KR102577766B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) a polymer-containing binder resin represented by the following formula (1); (B) a colorant comprising a first dye containing a compound represented by the following formula (2) and a second dye containing a compound represented by the following formula (3); (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a photosensitive resin composition containing a solvent, a photosensitive resin film manufactured using the photosensitive resin composition, and a color filter comprising the photosensitive resin film.
[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3, each substituent is as defined in the specification)

Description

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

This description relates to a photosensitive resin composition, a photosensitive resin film and a color filter manufactured using the same.

Liquid crystal display devices, one of the display devices, have advantages such as light weight, thinness, low cost, low power consumption, and excellent adhesion to integrated circuits, and their range of use is expanding to laptop computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, an active circuit section consisting of a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate on which ITO pixel electrodes are formed. A 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 of ) are arranged in a certain order, are stacked one after the other.

The pigment dispersion method, which is one of the methods of implementing a color filter, involves coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing the pattern of the shape to be formed, and then removing the unexposed area with a solvent. This is a method of forming a colored thin film by repeating a series of heat curing processes. The colored photosensitive resin composition used to manufacture color filters according to the pigment dispersion method generally consists 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 used to manufacture LCDs for mobile phones, laptops, monitors, and TVs. However, in recent years, photosensitive resin compositions for color filters using a pigment dispersion method, which has various advantages, are required to have not only excellent pattern characteristics but also further improved performance. In particular, the characteristics of high brightness and high contrast ratio along with high color reproduction rate are urgently required. However, even in the photosensitive resin composition for color filters using the pigment dispersion method, which has the above advantages, the process of refining the powder is difficult, and even after dispersion, the dispersion state must be stable within the dispersion, so various additives are required and the process is also very difficult. Furthermore, pigment dispersions have the disadvantage of difficult storage and transportation conditions to maintain optimal quality. Additionally, color filters manufactured from pigment-type photosensitive resin compositions have limitations in luminance and contrast ratio resulting from the size of pigment particles.

Accordingly, the need to develop dyes that have heat resistance and process margin characteristics similar to pigments has emerged as an alternative to pigments.

Meanwhile, an image sensor refers to an image capture device component that generates an image from a mobile phone camera or DSC (digital still camera). Depending on the manufacturing process and application method, it is broadly divided into a charge coupled device (CCD) image sensor and a charge coupled device (CCD) image sensor. It can be classified as a complementary metal oxide semiconductor (CMOS) image sensor. A color imaging device used in a solid-state imaging device or a complementary metal oxide semiconductor is a color filter ( It is common to install each color filter and separate the colors. Recently, the pattern size of the color filter installed in these color imaging devices is 2㎛ or less, which is 1/100 to 1/200 times the size of the color filter pattern for existing LCDs. Accordingly, increasing resolution and reducing residue are important items that determine the performance of the device.

In the case of color imaging devices for image sensors, smaller dispersed particles are required to form fine patterns. In order to meet these demands, there are attempts to implement a color filter with improved brightness and contrast ratio by introducing a dye that does not form particles instead of a pigment and manufacturing a photosensitive resin composition suitable for the dye. However, in the case of dyes, there is a problem that durability such as light resistance and heat resistance is inferior to that of pigments, and process margin characteristics (residue characteristics) are weak.

One embodiment is to provide a dye-type photosensitive resin composition with excellent durability and process margin characteristics (residue characteristics).

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

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

One embodiment includes (A) a polymer-containing binder resin represented by the following formula (1); (B) a colorant comprising a first dye containing a compound represented by the following formula (2) and a second dye containing a compound represented by the following formula (3); (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

R ^a and R ^b are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ^c to R ^h are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

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

R ¹ to R ⁴ 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,

At least one of R ¹ to R ⁴ includes a substituted or unsubstituted acrylate group at the terminal,

The acrylate group forms a direct bond with the chiral carbon,

R ¹³ to R ²⁸ 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 C1 to C20 alkyl group. It is a ringed C6 to C20 aryloxy group,

n is an integer from 1 to 10000.

The polymer represented by Formula 1 may have a weight average molecular weight of 1000 g/mol to 20000 g/mol.

The binder resin may further include an acrylic binder resin.

The polymer represented by Formula 1 may be included in the same amount as the acrylic binder resin.

At least one of R ¹ to R ⁴ may be represented by the following formula (4).

[Formula 4]

In Formula 4 above,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is represented by the following formula 4-1 or 4-2,

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* means chiral carbon,

**1 refers to the part connected to ** in Chemical Formula 4,

**2 refers to the portion connected to the oxygen atom constituting the ether group of Formula 4 above.

R ¹ or R ² and R ³ or R ⁴ may each independently be represented by Formula 5 or Formula 6 below.

[Formula 5]

[Formula 6]

In Formula 5 and Formula 6 above,

L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

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

R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* means chiral carbon.

R ¹ and R ³ are each independently a C6 to C20 aryl group substituted with a C1 to C10 alkyl group, and R ² and R ⁴ may each independently be represented by Formula 5 or Formula 6.

R ¹ and R ³ may each independently be represented by the following formulas 7-1 to 7-3.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Formula 7-1 to Formula 7-3,

R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.

The compound represented by Formula 2 may be represented by any one of the following Formulas 2-1 to 2-7.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

The first dye is a core-shell dye having a structure consisting of a core and a shell surrounding the core, and the core may include the compound represented by Formula 2.

The shell may be represented by Formula 8 or Formula 9 below.

[Formula 8]

[Formula 9]

In Formula 8 and Formula 9,

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The L ^a to L ^d may each independently be a substituted or unsubstituted C1 to C10 alkylene group.

The shell may be represented by Formula 8-1 or Formula 9-1 below.

[Formula 8-1]

[Formula 9-1]

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

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 core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following formulas 10-1 to 10-14.

[Formula 10-1]

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

[Formula 10-6]

[Formula 10-7]

[Formula 10-8]

[Formula 10-9]

[Formula 10-10]

[Formula 10-11]

[Formula 10-12]

[Formula 10-13]

[Formula 10-14]

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

At least one of R ¹³ to R ²⁸ may be represented by Formula 11 below.

[Formula 11]

In Formula 11 above,

R ²⁹ and R ³⁰ are each independently a halogen atom,

n1 and n2 are each independently integers from 0 to 5, provided that 1 ≤ n1+n2 ≤ 5.

Formula 11 may be represented by any one selected from the group consisting of Formulas 12-1 to 12-4 below.

[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Formula 12-4]

In Formulas 12-1 to 12-4,

R ²⁹ and R ³⁰ are each independently a halogen atom.

At least one of R ¹³ to R ²⁸ may be represented by Formula 11, and at least one of R ¹³ to R ²⁸ may be represented by Formula 13 below.

[Formula 13]

The compound represented by Formula 3 may be represented by any one of Formulas 14 to 23 below.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

The first dye and the second dye may each independently be a green dye.

The first dye may be included in a smaller amount than the second dye.

The colorant may further include a yellow pigment.

The photosensitive resin composition includes 1% to 20% by weight of the binder resin, based on the total amount of the photosensitive resin composition; 30% to 70% by weight of the colorant; 1% to 10% by weight of the photopolymerizable compound; 0.1% to 5% by weight of the photopolymerization initiator; And it may include 15% by weight to 50% by weight 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 (meth)acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. It can be included.

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

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

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

The photosensitive resin composition according to one embodiment can implement a color filter with excellent durability and process characteristics by using two types of green dye having different specific structures together with a silicone-acrylic polymer having a specific structure.

Figure 1 is a diagram showing the cage width of the shell represented by Chemical Formula 8-1.
Figure 2 is a photograph of a pattern after developing the photosensitive resin composition according to Example 1.
Figure 3 is a photograph of a pattern after developing the photosensitive resin composition according to Example 2.
Figure 4 is a photograph of a pattern after developing the photosensitive resin composition according to Comparative Example 1.

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 the compound is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, or already. 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. , C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise specified herein, “heterocycloalkyl group”, “heterocycloalkenyl group”, “heterocycloalkynyl group”, and “heterocycloalkylene group” refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl group, respectively. It means that at least one hetero atom of N, O, S or P is present in the ring compound of ren.

Unless otherwise specified herein, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible.

Unless otherwise specified herein, “combination” means mixing or copolymerization.

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

Also, unless otherwise specified in the specification, “*” refers to a chiral carbon.

Additionally, unless otherwise specified herein, “**” refers to a portion connected to the same or different atom or chemical formula.

A photosensitive resin composition according to one embodiment includes (A) a polymer-containing binder resin represented by the following formula (1); (B) a colorant comprising a first dye containing a compound represented by the following formula (2) and a second dye containing a compound represented by the following formula (3); (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

R ^a and R ^b are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ^c to R ^h are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

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

R ¹ to R ⁴ 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,

At least one of R ¹ to R ⁴ includes a substituted or unsubstituted acrylate group at the terminal,

The acrylate group forms a direct bond with the chiral carbon,

R ¹³ to R ²⁸ 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 C1 to C20 alkyl group. It is a ringed C6 to C20 aryloxy group,

n is an integer from 1 to 10000.

A key material in the production of high-brightness color filters is a colorant, and a pigment-type photosensitive resin composition is applied to existing color filters. Pigments have excellent fairness, but there is a limit to finely dispersing pigment particles that affect brightness improvement (pigment-type photosensitive resin compositions have a slight improvement in brightness when pigment particles are dispersed below 50 nm to increase brightness. There is a problem of contrast ratio reduction due to particle aggregation due to dispersion destabilization), and it is one of the causes of ACC defects, which is a problem in recent LCD displays.

Dyes have high solubility in a single molecule state and have high brightness and high contrast ratio characteristics compared to pigments. However, because they are less heat-resistant and durable than pigments, they are vulnerable to processing solvents used in the LCD panel manufacturing process, causing color change and reduced brightness. There is. Accordingly, there were limitations in completely replacing pigments with dyes, and methods such as limiting the content of dyes or applying epoxy-based binder resins with good chemical resistance were used to solve this problem, but this resulted in lower brightness and lower dye content. It could be said that it is not a fundamental solution in that it does not sufficiently express the characteristics it possesses.

In addition, as part of efforts to improve dye-type photosensitive resin compositions that lack durability, there have been attempts to improve durability by adjusting the weight ratio of the binder resin and photopolymerizable compound or adjusting the sensitivity of the photopolymerization initiator. However, in these attempts, the residue There is a disadvantage in that the process characteristics are insufficient.

Accordingly, after several trials and errors, the present inventors have developed a dye-type photosensitive resin composition that is a dye-type composition but has excellent durability and residue characteristics.

(A) Binder resin

The binder resin in the photosensitive resin composition according to one embodiment includes a polymer (silicone acrylic polymer) represented by Formula 1 above.

The photosensitive resin composition to which the polymer-containing binder resin represented by Formula 1 is applied has stronger hydrophobicity compared to the photosensitive resin composition to which the non-silicone acrylic binder resin used conventionally is applied, and may have excellent residue characteristics on the organic or inorganic layer, and at the same time, The weak heat resistance of dyes can also be supplemented (durability supplemented).

For example, the polymer represented by Formula 1 may have a weight average molecular weight of 1000 g/mol to 20000 g/mol.

In addition, even if it is a silicone-acrylic polymer, if a silicone-acrylic polymer whose structure is not represented by Formula 1 is used, the weak durability of the residue property improvement dye cannot be simultaneously improved. For example, when it has a structure like **-O-Si-O-Si-O-Si-O-** or when silicon and oxygen atoms form a ring structure (cyclic siloxane, etc.), acrylate groups are added at both ends. If it is not present, it is impossible to improve durability and process characteristics at the same time.

Meanwhile, the binder resin may further include an acrylic binder resin.

The acrylic binder resin is a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight, based on the total amount of the alkali-soluble resin.

The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and 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; These can be mentioned, and these can be used alone or in a mixture of two or more.

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

The weight average molecular weight of the acrylic binder resin may be 8,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, it has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

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

For example, the polymer represented by Formula 1 may be included in the same amount as the acrylic binder resin.

The binder resin may be included in an amount of 1% to 20% by weight, for example, 5% to 15% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above content range, developability is excellent when manufacturing a color filter, and crosslinking properties are improved to obtain excellent surface smoothness.

(B) Colorant

The colorant used in the photosensitive resin composition according to one embodiment includes a first dye containing the compound represented by Formula 2 and a second dye containing the compound represented by Formula 3.

In general, squarylium-based compounds have excellent green spectral characteristics and a high molar extinction coefficient and can be used as green dyes. However, due to its inferior durability compared to pigments, a decrease in luminance may occur during the baking process after manufacturing color resist. The first dye according to one embodiment includes a squarylium-based compound represented by Formula 2, and the acrylate group in the compound represented by Formula 2 forms a direct bond with chiral carbon, thereby improving durability. Accordingly, a color filter with high brightness and high contrast ratio can be implemented.

In Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 4 below.

[Formula 4]

In Formula 5 above,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is represented by the following formula 4-1 or 4-2,

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* means chiral carbon,

**1 refers to the part connected to ** in Chemical Formula 4,

**2 refers to the portion connected to the oxygen atom constituting the ether group of Formula 4 above.

For example, in Formula 2, at least one of R ¹ and R ² may be represented by Formula 4 below, and at least one of R ³ and R ⁴ may be represented by Formula 4 below.

Specifically, “R ¹ or R ² ” and “R ³ or R ⁴ ” may each independently be represented by Formula 5 or Formula 6 below.

[Formula 5]

[Formula 6]

In Formula 5 and Formula 6 above,

L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

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

R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* means chiral carbon.

R ¹ and R ³ are each independently a C6 to C20 aryl group substituted with a C1 to C10 alkyl group, and R ² and R ⁴ may each independently be represented by Formula 5 or Formula 6.

For example, R ¹ and R ³ may each independently be a C6 to C20 aryl group substituted with 1 to 3 C1 to C10 alkyl groups.

For example, R ¹ and R ³ may each independently be represented by Formula 7-1 to Formula 7-3 below.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Formula 7-1 to Formula 7-3,

R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.

When the compound represented by Formula 2 is used in a photosensitive resin composition (for example, as a dye), its solubility in a solvent described later may be 5 or more, for example, 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 (e.g., dye) is within the above range, compatibility and coloring power with other components in the photosensitive resin composition, that is, the binder resin, photopolymerizable compound, and photopolymerization initiator, can be secured, and precipitation of the dye is prevented. It can be.

The compound represented by Formula 2 may have excellent heat resistance. That is, when measured with a thermogravimetric analyzer (TGA), the thermal decomposition temperature may be 200°C or higher, for example, 200°C to 300°C.

As shown in the diagram below, the compound represented by Formula 2 has three resonance structures, but in this specification, for convenience, the compound represented by Formula 1 is shown only with one resonance structure. That is, the compound represented by Formula 1 may be represented by any one of the three resonance structures.

[scheme]

The compound represented by Formula 2 may be represented by any one selected from the group consisting of compounds represented by Formulas 2-1 to 2-7 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

For example, the first dye is a core-shell dye having a structure consisting of a core and a shell surrounding the core, and the core may include the compound represented by Formula 2. Specifically, the shell may be a macrocyclic compound, and the shell may form a coating layer while surrounding the compound represented by Formula 2.

In one embodiment, the shell corresponding to the macrocyclic compound surrounds the compound represented by Formula 2, that is, by having a structure in which the compound represented by Formula 2 exists inside the macrocycle, The durability of core-shell dye can be improved, and thus a color filter with high brightness and high contrast ratio can be implemented.

The length of the compound represented by 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 Formula 2 has a length within the above range, a core-shell dye having a structure of a core and a shell surrounding it can be easily formed. In other words, as the compound represented by Formula 2 has a length within the above range, a shell of the macrocyclic compound can be obtained in a structure that surrounds the compound represented by Formula 2. When other compounds that do not fall within the above range are used, it is difficult to expect improvement in durability as it is difficult to form a structure where the shell surrounds the core compound.

The compound represented by Formula 2 included in or constituting the core 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 brightness and high contrast ratio can be obtained by using a core-shell dye using the compound represented by Formula 1 having the above spectral characteristics as a core, for example, a green dye.

The shell surrounding the core containing the compound represented by Formula 2 may be represented by Formula 8 or Formula 9 below.

[Formula 8]

[Formula 9]

In Formula 8 and Formula 9,

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

In Formula 8 or Formula 9, L ^a to L ^d 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 core containing the compound represented by Formula 2 above.

For example, the core-shell dye according to one embodiment is a non-covalent bond, that is, a hydrogen bond, between the oxygen atom of the compound represented by Formula 2 and the nitrogen atom of the shell represented by Formula 8 or Formula 9. may include.

The shell may be represented by, for example, Formula 8-1 or Formula 9-1 below.

[Formula 8-1]

[Formula 9-1]

The cage width of the shell may be 6.5Å to 7.5Å, and the volume of the shell may be 10Å to 16Å. As used herein, the cage width refers to the distance inside the shell, for example, the distance between two different phenylene groups with methylene groups connected to both sides in the shell represented by Formula 8-1 or Formula 9-1. (See Figure 1). When the shell has a cage width within the above range, a core-shell dye with a structure surrounding a core containing the compound represented by Formula 2 can be obtained, and thus the core-shell dye is added to the photosensitive resin composition. If this is done, a color filter with excellent durability and high brightness can be implemented.

The core-shell dye may include a core containing the compound represented by Formula 2 and the shell at a molar ratio of 1:1. When the core and shell are present in the above molar ratio, a coating layer (shell) surrounding the core containing the compound represented by Formula 2 can be well formed.

For example, the core-shell dye may be represented by any one selected from the group consisting of compounds represented by Formulas 10-1 to 10-14 below, but is not necessarily limited thereto.

[Formula 10-1]

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

[Formula 10-6]

[Formula 10-7]

[Formula 10-8]

[Formula 10-9]

[Formula 10-10]

[Formula 10-11]

[Formula 10-12]

[Formula 10-13]

[Formula 10-14]

Meanwhile, in order to improve the durability of the dye-type photosensitive resin composition, the development of a photosensitive resin composition for color filters using phthalocyanine-based green dye has been actively underway in recent years, but there have been limitations in the development of the dye-type photosensitive resin composition. When the phthalocyanine-based green dye is applied alone, a transmittance of 1% to 1.5% compared to the pigment-type photosensitive resin composition is obtained, but it does not reach a transmittance higher than that. (On the other hand, when the conventional squaryl-based green dye is applied alone, a transmittance of 3% to 4% or more is achieved compared to the pigment-type photosensitive resin composition, but the luminance is lowered in the color filter process due to lack of heat resistance and chemical resistance. There was a problem.)

However, the photosensitive resin composition according to one embodiment uses a colorant mixed with a phthalocyanine-based dye and a squaryl-based dye, thereby maintaining high transmission, high brightness, and high contrast ratio characteristics compared to a pigment-type photosensitive resin composition, and at the same time improving heat resistance and chemical resistance. It can be improved. According to one embodiment, the squaryl-based dye has a core-shell structure, the core is represented by the formula 2, and the phthalocyanine-based dye is represented by the formula 3, and the green dye consisting of the core-shell structure And when the mixed colorant of the green dye represented by Formula 3 is used together with the polymer represented by Formula 1, not only can it have high luminance and contrast ratio while maintaining excellent color characteristics, but also improve durability and residue properties at the same time. You can do it.

In the green dye represented by Formula 3, at least one of R ¹³ to R ²⁸ may be represented by Formula 11 below.

[Formula 11]

In Formula 11 above,

R ²⁹ and R ³⁰ are each independently a halogen atom,

n1 and n2 are each independently integers from 0 to 5, provided that 1 ≤ n1+n2 ≤ 5.

The green dye represented by Formula 3 has excellent green spectral characteristics and a high molar extinction coefficient. Furthermore, the green dye represented by Formula 3 contains a substituent represented by Formula 11, and thus can exhibit excellent solubility in organic solvents and excellent brightness and contrast ratio when applied to a color filter.

Formula 11 may be represented by any one selected from the group consisting of Formulas 12-1 to 12-4 below.

[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Formula 12-4]

In Formulas 12-1 to 12-4,

R ²⁹ and R ³⁰ are each independently a halogen atom.

The substituents represented by Formulas 12-1 to 12-4 are all aryloxy groups in which one or more halogen atoms are substituted, especially when the halogen atoms are substituted in the ortho and/or para positions, Brightness and contrast ratio can be further improved. In addition, in the case where the halogen atom is substituted at both the ortho and para positions (two halogen atoms are substituted), the halogen atom is substituted only at the ortho or para position (one halogen atom is substituted). There is an effect of improving luminance and contrast ratio compared to the case of halogen atom substitution. However, when the halogen atom is substituted at the meta position (even if another halogen atom is substituted at the ortho and/or para position), the effect of improving luminance and contrast ratio is minimal.

That is, in the substituent represented by Formula 11, for example, the substituent represented by Formula 12-1 to Formula 12-4, i) when at least one halogen atom is substituted in the meta position, ii) the halogen atom is ortho ( When only one of the ortho) and para positions is substituted, iii) When the halogen atom is substituted at both the ortho and para positions, in the order (i → ii → iii) Brightness and contrast ratio can be further improved.

At least one of R ¹³ to R ²⁸ may be represented by Formula 11, and at least one of R ¹³ to R ²⁸ may be represented by Formula 13 below.

[Formula 13]

For example, the substituent represented by Formula 13 may be represented by Formula 13-1 below.

[Formula 13-1]

At least one of R ¹³ to R ¹⁶ is represented by Formula 11, at least one of R ¹⁷ to R ²⁰ is represented by Formula 13, and at least one of R ²¹ to R ²⁴ is represented by Formula 13, , at least one of R ²⁵ to R ²⁸ may be represented by Formula 13.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 13, R ²² or R ²³ is represented by Formula 13, and R ²⁶ or R ²⁷ Can be represented by Formula 13 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 13, R ²² or R ²³ is represented by Formula 13, and R ²⁶ or R ²⁷ is represented by Formula 13, and all others not represented by Formula 11 and Formula 13 may be halogen atoms.

At least one of R ¹³ to R ¹⁶ is represented by Formula 11, at least one of R ¹⁷ to R ²⁰ is represented by Formula 11, and at least one of R ²¹ to R ²⁴ is represented by Formula 13, , at least one of R ²⁵ to R ²⁸ may be represented by Formula 13.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 13, and R ²⁶ or R ²⁷ Can be represented by Formula 13 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 13, and R ²⁶ or R ²⁷ is represented by Formula 13, and all others not represented by Formula 11 and Formula 13 may be halogen atoms.

At least one of R ¹³ to R ¹⁶ is represented by Formula 11, at least one of R ¹⁷ to R ²⁰ is represented by Formula 13, and at least one of R ²¹ to R ²⁴ is represented by Formula 11, , at least one of R ²⁵ to R ²⁸ may be represented by Formula 13.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 13, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ Can be represented by Formula 13 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 13, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ is represented by Formula 13, and all others not represented by Formula 11 and Formula 13 may be halogen atoms.

At least one of R ¹³ to R ¹⁶ is represented by Formula 11, at least one of R ¹⁷ to R ²⁰ is represented by Formula 11, and at least one of R ²¹ to R ²⁴ is represented by Formula 11, , at least one of R ²⁵ to R ²⁸ may be represented by Formula 13.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ Can be represented by Formula 13 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ is represented by Formula 13, and all others not represented by Formula 11 and Formula 13 may be halogen atoms.

At least one of R ¹³ to R ¹⁶ is represented by Formula 11, at least one of R ¹⁷ to R ²⁰ is represented by Formula 11, and at least one of R ²¹ to R ²⁴ is represented by Formula 11, , at least one of R ²⁵ to R ²⁸ may be represented by Formula 11 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ Can be represented by Formula 11 above.

For example, R ¹⁴ or R ¹⁵ is represented by Formula 11, R ¹⁸ or R ¹⁹ is represented by Formula 11, R ²² or R ²³ is represented by Formula 11, and R ²⁶ or R ²⁷ is represented by Formula 11, and all remainders not represented by Formula 11 may be halogen atoms.

For example, the green dye of Formula 3 may be represented by any one of Formulas 14 to 23 below, but is not necessarily limited thereto.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

The green dye represented by Formula 3 includes, for example, a substituent represented by any one of Formulas 12-1 to 12-4, so that more vivid colors can be expressed even in small amounts, and when used as a colorant, it reduces luminance or It is possible to manufacture display elements with excellent color characteristics such as contrast ratio. For example, the green dye may have maximum transmittance in the wavelength range of 445 nm to 560 nm.

The colorant may further include at least one of other green dyes, green pigments, yellow dyes, and yellow pigments in addition to the green dye represented by Formula 2 and the green dye represented by Formula 3, and may be represented by Formulas 2 and 3. Other green dyes, green pigments, yellow dyes and yellow pigments not shown may be known dyes and pigments.

The first dye containing the green dye represented by Formula 2 may be included in a smaller amount than the second dye containing the green dye represented by Formula 3. For example, the first dye and the second dye may be included in a weight ratio of 1:1.1 to 1:2.

For example, when the colorant further includes a yellow pigment, the yellow pigment may be included in an amount greater than the content of each of the first dye and the second dye.

The colorant may be included in an amount of 30% to 70% by weight, for example, 40% to 60% by weight, 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 achieved at the desired color coordinate.

(C) Photopolymerizable compound

The photopolymerizable compound may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern with excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization upon exposure to light in the pattern formation process.

Specific examples of the photopolymerizable compound 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, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri( Meta)acrylate, tris(meth)acryloyloxyethyl phosphate, novolak epoxy (meth)acrylate, etc. are mentioned.

Examples of commercially available products of the photopolymerizable compound are as follows. Examples of the monofunctional ester of (meth)acrylic acid include Aronix M-101 ^® , Aronix M-111 ^® , and Aronix M-114 ^® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD TC-110S ^® , KAYARAD TC-120S ^® , etc.; Examples include V-158 ^® and V-2311 ^® manufactured by Osaka Yuki Chemical Co., Ltd. Examples of the above-mentioned difunctional ester of (meth)acrylic acid include Aronix M-210 ^® , Aronix M-240 ^® , and Aronix M-6200 ^® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , KAYARAD HX-220 ^® , KAYARAD R-604 ^® , etc.; Examples include V-260 ^® , V-312 ^® , and V-335 HP ^® manufactured by Osaka Yuki Chemical Engineering Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronix M-309 ^® , Aronix M-400 ^® , Aronix M-405 ^® , and Aronix M-450 ^® manufactured by Toagosei Chemicals Co., Ltd. , Aronix M-7100 ^® , Aronix M-8030 ^® , Aronix M-8060 ^{® ,} etc.; Nihon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , KAYARAD DPCA-20 ^® , KAYARAD DPCA-30 ^® , KAYARAD DPCA-60 ^® , KAYARAD DPCA-120 ^® , etc.; Examples include V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , and V-400 ^® from Osaka Yuki Kayaku Kogyo Co., Ltd. The above products can be used alone or in combination of two or more types.

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

The photopolymerizable compound may be included in an amount of 1% to 10% by weight, for example, 3% to 8% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above content range, pattern characteristics and developability are excellent when manufacturing a color filter.

(D) Photopolymerization initiator

The photopolymerization initiator may be 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.

Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

Examples of the benzophenone-based compounds 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, etc.

Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.

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

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-Biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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 compounds include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9- and ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone.

In addition to the above compounds, the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and fluorene-based compounds.

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

(E) Solvent

The solvent is not particularly limited, but specific examples include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as 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; Alternatively, there are compounds of keto acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. can be used alone or in a mixture of two or more types.

Considering miscibility and reactivity among the above solvents, glycol ethers such as ethylene glycol monoethyl ether are preferred; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone may be used.

The solvent may be included as the remainder of the total amount of the photosensitive resin composition, and may specifically be included in 15% by weight to 50% by weight. When the solvent is contained within the above range, the photosensitive resin composition has excellent applicability and can maintain excellent flatness in a film with a thickness of 3 μm or more.

(F) Other additives

The photosensitive resin composition contains malonic acid to prevent stains or spots upon application, to improve leveling performance, and to prevent the creation of residues due to non-development; 3-amino-1,2-propanediol; Silane-based coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Fluorine-based surfactant; It may further include additives such as radical polymerization initiators.

Additionally, the photosensitive resin composition may further include additives such as an epoxy compound to improve adhesion to the substrate.

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

The content of the additive can be easily adjusted depending on the desired physical properties.

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

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

On a glass substrate on which nothing has been applied, or on a glass substrate on which a protective film, _SiN , respectively, are applied to a thickness of 1㎛ to 3㎛. After application, light is irradiated to form the pattern required for the color filter. After irradiating light, the applied layer is treated with an alkaline developer, so that the unirradiated portion of the applied layer is dissolved and the pattern required for the color filter is formed. By repeating this process according to the number of required R, G, and B colors, a color filter with a desired pattern can be obtained.

In addition, in the above process, crack resistance, solvent resistance, etc. can be further improved by heating the image pattern obtained through development again or hardening it by irradiation with actinic rays, etc.

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

(Preparation of first dye)

(Synthesis Example 1: Synthesis of Intermediate A-1)

[Scheme 1]

Aniline (10 mol), 1-Bromo-2,4-dimethyl-benzene (10 mol), Pd ₂ (dba) ₃ (0.1 mol), and Xphos (0.1 mol) were added to toluene and heated to 100°C for 24 hours. It was stirred. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate A-1.

(Synthesis Example 2: Synthesis of Intermediate A-2)

Intermediate A-2 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that 4-Bromotoluene was used instead of 1-Bromo-2,4-dimethyl-benzene.

(Synthesis Example 3: Synthesis of Intermediate A-3)

Intermediate A-3 was obtained by synthesizing in the same manner as Synthesis Example 1, except that Mesityl Bromide was used instead of 1-Bromo-2,4-dimethyl-benzene.

(Synthesis Example 4: Synthesis of Intermediate B-1)

[Scheme 2]

Intermediate A-1 (10 mol), 1,2-Butylene Oxide (10 mol), and sodium hydride (12 mol) were added to N,N-dimethylformamide, heated to 90°C, and stirred for 24 hours. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate B-1.

(Synthesis Example 5: Synthesis of Intermediate B-2)

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

(Synthesis Example 6: Synthesis of Intermediate B-3)

Intermediate B-3 was obtained by synthesis in the same manner as Synthesis Example 4, except that Intermediate A-3 was used instead of Intermediate A-1.

(Synthesis Example 7: Synthesis of Intermediate B-4)

Intermediate B-4 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that 2,3-Butylene Oxide was used instead of 1,2-Butylene Oxide.

(Synthesis Example 8: Synthesis of Intermediate B-5)

Intermediate B-5 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that 1,2-Epoxypentane was used instead of 1,2-Butylene Oxide.

(Synthesis Example 9: Synthesis of Intermediate B-6)

Intermediate B-6 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that 1,2-Epoxyhexane was used instead of 1,2-Butylene Oxide.

(Synthesis Example 10: Synthesis of Intermediate B-7)

Intermediate B-7 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that 1,2-Epoxycyclohexane was used instead of 1,2-Butylene Oxide.

(Synthesis Example 11: Synthesis of Intermediate C-1)

[Scheme 3]

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

(Synthesis Example 12: Synthesis of Intermediate C-2)

Intermediate C-2 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-2 was used instead of Intermediate B-1.

(Synthesis Example 13: Synthesis of Intermediate C-3)

Intermediate C-3 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-3 was used instead of Intermediate B-1.

(Synthesis Example 14: Synthesis of Intermediate C-4)

Intermediate C-4 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-4 was used instead of Intermediate B-1.

(Synthesis Example 15: Synthesis of Intermediate C-5)

Intermediate C-5 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-5 was used instead of Intermediate B-1.

(Synthesis Example 16: Synthesis of Intermediate C-6)

Intermediate C-6 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-6 was used instead of Intermediate B-1.

(Synthesis Example 16: Synthesis of Intermediate C-7)

Intermediate C-7 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate B-7 was used instead of Intermediate B-1.

(Synthesis Example 17: Synthesis of the compound represented by Formula 2-1)

[Scheme 4]

Intermediate C-1 (60 mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL) and refluxed to produce The water is removed using a Dean-stark distillation device. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain the compound represented by Chemical Formula 2-1 (Maldi-tof MS: 752.38 m/z).

(Synthesis Example 18: Synthesis of the compound represented by Formula 2-2)

A compound represented by the following formula 2-2 was obtained by synthesis in the same manner as in Synthesis Example 17, except that Intermediate C-2 was used instead of Intermediate C-1.

[Formula 2-2]

Maldi-tof MS: 724.35 m/z

(Synthesis Example 19: Synthesis of the compound represented by Formula 2-3)

A compound represented by the following formula 2-3 was obtained by synthesis in the same manner as in Synthesis Example 17, except that Intermediate C-3 was used instead of Intermediate C-1.

[Formula 2-3]

Maldi-tof MS: 780.41 m/z

(Synthesis Example 20: Synthesis of the compound represented by Formula 2-4)

A compound represented by the following formula 2-4 was obtained by synthesis in the same manner as in Synthesis Example 17, except that intermediate C-4 was used instead of intermediate C-1.

[Formula 2-4]

Maldi-tof MS: 752.38 m/z

(Synthesis Example 21: Synthesis of the compound represented by Formula 2-5)

A compound represented by the following formula 2-5 was obtained by synthesis in the same manner as in Synthesis Example 17, except that Intermediate C-5 was used instead of Intermediate C-1.

[Formula 2-5]

Maldi-tof MS: 780.41 m/z

(Synthesis Example 22: Synthesis of the compound represented by Formula 2-6)

A compound represented by the following formula 2-6 was obtained by synthesis in the same manner as in Synthesis Example 17, except that Intermediate C-6 was used instead of Intermediate C-1.

[Formula 2-6]

Maldi-tof MS: 808.45m/z

(Synthesis Example 23: Synthesis of the compound represented by Formula 2-7)

A compound represented by the following formula 2-7 was obtained by synthesis in the same manner as in Synthesis Example 17, except that Intermediate C-7 was used instead of Intermediate C-1.

[Formula 2-7]

Maldi-tof MS: 804.41m/z

(Synthesis Example 24: Synthesis of Intermediate D-1)

[Scheme 5]

2-Bromoethanol (10 mmol), 3,4-Dihydro-2H-pyran (10 mmol) and p-Toluenesulfonic acid monohydrate (0.05 mmol) were added to dichloromethane and stirred for 1 hour. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. Intermediate A-1 was added to N,N-dimethylformamide, sodium hydride (12 mol) was added dropwise, and stirred for 2 hours. The organic matter extracted above was added dropwise and stirred for 12 hours. Add ethyl acetate to this solution, wash it twice with water, extract the organic layer, remove the solvent, and add it dropwise to methanol along with p-Toluenesulfonic acid monohydrate (0.05 mmol). After stirring for 2 hours, ethyl acetate was added, washed twice with water, the organic layer was extracted, the solvent was removed, and the mixture was separated by column chromatography to obtain intermediate D-1.

(Synthesis Example 25: Synthesis of Intermediate D-2)

Intermediate D-2 was obtained by synthesizing in the same manner as in Synthesis Example 24, except that 5-Bromo-1-pentanol was used instead of 2-Bromoethanol.

(Synthesis Example 26: Synthesis of Intermediate E-1)

Intermediate E-1 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate D-1 was used instead of Intermediate B-1.

(Synthesis Example 27: Synthesis of Intermediate E-2)

Intermediate E-2 was obtained by synthesis in the same manner as Synthesis Example 11, except that Intermediate D-2 was used instead of Intermediate B-1.

(Reference Synthesis Example 1: Synthesis of the compound represented by Formula F-1)

A compound represented by the following formula F-1 was obtained by synthesis in the same manner as Synthesis Example 17, except that Intermediate E-1 was used instead of Intermediate C-1.

[Formula F-1]

Maldi-tof MS: 696.32 m/z

(Reference Synthesis Example 2: Synthesis of the compound represented by Formula F-2)

A compound represented by the following formula F-2 was obtained by synthesis in the same manner as Synthesis Example 17, except that Intermediate E-2 was used instead of Intermediate C-1.

[Formula F-2]

Maldi-tof MS: 780.41 m/z

(Synthesis Example 28: Synthesis of core-shell dye represented by Chemical Formula 10-1)

[Scheme 6]

After dissolving the compound represented by Formula 2-1 (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform and added dropwise simultaneously for 5 hours at room temperature. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 10-1 (Maldi-tof MS: 1284.59 m/z).

(Synthesis Example 29: Synthesis of core-shell dye represented by Chemical Formula 10-2)

[Scheme 7]

Dissolve the compound represented by Formula 2-1 (5 mmol) in 600 mL chloroform solvent, and then add triethylamine (50 mmol). 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL 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 the compound represented by Chemical Formula 10-2 (Maldi-tof MS: 1286.58 m/z).

(Synthesis Example 30: Synthesis of core-shell dye represented by Chemical Formula 10-3)

A compound represented by the following Formula 10-3 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-2 was used instead of the compound represented by Formula 2-1.

[Formula 10-3]

Maldi-tof MS: 1256.56 m/z

(Synthesis Example 31: Synthesis of core-shell dye represented by Chemical Formula 10-4)

A compound represented by the following Formula 10-4 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-2 was used instead of the compound represented by Formula 2-1.

[Formula 10-4]

Maldi-tof MS: 1258.55 m/z

(Synthesis Example 32: Synthesis of core-shell dye represented by Chemical Formula 10-5)

A compound represented by the following Formula 10-5 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-3 was used instead of the compound represented by Formula 2-1.

[Formula 10-5]

Maldi-tof MS: 1312.62m/z

(Synthesis Example 33: Synthesis of core-shell dye represented by Chemical Formula 10-6)

A compound represented by Formula 10-6 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-3 was used instead of the compound represented by Formula 2-1.

[Formula 10-6]

Maldi-tof MS: 1314.62m/z

(Synthesis Example 34: Synthesis of core-shell dye represented by Chemical Formula 10-7)

A compound represented by the following Formula 10-7 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-4 was used instead of the compound represented by Formula 2-1.

[Formula 10-7]

Maldi-tof MS: 1284.59m/z

(Synthesis Example 35: Synthesis of core-shell dye represented by Chemical Formula 10-8)

A compound represented by the following Formula 10-8 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-4 was used instead of the compound represented by Formula 2-1.

[Formula 10-8]

Maldi-tof MS: 1286.58m/z

(Synthesis Example 36: Synthesis of core-shell dye represented by Chemical Formula 10-9)

A compound represented by the following Formula 10-9 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-5 was used instead of the compound represented by Formula 2-1.

[Formula 10-9]

Maldi-tof MS: 1232.62m/z

(Synthesis Example 37: Synthesis of core-shell dye represented by Chemical Formula 10-10)

A compound represented by the following Formula 10-10 was obtained by synthesizing in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-5 was used instead of the compound represented by Formula 2-1.

[Formula 10-10]

Maldi-tof MS: 1314.62m/z

(Synthesis Example 38: Synthesis of core-shell dye represented by Chemical Formula 10-11)

A compound represented by the following Formula 10-11 was obtained by synthesizing in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-6 was used instead of the compound represented by Formula 2-1.

[Formula 10-11]

Maldi-tof MS: 1340.66 m/z

(Synthesis Example 39: Synthesis of core-shell dye represented by Chemical Formula 10-12)

A compound represented by the following Formula 10-12 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-6 was used instead of the compound represented by Formula 2-1.

[Formula 10-12]

Maldi-tof MS: 1342.65m/z

(Synthesis Example 40: Synthesis of core-shell dye represented by Chemical Formula 10-13)

A compound represented by the following Formula 10-13 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula 2-7 was used instead of the compound represented by Formula 2-1.

[Formula 10-13]

Maldi-tof MS: 1336.62m/z

(Synthesis Example 41: Synthesis of core-shell dye represented by Chemical Formula 10-14)

A compound represented by Formula 10-14 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula 2-7 was used instead of the compound represented by Formula 2-1.

[Formula 10-14]

Maldi-tof MS: 1338.62 m/z

(Reference Synthesis Example 3: Synthesis of core-shell dye represented by formula G-1)

A compound represented by Formula G-1 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula F-1 was used instead of the compound represented by Formula 2-1.

[Formula G-1]

Maldi-tof MS: 1228.53 m/z

(Reference Synthesis Example 4: Synthesis of core-shell dye represented by formula G-2)

A compound represented by Formula G-2 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula F-1 was used instead of the compound represented by Formula 2-1.

[Formula G-2]

Maldi-tof MS: 1230.52 m/z

(Reference Synthesis Example 5: Synthesis of core-shell dye represented by formula G-3)

A compound represented by Formula G-3 was obtained by synthesis in the same manner as Synthesis Example 28, except that the compound represented by Formula F-2 was used instead of the compound represented by Formula 2-1.

[Formula G-3]

Maldi-tof MS: 1312.62 m/z

(Reference Synthesis Example 6: Synthesis of core-shell dye represented by formula G-4)

A compound represented by Formula G-4 was obtained by synthesis in the same manner as Synthesis Example 29, except that the compound represented by Formula F-2 was used instead of the compound represented by Formula 2-1.

[Formula G-4]

Maldi-tof MS: 1314.62 m/z

(Preparation of second dye)

Synthesis Example 42: Synthesis of 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile

Add 3,4,5,6-tetrachlorophthalonitrile (5g), 2-Phenylphenol (3.21g), K ₂ CO ₃ (3.9g), and acetone (25ml) to a 100ml flask and stir while heating to 70°C. After completion of the reaction, filter, wash with acetone, and distill the resulting liquid to obtain a solid. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile.

Synthesis Example 43: Synthesis of 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile

Add 3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dichlorophenol (3.06g), K ₂ CO ₃ (3.9g), and acetone (25ml) to a 100ml flask and stir while heating to 70°C. After completion of the reaction, filter, wash with acetone, and distill the resulting liquid to obtain a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile.

Synthesis Example 44: Synthesis of 3,4,6-Trichloro-5-(2,6-dibromo-phenoxy)-phthalonitrile

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dibromophenol (4.75g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide ( 25ml) and stir while heating to 70℃. After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2,6-dibromo-phenoxy)-phthalonitrile.

Synthesis Example 45: Synthesis of 3,4,6-Trichloro-5-(2,6-difluoro-phenoxy)-phthalonitrile

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-difluorophenol (2.45g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide ( 25ml) and stir while heating to 70°C. After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2,6-difluoro-phenoxy)-phthalonitrile.

Synthesis Example 46: Synthesis of 3,4,6-Trichloro-5-(2-chloro-phenoxy)-phthalonitrile

Add 3,4,5,6-tetrachlorophthalonitrile (5g), 2-chlorophenol (2.41g), K ₂ CO ₃ (3.9g), and acetone (25ml) to a 100ml flask and stir while heating to 70°C. After completion of the reaction, filter, wash with acetone, and distill the resulting liquid to obtain a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2-chloro-phenoxy)-phthalonitrile.

Synthesis Example 47: Synthesis of 3,4,6-Trichloro-5-(2-bromo-phenoxy)-phthalonitrile

3,4,5,6-tetrachlorophthalonitrile (5g), 2-bromophenol (3.25g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (25ml) in a 100ml flask. Add and stir while heating to 70°C. After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2-bromo-phenoxy)-phthalonitrile.

Synthesis Example 48: Synthesis of 3,4,6-Trichloro-5-(2-fluoro-phenoxy)-phthalonitrile

3,4,5,6-tetrachlorophthalonitrile (5g), 2-fluorophenol (2.10g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (25ml) in a 100ml flask. Add and stir while heating to 70°C. After completion of the reaction, extraction is performed with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2-fluoro-phenoxy)-phthalonitrile.

Synthesis Example 49: Synthesis of 3,4,6-Trichloro-5-(2,5-dichloro-phenoxy)-phthalonitrile

Add 3,4,5,6-tetrachlorophthalonitrile (5g), 2,5-dichlorophenol (3.06g), K ₂ CO ₃ (3.9g), and acetone (25ml) to a 100ml flask and stir while heating to 70°C. After completion of the reaction, filter, wash with acetone, and distill the resulting liquid to obtain a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered, and vacuum dried to obtain 3,4,6-Trichloro-5-(2,5-dichloro-phenoxy)-phthalonitrile.

Synthesis Example 50: Synthesis of the compound represented by Formula 14

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.5 g) of Synthesis Example 42 and 3,4,6-Trichloro-5-(2,6-) of Synthesis Example 43 Add dichloro-phenoxy)-phthalonitrile (0.49g), 1,8-Diazabicycloundec-7-ene (1.52g), and 1-pentanol (14g) and heat to 90℃ to dissolve the solid, then add zinc acetate (0.23g). Add and stir while heating to 140°C. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. Add the solid edichloromethane obtained after purification to dissolve the solid, and then add methanol to crystallize it. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (14).

[Formula 14]

Maldi-tof MS:1656.79 m/z

Synthesis Example 51: Synthesis of the compound represented by Formula 15

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.6 g) of Synthesis Example 42 and 3,4,6-Trichloro-5-(2,6-) of Synthesis Example 43 Add dichloro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g), and 1-pentanol (14g) and heat to 90℃ to dissolve the solid, then add zinc acetate (0.34g). Add and stir while heating to 140°C. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. Add the solid edichloromethane obtained after purification to dissolve the solid, and then add methanol to crystallize it. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (15).

[Formula 15]

Maldi-tof MS:1649.57 m/z

Synthesis Example 52: Synthesis of the compound represented by Formula 16

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1 g) of Synthesis Example 42 and 3,4,6-Trichloro-5-(2,6-dichloro) of Synthesis Example 43 -phenoxy)-phthalonitrile (2.9g), 1,8-Diazabicycloundec-7-ene (3g), and 1-pentanol (27g) were added and heated to 90°C to dissolve the solid. Then, zinc acetate (0.45g) was added and dissolved at 140°C. Stir while heating to ℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. Add the solid edichloromethane obtained after purification to dissolve the solid, and then add methanol to crystallize it. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (16).

[Formula 16]

Maldi-tof MS:1642.36 m/z

Synthesis Example 53: Synthesis of the compound represented by Formula 17

3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (0.87g) and 1-pentane of Synthesis Example 43 in a 100mL flask. Add all (7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (17).

[Formula 17]

Maldi-tof MS:1635.14 m/z

Synthesis Example 54: Synthesis of the compound represented by Formula 18

3,4,6-Trichloro-5-(2,6-dibromo-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (0.87g) and 1-pentane of Synthesis Example 44 in a 100mL flask. Add all (7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (18).

[Formula 18]

Maldi-tof MS:1990.78m/z

Synthesis Example 55: Synthesis of the compound represented by Formula 19

3,4,6-Trichloro-5-(2,6-difluoro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (0.87g) and 1-pentane of Synthesis Example 45 in a 100mL flask. Add all (7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (19).

[Formula 19]

Maldi-tof MS:1503.53 m/z

Synthesis Example 56: Synthesis of the compound represented by Formula 20

In a 100 mL flask, 3,4,6-Trichloro-5-(2-chloro-phenoxy)-phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol ( Add 7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (20).

[Formula 20]

Maldi-tof MS:1497.38 m/z

Synthesis Example 57: Synthesis of the compound represented by Formula 21

In a 100 mL flask, 3,4,6-Trichloro-5-(2-bromo-phenoxy)-phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol ( Add 7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (21).

[Formula 21]

Maldi-tof MS:1675.19 m/z

Synthesis Example 58: Synthesis of the compound represented by Formula 22

In a 100 mL flask, 3,4,6-Trichloro-5-(2-fluoro-phenoxy)-phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol ( Add 7g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.17g) and stir while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (22).

[Formula 22]

Maldi-tof MS:1431.57 m/z

Synthesis Example 59: Synthesis of the compound represented by Formula 23

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.6 g) of Synthesis Example 42 and 3,4,6-Trichloro-5-(2,5-) of Synthesis Example 49 Add dichloro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g), and 1-pentanol (14g) and heat to 90℃ to dissolve the solid, then add zinc acetate (0.34g). Add and stir while heating to 140°C. After completion of the reaction, precipitation is confirmed with methanol, filtered, and vacuum dried. The dried solid is purified by column chromatography. After purification, an appropriate amount of dichloromethane is added to the solid to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (23).

[Formula 23]

Maldi-tof MS:1649.57 m/z

(Photosensitive resin composition production)

The specifications of the ingredients used to prepare the photosensitive resin composition are as follows.

(A) Binder resin

(A-1) Methacrylic acid/benzyl methacrylate copolymer with a weight average molecular weight of 12,000 g/mol (mixed weight ratio 15wt%/85wt%)

(A-2) A polymer represented by the following formula 1A and having a weight average molecular weight of 5,000 g/mol

[Formula 1A]

(B) Colorant

first dye

(B-1) Core-shell dye prepared in Synthesis Example 28 (represented by Chemical Formula 10-1)

(B-2) Core-shell dye prepared in Synthesis Example 41 (represented by Chemical Formula 10-14)

(B-3) Core-shell dye prepared in Reference Synthesis Example 3 (represented by Chemical Formula G-1)

(B-4) Core-shell dye prepared in Reference Synthesis Example 4 (represented by Chemical Formula G-2)

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

(B-6) Core-shell dye prepared in Reference Synthesis Example 6 (represented by formula G-4)

secondary dye

(B-7) Core-shell dye prepared in Synthesis Example 50 (represented by Formula 14)

(B-8) Core-shell dye prepared in Synthesis Example 59 (represented by Formula 23)

pigment

(B-9) C.I. Pigment Yellow 138 (SANYO)

(C) Photopolymerizable compound

Dipentaerythritol hexaacrylate (Japanese gunpowder)

(D) Photopolymerization initiator

(D-1) 1,2-octanedione (TCI)

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

(E) Solvent

Propylene glycol methyl ether acetate (SIGMA-ALDRICH)

(F) Additives

Surfactant (F-554, DIC)

Examples 1 to 10 and Comparative Examples 1 to 8

A photosensitive resin composition was prepared by mixing each component in the composition shown in Tables 1 and 2 below. Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours, then dye (or pigment dispersion) was added and stirred for 30 minutes, then binder resin and photopolymerizable monomer were added and stirred at room temperature for 2 hours. It was stirred. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: weight%) Example One 2 3 4 5 6 7 8 9 10 (A) Binder resin A-1 4.0 - - - - - - - 3.0 5.0 A-2 4.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 5.0 3.0 (B) Colorant B-1 10.0 10.0 - 10.0 - 14.25 10.0 18.5 10.0 10.0 B-2 - - 10.0 - 10.0 - - - - - B-3 - - - - - - - - - - B-4 - - - - - - - - - - B-5 - - - - - - - - - - B-6 - - - - - - - - - - B-7 18.5 18.5 - - 18.5 14.25 30.0 10.0 18.5 18.5 B-8 - - 18.5 18.5 - - - - - - B-9 30.0 30.0 30.0 30.0 30.0 30.0 18.5 30.0 30.0 30.0 (C) Photopolymerizable compound 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (D) Photopolymerization initiator D-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent 27.3 27.3 27.3 27.3 27.3 27.3 27.3 27.3 27.3 27.3 (F) Additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total 100 100 100 100 100 100 100 100 100 100

(Unit: weight%) Comparative example One 2 3 4 5 6 7 8 (A) Binder resin A-1 8.0 4.0 4.0 4.0 - - - - A-2 - 4.0 4.0 4.0 8.0 8.0 8.0 8.0 (B) Colorant B-1 10.0 28.5 - - - - - - B-2 - - - - - - - - B-3 - - - - 10.0 - - - B-4 - - - - - 10.0 - - B-5 - - - - - - 10.0 - B-6 - - - - - - - 10.0 B-7 18.5 - 28.5 - 18.5 18.5 18.5 18.5 B-8 - - - - - - - - B-9 30.0 30.0 30.0 58.5 30.0 30.0 30.0 30.0 (C) Photopolymerizable compound 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (D) Photopolymerization initiator D-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent 27.3 27.3 27.3 27.3 27.3 27.3 27.3 27.3 (F) Additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total 100 100 100 100 100 100 100 100

(evaluation)

Evaluation 1: Durability evaluation

The photosensitive resin composition prepared in Examples 1 to 10 and Comparative Examples 1 to 8 was applied to a thickness of 1 ㎛ to 3 ㎛ on a degreased 1 mm thick glass substrate, and heated on a hot plate at 90°C for 2 hours. After drying for several minutes, a film was obtained. Subsequently, the coating film was exposed using a high-pressure mercury lamp with a dominant wavelength of 365 nm, and then first dried in an oven at 230°C for 20 minutes. The resulting substrate was soaked in NMP (N-methylpyrrolidone) solution for 10 minutes at room temperature. After immersion, the before and after transmittance spectra were obtained, the ΔGx value was measured using a spectrophotometer (MCPD3000, Otsuka Electronic), and the ΔEab* value was calculated using Equation 1 below. Afterwards, it was dried a second time under the same conditions and the ΔGx value and ΔEab* value were calculated using the same method. The measurement results are shown in Table 3 below.

[Equation 1]

ΔEab* = {(ΔL*) ² ＋(Δa*) ² ＋(Δb*) ² } x 1/2

(The smaller the ΔEab* value, the better the durability)

ΔGx ΔEab* Example 1 1st drying -0.003 2.8 Secondary drying -0.004 2.5 Example 2 1st drying -0.002 2.3 Secondary drying -0.002 2.1 Example 3 1st drying -0.003 2.3 Secondary drying -0.002 2.1 Example 4 1st drying -0.003 2.4 Secondary drying -0.002 2.1 Example 5 1st drying -0.002 2.4 Secondary drying -0.002 2.2 Example 6 1st drying -0.004 2.9 Secondary drying -0.006 2.8 Example 7 1st drying -0.005 2.9 Secondary drying -0.007 2.8 Example 8 1st drying -0.007 3.0 Secondary drying -0.007 3.0 Example 9 1st drying -0.004 2.8 Secondary drying -0.006 2.8 Example 10 1st drying -0.005 2.8 Secondary drying -0.004 2.7 Comparative Example 1 1st drying -0.004 3.5 Secondary drying -0.006 3.1 Comparative Example 2 1st drying -0.05 5.4 Secondary drying -0.06 5.1 Comparative Example 3 1st drying -0.06 5.7 Secondary drying -0.07 5.6 Comparative Example 4 1st drying -0.08 5.8 Secondary drying -0.10 5.8 Comparative Example 5 1st drying -0.03 4.6 Secondary drying -0.03 4.3 Comparative Example 6 1st drying -0.03 4.5 Secondary drying -0.02 4.4 Comparative Example 7 1st drying -0.03 4.5 Secondary drying -0.02 4.3 Comparative Example 8 1st drying -0.04 4.3 Secondary drying -0.03 4.2

Evaluation 2: Process margin evaluation

The photosensitive resin composition according to Examples 1 to 5 and Comparative Example 1 was coated on a glass substrate using a coating machine (MIKASA), and then dried at 90°C on a hot plate to obtain a coating film. The obtained coating film was irradiated with light at an exposure dose of 50 mJ/cm ² and then developed to reveal a pattern. The developer was used by diluting Hoemyung's KOH solution, and the time (seconds) (BP) for the pattern to appear was measured. At this time, BP must be at least 43Sec or less. The patterned substrate for which development was completed was baked under oven conditions (230°C) for 30 minutes to complete pattern formation.

The completed pattern was optically zoomed 500 times through an optical microscope to measure the residue inside the identified hole. The results are shown in Table 4 below and Figures 2 to 4.

O: No residue found under the microscope

△: Some residue was found under the microscope.

X: A lot of residue was found under the microscope

Process margin characteristics Example 1 △ Example 2 O Example 3 O Example 4 O Example 5 O Example 6 △ Example 7 △ Example 8 △ Example 9 △ Example 10 △ Comparative Example 1 X Comparative Example 2 X Comparative Example 3 X Comparative Example 4 X Comparative Example 5 X Comparative Example 6 X Comparative Example 7 X Comparative Example 8 X

From Table 3, Table 4, and FIGS. 2 to 4, the photosensitive resin composition according to one embodiment includes a colorant mixed with a silicone-acrylic polymer of a specific structure and two types of green dyes of a specific structure, thereby providing excellent durability and processability. It can be confirmed that it has both margin characteristics (residue characteristics).

The present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art will be able to form other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

Claims (20)

(A) a polymer-containing binder resin represented by the following formula (1);
(B) a colorant comprising a first dye containing a compound represented by the following formula (2) and a second dye containing a compound represented by the following formula (3);
(C) photopolymerizable compound;
(D) photopolymerization initiator; and
(E) Solvent
Photosensitive resin composition comprising:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
R ^a and R ^b are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ^c to R ^h are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
L' and L'' are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹ to R ⁴ 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,
At least one of R ¹ to R ⁴ includes a substituted or unsubstituted acrylate group at the terminal,
The acrylate group forms a direct bond with the chiral carbon,
R ¹³ to R ²⁸ 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 C1 to C20 alkyl group. It is a ringed C6 to C20 aryloxy group,
n is an integer from 1 to 10000.
According to paragraph 1,
The polymer represented by Formula 1 is a photosensitive resin composition having a weight average molecular weight of 1000 g/mol to 20000 g/mol.
According to paragraph 1,
The binder resin is a photosensitive resin composition further comprising an acrylic binder resin.
According to paragraph 1,
A photosensitive resin composition wherein at least one of R ¹ to R ⁴ is represented by the following formula (4):
[Formula 4]

In Formula 4 above,
R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is represented by the following formula 4-1 or 4-2,
[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,
L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,
R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,
R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
* means chiral carbon,
**1 refers to the part connected to ** in Chemical Formula 4,
**2 refers to the portion connected to the oxygen atom constituting the ether group of Formula 4 above.
According to paragraph 1,
The photosensitive resin composition wherein R ¹ or R ² and R ³ or R ⁴ are each independently represented by the following Formula 5 or Formula 6:
[Formula 5]

[Formula 6]

In Formula 5 and Formula 6 above,
L ³ is a substituted or unsubstituted C1 to C10 alkylene group,
R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,
R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
* means chiral carbon.
According to clause 5,
The photosensitive resin composition wherein R ¹ and R ³ are each independently represented by the following formulas 7-1 to 7-3:
[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Formula 7-1 to Formula 7-3,
R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.
According to paragraph 1,
The compound represented by Formula 2 is a photosensitive resin composition represented by any one of the following Formulas 2-1 to 2-7.
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

According to paragraph 1,
The first dye is a core-shell dye having a structure consisting of a core and a shell surrounding the core,
The core is a photosensitive resin composition comprising a compound represented by Formula 2.
According to clause 8,
The shell is a photosensitive resin composition represented by the following Chemical Formula 8-1 or Chemical Formula 9-1.
[Formula 8-1]

[Formula 9-1]

According to clause 8,
The core-shell dye is a photosensitive resin composition represented by any one selected from the group consisting of compounds represented by the following formulas 10-1 to 10-14.
[Formula 10-1]

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

[Formula 10-6]

[Formula 10-7]

[Formula 10-8]

[Formula 10-9]

[Formula 10-10]

[Formula 10-11]

[Formula 10-12]

[Formula 10-13]

[Formula 10-14]

According to paragraph 1,
A photosensitive resin composition wherein at least one of R ¹³ to R ²⁸ is represented by the following formula (11):
[Formula 11]

In Formula 11 above,
R ²⁹ and R ³⁰ are each independently a halogen atom,
n1 and n2 are each independently integers from 0 to 5, provided that 1 ≤ n1+n2 ≤ 5.
According to clause 11,
Formula 11 is a photosensitive resin composition represented by any one selected from the group consisting of the following Formulas 12-1 to 12-4:
[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Formula 12-4]

In Formulas 12-1 to 12-4,
R ²⁹ and R ³⁰ are each independently a halogen atom.
According to clause 11,
At least one of R ¹³ to R ²⁸ is represented by Formula 11,
At least one of R ¹³ to R ²⁸ is a photosensitive resin composition represented by the following formula (13).
[Formula 13]

According to paragraph 1,
The compound represented by Formula 3 is a photosensitive resin composition represented by any one of Formulas 14 to 23 below.
[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

According to paragraph 1,
A photosensitive resin composition wherein the first dye is contained in a smaller amount than the second dye.
According to paragraph 1,
The photosensitive water composition wherein the colorant further includes a yellow pigment.
According to paragraph 1,
The photosensitive resin composition is, with respect to the total amount of the photosensitive resin composition,
1% to 20% by weight of the binder resin;
30% to 70% by weight of the colorant;
1% to 10% by weight of the photopolymerizable compound;
0.1% to 5% by weight of the photopolymerization initiator; and
15% to 50% by weight of the solvent
A photosensitive resin composition containing a.
According to paragraph 1,
The photosensitive resin composition further contains malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent containing a vinyl group or (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 manufactured using the photosensitive resin composition of any one of claims 1 to 18.
A color filter comprising the photosensitive resin film of claim 19.