen atom, and R ¹² to R ¹⁵ may each independently be a hydrogen atom or a substituted or halogen atom.

For example, in Formula 3-1, R ¹¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group), R ¹² to R ¹⁵ may each independently represent a hydrogen atom.

For example, R ¹¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group), and at least one of R ¹² to R ¹⁵ One may be a substituted or unsubstituted C1 to C20 alkyl group.

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

[Formula 3-1-1]

[Formula 3-1-2]

[Formula 3-1-3]

In Formula 3-1-1 to Formula 3-1-3,

R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

R ¹⁷ and R ¹⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ 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" means the distance inside the shell, for example, the distance between two different phenylene groups to which methylene groups are connected to both sides in the shell represented by Chemical Formula 3 (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-A to 3-E, but is not necessarily limited thereto.

[Formula 3-A]

[Formula 3-B]

[Formula 3-C]

[Formula 3-D]

[Formula 3-E]

For example, the core-shell structured dye may be represented by Chemical Formula A-1 or Chemical Formula A-2, but is not necessarily limited thereto.

[Formula A-1]

[Formula A-2]

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

For example, the phthalocyanine-based dye may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

R ¹⁰¹ to R ¹¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C3 to C20 aryl group. A cyclic C6 to C20 aryloxy group,

However, at least one of R ¹⁰¹ to R ¹⁰⁴ , at least one of R ¹⁰⁵ to R ¹⁰⁸ , and at least one of R ¹⁰⁹ to R ¹¹² are each independently represented by the following formula (5),

At least one of R ¹¹³ to R ¹¹⁶ is represented by a halogen atom or the following formula (5),

[Formula 5]

In Formula 5,

R ¹¹⁷ and R ¹¹⁸ are each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.

For example, Chemical Formula 5 may be represented by any one of Chemical Formulas 5-1 to 5-4.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

For example, the phthalocyanine-based dye may be represented by any one of the following Chemical Formulas 6 to 8, but is not necessarily limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

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.

However, the colorant in the photosensitive resin composition according to one embodiment may be composed of only the above three kinds of dyes, and in this case, compared to the case where a pigment is additionally included, problems such as reduced durability may not occur. That is, when using a colorant composed of only the three kinds of dyes without a pigment, since the amount of colorant used can be greatly reduced, it is possible to secure fairness and reliability even in a thin thickness.

The colorant may be included in an amount of 1 wt % to 15 wt %, for example, 1 wt % to 10 wt %, for example, 1 wt % to 5 wt %, for example, 1 wt % to 3 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.

The photosensitive resin composition according to one embodiment may further include a 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 (acrylic binder 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 further include an epoxy-based binder resin together with the acrylic-based binder resin.

The epoxy-based binder resin is a monomer or oligomer that can be polymerized by heat, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

The epoxy-based binder resin may further include a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cyclic aliphatic epoxy resin, and an aliphatic polyglycidyl ether.

As commercial products of these compounds, YX4000, YX4000H, YL6121H, YL6640, YL6677 from Ukashell Epoxy Co., Ltd.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Epicoat 180S75 from Ukashell Epoxy Co., Ltd.; Bisphenol A type epoxy resins include Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 from Yukashell Epoxy Co., Ltd.; Bisphenol F-type epoxy resins include Epicoat 807 and 834 from Yukashell Epoxy Co., Ltd.; Phenol noblock type epoxy resins include Epicoat 152, 154, 157H65 from Yukashell Epoxy Co., Ltd. and EPPN 201, 202 from Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CY175, CY177 and CY179 from CIBA-GEIGY A.G, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from U.C.C, Shodyne 509 from Showa Denko Co., Ltd. , Araldite CY-182, CY-192 and CY-184 from CIBA-GEIGY A.G, Epichron 200 and 400 from Dainipbon Ink Kogyo Co., Ltd., Epicoat 871 and 872 from Ukashell Epoxy Co., Ltd. and EP1032H60, ED-5661 and ED-5662 from Celanese Coating Co., Ltd.; Examples of aliphatic polyglycidyl ether include Epicoat 190P and 191P from Yukashell Epoxy Co., Ltd., Epolite 100MF from Kyoeisha Yushi Kagaku Kogyo Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd. can

The binder resin may be included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 15 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.

The photosensitive resin composition according to one embodiment may further include a 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 1 wt % to 20 wt %, for example, 1 wt % to 15 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.

The photosensitive resin composition according to an embodiment may further include a 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 10 wt %, for example, 0.1 wt % to 5 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.

The photosensitive resin composition according to one embodiment may further include a 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 35% 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.

Meanwhile, 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.

Another embodiment provides an electronic device including the color filter, such as a display device and a camera.

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.

(Dye manufacturing)

(Preparation Example 1: Preparation of a compound represented by Formula 1-1)

Dissolve 7- (Diethylamino) -2- oxo- 2H- chromene- 3- carbaldehyde 　 8.15 mmol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 4.08 mmol and sodium acetate 163 mmol in acetic acid 　 40 mL, The mixture was stirred at 90°C for 10 hours. 200 mL of water was then added to the reaction mixture. The resulting precipitate was filtered, dissolved in diloromethane, and washed with water in a separatory funnel.

The dichlromethane layer recovered from the separatory funnel was dried with MgSO ₄ and then purified by silica gel column chromatography to obtain a compound represented by Formula 1-1 below.

[Formula 1-1]

Maldi-tof MS : 816 m/z

(Preparation Example 2: Preparation of a compound represented by Formula 1-2)

7- (Diethylamino) - 2- oxo- 2H- chromene- 3- carbaldehyde instead of 7- (4- (2-isobutyl-2,4-dimetylphenyl) amino) - 2- oxo- 2H- chromene- 3- carbaldehyde A compound represented by Formula 1-2 was obtained in the same manner as in Preparation Example 1 except for one.

[Formula 1-2]

Maldi-tof MS: 1024 m/z

(Preparation Example 3: Preparation of a compound represented by Formula 1-3)

7- (Diethylamino) - 2- oxo- 2H- chromene- 3- carbaldehyde 　 Instead of 7- (4-diphenylamino) - 2- oxo- 2H- chromene- 3- Carbaldehyde Same as in Preparation Example 1 except for changing Thus, a compound represented by Chemical Formula 1-3 was obtained.

[Formula 1-3]

Maldi-tof MS: 1008 m/z

(Preparation Example 4: Preparation of a compound represented by Formula A-1)

2,4-dimethyldiphenylamine (10 mol), 1,2-epoxycyclohexane (12 mol), and sodium hydride (12 mol) were added to N,N-dimethylformamide, heated to 90°C, and stirred for 24 hours. did After adding 15 mmol of iodomethyl, the mixture was stirred for 3 hours.

Ethyl acetate was added to the solution and washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain Intermediate 1 compound.

Intermediate 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. It was removed with a Dean-stark distillation apparatus. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain an intermediate 2 compound.

After dissolving Intermediate 2 (5 mmol) in 600 mL of chloroform solvent, triethylamine (50 mmol) was added, and 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform for 5 hours at room temperature. simultaneous loading during After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula A-1 below.

[Formula A-1]

Maldi-tof MS: 1231 m/z

(Preparation Example 5: Preparation of a compound represented by Formula A-2)

Intermediate 2 of Formula A-1 was synthesized in the same manner. After dissolving Intermediate 2 (5 mmol) in 600mL chloroform solvent, triethylamine (50mmol) was added, 2,6-pyridinedicarbonyl dichloride (20 mmol) and Tetrafluoro-p-xylylenediamine (20 mmol) were dissolved in 60mL chloroform, and room temperature were dropped simultaneously for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Formula A-2 below.

[Formula A-2]

Maldi-tof MS: 1375 m/z

(Preparation Example 6: Preparation of a compound represented by Formula 6)

3,4,5,6-tetrachlorophthalonitrile (5 g), 2,4-di-t-butylphenol (3.8 g), K ₂ CO ₃ (3.898 g), and N,N-Dimethylformamide (50 ml) were added to a 100 ml flask. It was added and stirred while heating to 70 °C. After completion of the reaction, extraction with EA (ethyl acetate) and concentration of the EA/hexane column-purified liquid by column chromatography to obtain a solid, and vacuum drying of the solid to obtain 3,5,6-Trichloro-4-( 2,4-di- tert -butylphenoxy)-phthalonitrile was obtained.

3,5,6-Trichloro-4-(2,4-di- tert -butylphenoxy)-phthalonitrile (1.45 g), 1,8-Diazabicycloundec-7-ene (0.38 g), 1-pentanol ( 7 g) was added and heated to 90 ° C. After the solid melted, zinc acetate (0.15 g) was added and stirred while continuously heating to 140 ° C. After completion of the reaction, the precipitate was filtered with MeOH and dried under vacuum. The dried solid is purified by column chromatography. A small amount of dichloromethane was added to the obtained solid to dissolve the solid, and methanol was added to crystallize the solid. At this time, the obtained solid was filtered and vacuum dried to obtain a compound represented by Formula 6 below.

[Formula 6]

Maldi-tof MS : 1809 m/z

(Preparation Example 7: Preparation of a compound represented by Formula 7)

3,4,5,6-tetrachlorophthalonitrile (5g), 2-Phenylphenol (3.21g), K ₂ CO ₃ (3.9g), and acetone (25ml) were added to a 100ml flask and stirred while heating to 70°C. After completion of the reaction, the solid obtained by distilling the liquid obtained by washing with acetone was filtered and dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered, and vacuum dried to obtain 4-(Biphenyl-2-yloxy)-3,5, 6-trichloro-phthalonitrile was obtained.

4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.6 g), 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90°C to melt the solid, then zinc acetate (0.34g) was added and stirred while heating to 140°C. . After completion of the reaction, precipitation was confirmed with methanol, followed by filtration and vacuum drying, and the dried solid was purified by column chromatography. Dichloromethane was appropriately added to the solid obtained after purification to dissolve the solid, and then methanol was added to crystallize. The crystallized solid was filtered and vacuum dried to obtain a compound represented by Formula 7 below.

[Formula 7]

Maldi-tof MS: 1650 m/z

(Preparation Example 8: Preparation of a compound represented by Formula 8)

3,4,5,6-tetrachlorophthalonitrile (5 g), 2-cyclohexylphenol (3.3143 g), K ₂ CO ₃ (3.898 g) and N,N-Dimethylformamide (50 ml) were added to a 100 ml flask and heated to 70 °C. Stir. After completion of the reaction, extraction with EA (ethyl acetate) and concentration of the EA/hexane column-purified liquid by column chromatography to obtain a solid, and vacuum drying of the solid to obtain 3,5,6-Trichloro-4-( A 2-cyclohexylphenoxy)-phthalonitrile compound was obtained.

3,5,6-Trichloro-4-(2-cyclohexylphenoxy)-phthalonitrile (1.5 g), the above 3,4,5,6-tetrachlorophthalonitrile (0.33 g)) and 1,8-Diazabicycloundec-7-ene in a 100 ml flask (1.3g) 1-pentanol (15 ml) was added and heated to 90 °C, and after the solid melted, zinc acetate (0.23 g) was added and stirred while continuously heating to 140 °C. After completion of the reaction, the precipitate was filtered with MeOH, dried under vacuum, and the dried solid was purified by column chromatography. A small amount of dichloromethane was added to the obtained solid to dissolve the solid, and methanol was added to crystallize the solid. At this time, the obtained solid was filtered and vacuum dried to obtain a compound represented by Formula 8 below.

[Formula 8]

Maldi-tof MS: 1548 m/z

(Preparation of photosensitive resin composition)

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

(A) colorant

(dyes)

(A1) dye prepared in Preparation Example 1 (represented by Chemical Formula 1-1)

(A2) dye prepared in Preparation Example 2 (represented by Formula 1-2)

(A3) dye prepared in Preparation Example 3 (represented by Chemical Formula 1-3)

(A4) dye prepared in Preparation Example 4 (represented by Formula A-1)

(A5) dye prepared in Preparation Example 5 (represented by Formula A-2)

(A6) dye prepared in Preparation Example 6 (represented by Formula 6)

(A7) dye prepared in Preparation Example 7 (represented by Formula 7)

(A8) dye prepared in Preparation Example 8 (represented by Formula 8)

(Pigment)

(A9) C.I. Green Pigment 58 (SANYO)

(A10) C.I. Yellow Pigment 138 (SANYO)

(B) binder resin

(B1) acrylic binder resin (RY25, SHOWA DENKO)

(B2) Epoxy-based binder resin (EHPE3150, DAICEL)

(C) photopolymerizable monomer

Dipentaerythritol hexaacrylate (Japan Explosives)

(D) photopolymerization initiator

SPI-03 (Samyang Corporation)

(E) solvent

Propylene glycol monomethyl ether acetate (PGMEA)

Examples 1 to 6 and Comparative Examples 1 to 4

A photosensitive resin composition was prepared by mixing each component according to the composition shown in Table 1 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 comparative example One 2 3 4 5 6 One 2 3 4 (A) colorant
A1 1.1 - - - - - - - 1.1 - A2 - 1.1 - - - - - - - - A3 - - 1.1 1.1 1.1 1.1 - - - - A4 0.2 0.2 0.2 - - - - 0.2 - - A5 - - - 0.2 0.2 0.2 - - - - A6 - - - - - 0.5 - - - - A7 0.5 0.5 0.5 0.5 - - 0.5 - - - A8 - - - - 0.5 - - - - - A9 - - - - - - 21.1 21.4 20.5 21.6 A10 12.1 12.1 12.1 12.1 12.1 12.1 7.0 7.0 7.0 7.0 (B) binder resin B1 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 B2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (C) photopolymerizable monomer 7.3 7.3 7.3 7.3 7.3 7.3 7.3 7.3 7.3 7.3 (D) photopolymerization initiator 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 (E) solvent 70.1 70.1 70.1 70.1 70.1 70.1 55.9 55.9 55.9 55.9

(evaluation)

Rating: Reliability Rating

The photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was applied to a thickness of 1 μm to 3 μm on a glass substrate having a thickness of 1 mm washed and degreased, 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 thickness and transmittance were measured using a contact type measuring instrument (Tenco) and an MCPS measuring instrument. It was evaluated, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Thickness (nm) (@Gy0.566) 2.21 2.13 2.01 1.94 1.87 2..03 3.63 3.55 2.89 >5.00 Transmittance (%) (@Gy0.566) 104 104 104 103 102 103.8 100 100.5 98.8 <80

From Table 2, it can be confirmed that the photosensitive resin composition according to one embodiment has excellent transmittance even at a thin thickness, so it is excellent in processability and reliability, and it can be easily expected that the color purity will also be excellent because there is no decrease in transmittance.

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 as. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (25)

As a photosensitive resin composition containing a colorant,
The colorant is a photosensitive resin composition comprising a dye represented by Formula 1, a dye having a core-shell structure, and a phthalocyanine-based dye:
[Formula 1]

In Formula 1,
X is an oxygen atom or a sulfur atom,
L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;
R ¹ to R ⁴ are each independently a hydrogen atom, 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,
L ¹ is a photosensitive resin composition represented by the following formula L-1:
[Formula L-1]

In the above formula L-1,
R ⁵ and R ⁶ are each independently a hydrogen atom or a C1 to C20 alkyl group unsubstituted or substituted with a halogen group.
According to claim 1,
The dye represented by Chemical Formula 1 is a photosensitive resin composition represented by any one of Chemical Formulas 1-1 to 1-3.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

According to claim 1,
The dye represented by Formula 1 is included in a higher content than the dye of the core-shell structure,
The dye represented by Formula 1 is included in a greater content than the phthalocyanine-based dye photosensitive resin composition.
According to claim 4,
The photosensitive resin composition in which the phthalocyanine-based dye is included in a larger amount than the dye of the core-shell structure.
According to claim 1,
The dye represented by Chemical Formula 1 is included in an amount greater than the content of the dye of the core-shell structure and the content of the phthalocyanine-based dye.
According to claim 1,
The core-shell structured dye is a photosensitive resin composition composed of a core represented by the following formula (2) and a shell represented by the following formula (3):
[Formula 2]

In Formula 2,
R ⁷ to R ¹⁰ 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;
[Formula 3]

In Formula 3,
R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);
R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or 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 ² and L ³ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
According to claim 7,
The length of the core represented by the formula (2) is 1nm to 3nm photosensitive resin composition.
According to claim 7,
The core represented by Formula 2 is a photosensitive resin composition having a maximum absorption peak at a wavelength of 530 nm to 680 nm.
According to claim 7,
The core represented by Chemical Formula 2 is a photosensitive resin composition represented by any one of Chemical Formulas 2-1 to 2-6.
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

According to claim 7,
The shell represented by Chemical Formula 3 is a photosensitive resin composition represented by Chemical Formula 3-1:
[Formula 3-1]

In Formula 3-1,
R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group);
R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;
n is an integer from 0 to 3;
According to claim 7,
The shell represented by Chemical Formula 3 is a photosensitive resin composition represented by any one of the following Chemical Formulas 3-1-1 to 3-1-3:
[Formula 3-1-1]

[Formula 3-1-2]

[Formula 3-1-3]

In Formula 3-1-1 to Formula 3-1-3,
R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group;
R ¹⁷ and R ¹⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-C(=O)OR ¹⁶ (R ¹⁶ is a substituted or unsubstituted C1 to C20 alkyl group).
According to claim 7,
The photosensitive resin composition in which the shell represented by Chemical Formula 3 has a cage width of 6.5 Å to 7.5 Å.
According to claim 7,
The shell represented by Chemical Formula 3 is a photosensitive resin composition represented by any one of Chemical Formulas 3-A to 3-E.
[Formula 3-A]

[Formula 3-B]

[Formula 3-C]

[Formula 3-D]

[Formula 3-E]

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 phthalocyanine-based dye is a photosensitive resin composition represented by the following formula (4):
[Formula 4]

In Formula 4,
R ¹⁰¹ to R ¹¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C3 to C20 aryl group. A cyclic C6 to C20 aryloxy group,
However, at least one of R ¹⁰¹ to R ¹⁰⁴ , at least one of R ¹⁰⁵ to R ¹⁰⁸ , and at least one of R ¹⁰⁹ to R ¹¹² are each independently represented by the following formula (5),
At least one of R ¹¹³ to R ¹¹⁶ is represented by a halogen atom or the following formula (5),
[Formula 5]

In Formula 5,
R ¹¹⁷ and R ¹¹⁸ are each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.
According to claim 16,
Chemical Formula 5 is a photosensitive resin composition represented by any one of Chemical Formulas 5-1 to 5-4.
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

According to claim 1,
The photosensitive resin composition further comprises a pigment.
According to claim 1,
The colorant is included in an amount of 1% to 15% by weight based on the total amount of the photosensitive resin composition.
According to claim 1,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent.
According to claim 20,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
1% to 15% by weight of the colorant;
1% to 20% by weight of the binder resin;
1% to 20% by weight of the photopolymerizable monomer;
0.1% to 10% by weight of the photopolymerization initiator; and
The remaining amount of the solvent
Photosensitive resin composition comprising a.
According to claim 20,
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 22.
A color filter comprising the photosensitive resin film of claim 23 .
An electronic device comprising the color filter of claim 24.

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