KR102624672B1 - Photosensitive resin composition, photosensitive resin using the same and color filter - Google Patents

Abstract

(A) a colorant containing a blue pigment, a dye represented by the following formula (1), and a phthalocyanine-based dye; (B) binder resin; (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a solvent, wherein the compound represented by Formula 1 is contained in an amount of 10% by weight or less based on the total amount of the photosensitive resin composition, and the phthalocyanine-based dye is contained in an amount of 25% by weight or less based on the total amount of the photosensitive resin composition. A photosensitive resin composition, a photosensitive resin film, and a color filter manufactured using the photosensitive resin composition are provided.
[Formula 1]

(In Formula 1 above, each substituent is as defined in the specification.)

Description

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

This description relates to a photosensitive resin composition, a photosensitive resin film and 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, so 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 (light blocking layer), 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. It is composed.

A color filter is a black matrix (light-shielding 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), etc.) to form each pixel. It has a structure in which the pixel units, in which the three primary colors of blue (B) are arranged in a certain order, are stacked one after another.

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 using the pigment dispersion method generally consists of an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method having the above characteristics is actively used to manufacture LCDs for mobile phones, laptops, monitors, TVs, etc.

However, in recent years, even for photosensitive resin compositions for color filters using pigment dispersion methods, which have various advantages, the process of micronizing 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. And in the case of color imaging devices for image sensors, smaller dispersed particles are required to form fine patterns. In order to meet such demands, attempts are being made to implement color filters with improved color characteristics such as brightness and contrast ratio by manufacturing photosensitive resin compositions that introduce non-particle dyes instead of or together with pigments. However, dye-type Photosensitive resin compositions have a problem of lower durability compared to pigment-type photosensitive resin compositions.

Meanwhile, in the case of blue resist, violet dye or pigment is generally applied to blue pigment to match color coordinates and increase luminance. However, in order to increase the color gamut, aim for a color coordinate (high color coordinate) with a low Bx (while keeping By constant), or to block blue light in the region of 450 nm or less to reduce eye damage that may occur when exposed to blue light for a long time. Efforts to do so have been underway recently.

In terms of device configuration, there are ways to apply a light-shielding film or change the backlight (Back Light Unit (BLU)).

When adding a blue light blocking film, one more step is added to the process, and when applying a backlight with a short wavelength area cut, the entire factory line must be changed, which takes a huge amount of time and money.

In terms of resist composition, there is a method of reducing the width of the transmission spectrum by applying an excessive amount of a beta-type blue pigment with a low Bx instead of the mainly used epsilon-type blue pigment. In this case, the luminance is greatly reduced.

One embodiment is to control the content of a dye with a spectral characteristic of strongly absorbing a very narrow wavelength band in a specific area along with a phthalocyanine dye and mix it with a blue pigment to obtain high color coordinates (coordinates where only the Bx coordinate value is low at a certain By coordinate value). ), while providing a photosensitive resin composition that can improve brightness and durability.

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 of the present invention includes (A) a colorant including a blue pigment, a dye represented by the following formula (1), and a phthalocyanine-based dye; (B) binder resin; (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a solvent, wherein the compound represented by Formula 1 is contained in an amount of 10% by weight or less based on the total amount of the photosensitive resin composition, and the phthalocyanine-based dye is contained in an amount of 25% by weight or less based on the total amount of the photosensitive resin composition. A photosensitive resin composition is provided.

[Formula 1]

In Formula 1,

M is Cu, Co, VO, Zn, Pt or In,

L ¹ to L ⁴ are each independently *-C(=O)O-* or *-S(=O) ₂ NH-*,

R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ⁵ to R ¹² are each independently a hydrogen atom or a halogen atom.

The dye represented by Formula 1 may be included in a smaller amount than the phthalocyanine-based dye.

The dye represented by Formula 1 and the phthalocyanine-based dye may be included in a weight ratio of 1:1.1 to 1:2.

L ¹ to L ⁴ are each independently *-C(=O)O-*, and R ¹ to R ⁴ may each independently be a substituted or unsubstituted C1 to C20 alkyl group.

The dye represented by Formula 1 may have maximum absorption in the wavelength range of 400 nm to 435 nm.

The compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-14.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

In Formula 1-1 or Formula 1-14,

M is Cu, Co, VO, Zn, Pt or In.

The phthalocyanine-based dye may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R ¹³ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group.

In Formula 2, at least one of R ¹³ to R ¹⁶ and at least one of R ²¹ to R ²⁴ may be a C6 to C20 aryloxy group substituted with a halogen atom, and at least one of R ¹⁷ to R ²⁰ and R ²⁵ to R ²⁸ At least one of them may be a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group.

In Formula 2, any one of R ¹⁴ and R ¹⁵ and any one of R ²² and R ²³ may be a C6 to C20 aryloxy group substituted with a halogen atom, and any one of R ¹⁸ and R ¹⁹ and R ²⁶ and R ²⁷ Any one of them may be a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group.

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

The binder resin may be an acrylic binder resin. In this case, the acrylic binder resin may have a weight average molecular weight of 5000 g/mol to 15000 g/mol and an acid value of 80 mgKOH/g to 130 mgKOH/g. You can.

The photosensitive resin composition includes 30% by weight to 50% by weight of the colorant, based on the total amount of the photosensitive resin composition; 1% to 10% by weight of the binder resin; 1% to 10% by weight of the photopolymerizable compound; It may include 0.1% to 5% by weight of the photopolymerization initiator and the remaining amount of the solvent.

The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

The photosensitive resin composition may have a Bx value of 0.152 or less when the By value is 0.0600 in CIE color coordinates.

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

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

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

The photosensitive resin composition according to one embodiment minimizes the amount of dye having a spectral characteristic of strongly absorbing light in a very narrow wavelength range in a specific region, thereby preventing a decrease in luminance and durability, while realizing a low Bx color coordinate in a high-color blue resist.

Figure 1 is a graph showing the transmission spectrum of photosensitive resin compositions according to Examples 1 to 4, Comparative Examples 1, and Comparative Examples 2.

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, “substituted” or “substituted” means that one or more hydrogen atoms in the functional groups of the present invention are halogen atoms (F, Br, Cl or I), hydroxy groups, nitro groups, cyano groups, amino groups ( NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), where R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other and are each independently a C1 to C10 alkyl group), an amidino group, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic groups.

Unless otherwise specified herein, “alkyl group” means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and “cycloalkyl group” means a C3 to C20 cycloalkyl group, specifically C3 refers to a C1 to C18 cycloalkyl group, “alkoxy group” refers to a C1 to C20 alkoxy group, specifically refers to a C1 to C18 alkoxy group, and “aryl group” refers to a C6 to C20 aryl group, specifically refers to a C6 to C20 aryl group. means a C18 aryl group, “alkenyl group” means a C2 to C20 alkenyl group, specifically means a C2 to C18 alkenyl group, and “alkylene group” means a C1 to C20 alkylene group, specifically a C1 to C18 alkylene group, and “arylene group” refers to a C6 to C20 arylene group, specifically, a C6 to C16 arylene group.

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

Unless otherwise defined herein, “combination” means mixing or copolymerization. Additionally, “copolymerization” refers to block copolymerization to random copolymerization, and “copolymer” refers to block copolymerization to random 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.

In this specification, CIE color coordinates refer to CIE1931 color coordinates.

As used herein, cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following formulas 3-1 to 3-11 are included in the backbone of the resin.

Additionally, unless otherwise defined in the specification, “*” means a portion connected to the same or different atom or chemical formula.

One embodiment includes (A) a colorant including a blue pigment, a dye represented by the following formula (1), and a phthalocyanine-based dye; (B) binder resin; (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) a solvent, wherein the compound represented by Formula 1 is contained in an amount of 10% by weight or less based on the total amount of the photosensitive resin composition, and the phthalocyanine-based dye is contained in an amount of 25% by weight or less based on the total amount of the photosensitive resin composition. A photosensitive resin composition is provided.

[Formula 1]

In Formula 1,

M is Cu, Co, VO, Zn, Pt or In,

L ¹ to L ⁴ are each independently *-C(=O)O-* or *-S(=O) ₂ NH-*,

R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ⁵ to R ¹² are each independently a hydrogen atom or a halogen atom.

Among existing color filter resists, in the case of blue resist, it is common to add some violet colorant to the blue pigment to adjust color coordinates and increase luminance. However, recently, the color coordinates (high color coordinates) of the new blue to increase the color gamut have tended to make Bx smaller. In order to implement a blue color filter with such a high color reproduction rate, it is necessary to create a narrow transmission spectrum around 450nm, which is the wavelength of the light source, blue LED. To this end, the previously commonly used epsilon blue (e.g. C.I. Pigment Blue 15:6) must be used. Instead of using beta blue pigments (e.g. C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, etc.), there is also a proposal to produce a resist that increases the PWC and reduces the width of the transmission spectrum. However, in this case, there is a problem that the existing luminance is very low.

Meanwhile, through repeated research, the present inventors have confirmed that a narrow blue spectrum can be achieved by applying a dye that has a maximum absorption at a wavelength of 430 nm or less and a transmittance of more than 95% at a wavelength of 450 nm or more. However, the durability It was found that there is a disadvantage in that it is difficult to apply excessive amounts of these dyes due to the limitations of .

According to one embodiment, while lowering Bx to implement high-color coordinates, a specific structure, that is, a structure of a dye that cuts the violet region, is formed in the formula above to prevent a decrease in luminance and durability compared to when using beta blue. It is limited to 1, and it is used together with epsilon blue (blue pigment) and phthalocyanine dye, and the content of the dye represented by Formula 1 and the phthalocyanine dye is 10% by weight or less and 25% by weight, respectively, based on the total amount of the photosensitive resin composition. It was controlled to be below. (Same By standard) In order to lower Bx, the content of blue pigment and dye that cuts the violet region must be lowered. In one embodiment, the blue pigment and the dye represented by Formula 1 are used together with a phthalocyanine dye. By doing so, the total amount of dye used for cutting blue pigments and violet areas can be greatly reduced. In addition, the dye that cuts the violet region mainly absorbs light in the wavelength range of 420 nm or less due to its structure represented by Formula 1, and the transmittance in the wavelength range after 450 nm is more than 95%, so The luminance loss of the main spectrum from the light source can be minimized, and the problem of luminance decrease due to a decrease in the amount of colorant used can also be prevented. In the case of the conventional photosensitive resin composition, which cannot implement high color coordinates because Bx is large, luminance and durability are superior to the composition according to one embodiment that can implement high color coordinates, but the current display market is demanding more compositions that can realize high color coordinates. , No matter how excellent the luminance and durability are, if it is difficult to implement high color coordinates, it is difficult to receive recognition in the current display market anymore. In light of this current situation, research on photosensitive resin compositions that can improve luminance and durability has become the latest trend, on the premise of realizing high color coordinates with low Bx, and the present inventors have also followed this trend and made numerous As a result of conducting research through trial and error, we were able to develop a photosensitive resin composition that can achieve a low Bx color coordinate while preventing a decrease in luminance and durability.

Below, each component is described in detail.

(A) Colorant

The colorant includes a blue pigment, a dye represented by Formula 1, and a phthalocyanine-based dye.

(blue pigment)

For example, the blue pigment may include epsilon blue pigment. For example, the blue pigment includes both “epsilon blue pigment” and “blue-hybrid pigment of ‘epsilon blue pigment’ and ‘Xanthene violet dye’” can do. In this case, it helps improve brightness compared to the case where Janssen-based violet dye is used alone. Additionally, including epsilon blue pigment may be advantageous in maintaining low transmittance in the wavelength range of 400 nm to 450 nm. That is, in this specification, the blue-hybrid blue pigment dispersion may mean a blue pigment dispersion in which the Janssen-based violet dye is mixed with the blue pigment dispersion in which the epsilon blue pigment is dispersed.

For example, the epsilon blue pigment is C.I. It may be Pigment Blue 15:6, etc.

For example, the blue pigment may be a derivative combined with an organic polymer.

For example, the blue pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment within the solvent.

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

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid. Salts, alkylamide alkylene oxide adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more.

Examples of commercially available dispersants include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 1% to 20% by weight based on the total amount of the pigment dispersion. When the dispersant is included within the above range, appropriate viscosity can be maintained and the dispersibility of the photosensitive resin composition is excellent, and thus optical, physical and chemical quality can be maintained when the product is applied.

Solvents for forming the pigment dispersion include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, and propylene glycol methyl ether.

The blue pigment dispersion may be included in an amount of 10% to 25% by weight, for example, 15% to 25% by weight, for example, 16% to 24% by weight, based on the total amount of the photosensitive resin composition. When the pigment dispersion is contained within the above range, it is advantageous to secure the process margin and the color reproduction rate and contrast ratio are excellent.

(Dye represented by Chemical Formula 1)

The dye represented by Formula 1 has spectral characteristics of strongly absorbing light in a very narrow region of 400 nm to 450 nm and has high solubility in organic solvents, so when a photosensitive resin composition containing it as a colorant is used, a color filter with excellent color gamut is produced. can be manufactured. The very narrow area of 400nm to 450nm is the Blue Light Hazard Area. The higher the transmittance in the wavelength range of 400nm to 450nm, the more difficult it is to implement high-color coordinates (lowering Bx). The lower the transmittance in the wavelength region, the easier it is to implement high-color coordinates (lowering Bx). Transmittance in the wavelength range of 400 nm to 450 nm is proportional to the area of the lower part of the transmittance graph, and by checking the transmission spectrum, it can be easily confirmed whether the transmittance is high or low (see Figure 1). Furthermore, a photosensitive resin film manufactured using a composition containing the dye represented by Formula 1 as a colorant has high color reproduction and low reflectance.

In Formula 1, the substitution positions of the substituents (*-L ¹ -R ¹ , *-L ² -R ² , *-L ³ -R ³ and *-L ⁴ -R ⁴ ) are ortho, Coming to the para position among meta and para may be advantageous in increasing absorbance in a narrow wavelength range of 400 nm to 450 nm. For example, the dye represented by Chemical Formula 1 in which the substitution positions of the substituents are para shows very strong absorbance at 400 nm to 450 nm, for example, 400 nm to 435 nm, so a composition containing it as a colorant has a low Bx and at the same time shows color. Reproducibility, color stability, light fastness, etc. may be excellent.

For example, in Formula 1, L ¹ to L ⁴ are each independently *-C(=O)O-*, and R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group. there is. In this case, the compatibility with the phthalocyanine-based dye is the best, and it has low transmittance in the wavelength range of 400 nm to 450 nm, making it possible to maintain low Bx and at the same time maintain excellent durability.

For example, the dye represented by Formula 1 may have maximum absorption in the wavelength range of 400 nm to 435 nm.

For example, the compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-14, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

In Formula 1-1 or Formula 1-14,

M is Cu, Co, VO, Zn, Pt or In.

For example, the dye represented by Formula 1 may be included in a smaller amount than the phthalocyanine-based dye described later. For example, the dye represented by Formula 1 and the phthalocyanine-based dye may be included in a weight ratio of 1:1.1 to 1:2. It may be more advantageous to include the dye represented by Formula 1 in a smaller amount than the phthalocyanine-based dye, specifically in the above weight ratio (while maintaining low Bx) in improving durability such as heat resistance and chemical resistance.

The dye represented by Formula 1 may be included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, based on the total amount of the photosensitive resin composition according to one embodiment.

(phthalocyanine dye)

The phthalocyanine-based dye may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R ¹³ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group.

For example, in Formula 2, at least one of R ¹³ to R ¹⁶ and at least one of R ²¹ to R ²⁴ may be a C6 to C20 aryloxy group substituted with a halogen atom, and at least one of R ¹⁷ to R ²⁰ and R ²⁵ to At least one of R ²⁸ may be a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group. Specifically, in Formula 2, any one of R ¹⁴ and R ¹⁵ and any one of R ²² and R ²³ may be a C6 to C20 aryloxy group substituted with a halogen atom, and any one of R ¹⁸ and R ¹⁹ and R ²⁶ And any one of R ²⁷ may be a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group. When the phthalocyanine dye represented by Formula 2 is like this, it has the best correspondence with the dye represented by Formula 1 described above, effectively improving durability such as heat resistance and chemical resistance (while maintaining low Bx). You can plan it.

The phthalocyanine-based dye may be included in an amount of 5% by weight to 20% by weight, for example, 5% by weight to 15% by weight, based on the total amount of the photosensitive resin composition according to one embodiment. When included in the above range, high color coordinates with low transmittance can be easily achieved in the wavelength range of 400 nm to 450 nm.

(B) Binder resin

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

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is 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% to 50% by weight, for example, 10% to 40% by weight, based on the total amount of the acrylic binder 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 (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Examples include, but are not limited to, acrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and these may be used alone or in combination of two or more types. there is.

For example, the photosensitive resin composition according to the above embodiment may include an acrylic binder resin.

The weight average molecular weight of the acrylic binder resin may be 5,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate when manufacturing a color filter.

The acid value of the acrylic binder resin may be 80 mgKOH/g to 130 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

For example, the photosensitive resin composition according to the embodiment may be a cardo-based binder resin or a mixture of the acrylic binder resin and a cardo-based binder resin.

The cardo-based binder resin may be represented by the following formula (3).

[Formula 3]

In Formula 3 above,

R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ¹⁰³ and R ¹⁰⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁰⁷ R ¹⁰⁸ , SiR ¹⁰⁹ R ¹¹⁰ (wherein R ¹⁰⁷ to R ¹¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following Any one of the linking groups represented by Formulas 3-1 to 3-11,

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

(In Formula 3-5 above,

R ^z is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.)

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

Z ² is an acid anhydride residue or an acid dianhydride residue,

z1 and z2 are each independently integers from 0 to 4.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. If the weight average molecular weight of the cardo-based binder resin is within the above range, a pattern can be easily formed without residue when manufacturing the light-shielding layer, there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may include a functional group represented by the following formula (4) at at least one of both ends.

[Formula 4]

In Formula 4 above,

Z ³ may be represented by the following formulas 4-1 to 4-7.

[Formula 4-1]

(In Formula 4-1, R ^h and R ⁱ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Formula 4-5, R ^j is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Formula 4-6]

[Formula 4-7]

The cardo-based binder resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic acid dianhydride, Anhydride compounds such as rylene tetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the binder resin includes a cardo-based binder resin, the photosensitive resin composition has excellent developability, good sensitivity during photocuring, and excellent fine pattern formation.

The binder resin may be included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability is excellent when manufacturing a color filter, crosslinking is improved, and excellent surface smoothness can be obtained.

(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 sufficiently polymerizing the compound upon exposure to light in the pattern formation process.

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

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® , M- ^111® , and M- ^114® manufactured by Toagosei Chemical Co., Ltd.; Nippon 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 Aronics M-210 ^® , M-240 ^® , and M-6200 ^® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , HX-220 ^® , 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 Aronics M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , and M manufactured by Toagosei Chemical Co., Ltd. -710 ^® , M-8030 ^® , M-8060 ^® , etc.; Nippon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , DPCA-20 ^® , Dong-30 ^® , Dong-60 ^® , Dong-120 ^® , etc.; Examples include V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , and Dong-400 ^® manufactured by 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 included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.

(D) Photopolymerization initiator

The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. You can use it.

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-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

Examples of the oxime-based compounds include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime) )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime-O- Acetate, etc. can be mentioned.

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 used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.

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 range, curing occurs sufficiently during exposure during the pattern formation process to obtain excellent reliability, the heat resistance, light resistance, and chemical resistance of the pattern are excellent, resolution and adhesion are also excellent, and no damage due to unreacted initiator is achieved. Deterioration of transmittance can be prevented.

(E) Solvent

The solvent may be a material that is compatible with, but does not react with, the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as 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 esters such as methyl lactate and ethyl lactate; Alkyl oxyacetic acid esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionate esters such as methyl 2-oxy-2-methyl propionate, ethyl 2-oxy-2-methyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as ethyl methyl propionate; esters such as ethyl 2-hydroxy propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxy acetate, and 2-hydroxy-3-methyl methyl butanoate; Keto acid esters such as ethyl pyruvate, and others include N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, considering compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate may be used.

The solvent may be included in the remaining amount, for example, 30 wt% to 60 wt%, such as 30 wt% to 50 wt%, for example, 40 wt% to 60 wt%, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, thereby improving processability when manufacturing a color filter.

(F) Other additives

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

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, methacryloyl group, isocyanate group, or epoxy group to improve adhesion to the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, and γ glycidoxy propyl trimethoxysilane. Examples include methoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, and these can be used alone or in combination of two or more types.

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

Additionally, the photosensitive resin composition may further include a surfactant, if necessary, to improve coating properties and prevent defects.

Examples of the surfactant include BM-1000 ^® and BM-1100 ^® from BM Chemie; Mecha pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^® , etc. from Dai Nippon Inki Chemicals Co., Ltd.; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® , etc. from Sumitomo 3M Co., Ltd.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® , etc.; Fluorine-based surfactants commercially available under names such as SH-28PA ^® , Dong-190 ^® , Dong-193 ^® , SZ-6032 ^® , and SF-8428 ^® from Toray Silicone Co., Ltd. can be used.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, coating uniformity is ensured, stains do not occur, and wetting on the glass substrate is excellent.

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

Meanwhile, the photosensitive resin composition according to one embodiment can implement CIE color coordinates with a Bx value of 0.152 or less when the By value is 0.0600. As described above, the photosensitive resin composition according to one embodiment is a photosensitive resin composition that can improve luminance and durability on the premise that it implements a high color coordinate with a low Bx, and can implement the CIE color coordinate as described above.

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

The pattern formation process in the photosensitive resin film is as follows.

A process of applying the photosensitive resin composition to a support substrate by spin coating, slit coating, inkjet printing, etc.; A step of drying the applied photosensitive resin composition to form a photosensitive resin composition film; A process of exposing the photosensitive resin composition film; A process of developing the exposed photosensitive resin composition film with an aqueous alkaline solution to produce a photosensitive resin film; and a step of heat treating the photosensitive resin film. Since the above process conditions are widely known in the field, detailed description will be omitted in this specification.

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

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

(Example)

(Synthesis of the compound represented by Formula 1)

Synthesis Example 1: Synthesis of the compound represented by Formula 1-1

Add 30 g (0.2 mol) of terephthalaldehydic acid to a round bottom flask, add 600 g of propionic acid, and stir. After adding 13.5 g (0.2 mol) of pyrrole to the reaction, the reaction was raised to 80°C and stirred for 1 hour, then heated to 130°C, stirred for 90 minutes, and then terminated. After lowering the reactant to room temperature (23°C), 300 g of acetone was added thereto, stirred at room temperature for 1 hour, and then filtered. Afterwards, the solid compound present on the filter was collected, washed with acetone, and dried to produce Intermediate (A) 8.3. g was synthesized.

Afterwards, 3 g (3.8 mmol) of intermediate (A) and 30 g of SOCl ₂ were added to a round-bottomed flask under a nitrogen atmosphere, stirred at 80°C for 12 hours, and excess SOCl ₂ was removed through distillation. After adding 45 g of chloroform, 2.96 g (18.24 mmol) of 2-hydroxybenzofluoride and 1.85 g (18.24 mmol) of triethylamine were added and stirred at room temperature for 24 hours. When the reaction is completed, it is washed with 10% NaCl solution and DI water and extracted with chloroform. Afterwards, solvents were removed through distillation and then 0.99 g of intermediate (B) was obtained using column chromatography.

Add 30 g (0.283 mol) of benzaldehyde to a round bottom flask, add 600 g of propionic acid, and stir. After adding 18.9 g (0.283 mol) of pyrrole to the stirred reactant, the temperature was raised to 80°C and stirred for 1 hour, then heated to 130°C and stirred for 90 minutes to terminate the reaction. After lowering the reactant to room temperature, 300 g of acetone was added thereto, stirred at room temperature for 1 hour, and then filtered. Afterwards, the solid compound present on the filter was collected, washed with acetone, and dried to synthesize 11.3 g of intermediate (E).

Afterwards, 11.3 g (18.4 mmol) of the intermediate (E) obtained above was added to the round bottom flask, then 50 g of chlorosulfonic acid and 200 g of methylene chloride were added thereto and stirred at room temperature for 5 hours. When the reaction is completed, the solvent and chlorosulfonic acid are removed through distillation, then 100 g and 2-ethylhexylamine (14.3 g 110.4 mmol) are added thereto and stirred at room temperature for 24 hours. When the reaction is completed, it is washed with 10% NaCl solution and DI water and extracted with methylene chloride. Afterwards, the solvent was removed through distillation and then 5.1 g of intermediate (F) was obtained using column chromatography.

Add 3.2 g (2.58 mmol) of the intermediate (F) to one round bottom flask, add 160 g of chloroform, and stir at 60°C. Add 1.42 g (7.74 mmol) of Zn(OAc) ₂ to another round bottom flask, then add 30 g of MeOH and stir at room temperature to dissolve Zn(OAc) ₂ . Afterwards, the Zn(OAc) ₂ solution was added to the flask containing the intermediate (B) and reacted with stirring for 2 hours. When the reaction is completed, the temperature is lowered to room temperature (23°C), extracted with MC, and washed with 10% NaCl and DI water. After removing the solvents through distillation, the reactant is dissolved in a minimum amount of MC and then slowly added dropwise to 100 g MeCN. The precipitate was filtered, washed with MeCN, and dried to obtain 3.1 g (yield: 92%) of a compound represented by the following Chemical Formula 1-1: In the compound represented by the following Chemical Formula 1-1, M is Zn.

[Formula 1-1]

MALDI-TOF 1200 m/z

(Synthesis of phthalocyanine dyes)

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

4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.6g), 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile (1.5g) in a 100mL flask. g), Add 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) 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. 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 2-1.

[Formula 2-1]

MALDI-TOF 1649.57 m/z

(Synthesis of photosensitive resin composition)

Examples 1 to 7 and Comparative Examples 1 to 5

The photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were prepared by mixing the components mentioned below in the composition shown in Table 1.

Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours, then a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 2 hours. Next, colorants and other additives were added to the obtained reaction product and stirred at room temperature for 2 hours. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) Colorant (A-1) 16.2 15.0 13.7 10.9 16.2 13.7 13.7 20.0 18.4 - 10.9 16.2 (A-2) 7.0 7.4 7.7 8.0 7.0 7.7 7.7 6.8 6.3 15.5 8.0 7.0 (A-3) 9.8 8.2 6.5 4.8 10.0 9.35 6.2 - 14.0 - 4.3 10.5 (A-4) 5.5 8.9 12.2 25.0 5.3 9.35 12.5 - - 26.5 25.5 4.8 (B) Binder resin 8.4 8.3 8.2 8.2 8.4 8.2 8.2 8.3 8.4 8.3 8.2 8.4 (C) Photopolymerizable compound 5.3 5.3 5.2 5.2 5.3 5.2 5.2 5.2 5.3 5.3 5.2 5.3 (D) Photopolymerization initiator (D-1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (D-2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (E) Solvent 47.0 46.4 45.7 37.1 47.0 45.7 45.7 58.9 46.8 43.5 37.1 47.0 (F) Other additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

(A) Colorant

(A-1) C.I. Pigment Blue 15:6 dispersion (Iridos; pigment solids 10%)

(A-2) Blue-Hybrid blue pigment dispersion (Iridos; epsilon blue pigment + Janssen violet dye)

(A-3) Dye of Synthesis Example 1

(A-4) Phthalocyanine-based dye of Synthesis Example 2

(B) Binder resin

Acrylic binder resin (SP-RY-25, Showadenko)

(C) Photopolymerizable compound

Dipentaerythritol hexaacrylate (DPHA) (Japan Gunpowder Co., Ltd.)

(D) Photopolymerization initiator

(D-1) Oxime-based initiator (Samyang; SPI02)

(D-2) Oxime-based initiator (Samyang; SPI03)

(E) Solvent

PGMEA (Pyohwasa)

(F) Additives

Fluorine-based surfactant (F-554, DIC)

(Evaluation 1) Color coordinates and luminance

The photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were applied to a thickness of 1 ㎛ to 3 ㎛ on a degreased and washed glass substrate with a thickness of 1 mm under conditions of 250 rpm to 350 rpm. , and dried on a hot plate at 90°C for 2 minutes to obtain a coating film. Subsequently, the entire surface was exposed using a high-pressure mercury lamp with a main wavelength of 365 nm under the condition of 40 mJ/cm ² , and then washed with water/developer = 1/0.8 using KOH developer (111 times diluted solution) in the developer. It was developed for 60 seconds under the conditions, and then washed with water for another 60 seconds to give the development history. Afterwards, it was dried in a hot air circulation drying furnace at 230°C for 20 minutes to obtain a color chip.

The produced color specimen was evaluated for color characteristics based on C light source using a spectrophotometer (MCPD3000, Otsuka Electronic), and luminance (Y) and contrast ratio were calculated based on CIE color coordinates (By 0.0600), and the results are shown in the table below. It is shown in 2.

CIE color coordinates Luminance contrast ratio Bx By Example 1 0.1511 0.0600 8.81 11720 Example 2 0.1511 0.0600 8.82 11830 Example 3 0.1511 0.0600 8.84 11941 Example 4 0.1511 0.0600 8.75 11784 Example 5 0.1511 0.0600 8.63 11778 Example 6 0.1511 0.0600 8.64 11779 Example 7 0.1511 0.0600 8.74 11789 Comparative Example 1 0.1555 0.0600 12.04 10712 Comparative Example 2 0.1510 0.0600 8.25 10736 Comparative Example 3 0.1504 0.0600 7.49 14002 Comparative Example 4 0.1505 0.0600 8.52 11705 Comparative Example 5 0.1514 0.0600 8.66 11734

(Evaluation 2) Heat resistance, chemical resistance and permeability

After evaluating the color characteristics of Evaluation 1, drying was performed once more for 20 minutes in a hot air circulation drying furnace at 230°C, then color coordinates and luminance were measured using the same equipment, and del was based on the color change values before and after the additional oven process. The heat resistance properties were confirmed by calculating the (E*) value. Chemical resistance was also confirmed by measuring the color coordinates and luminance in the same way, then immersing the sample in an NMP solution at room temperature for 10 minutes, and calculating the del(E*) value based on the color change values before and after immersion in the solution. The heat resistance and chemical resistance results are shown in Table 3 below.

In the case of transmittance, after obtaining a transmittance graph according to each wavelength through the photosensitive resin composition MCPD equipment according to Examples 1 to 7 and Comparative Examples 1 to 5, the area under the graph corresponding to 400 nm to 450 nm was obtained, and the relative areas of the remaining photosensitive resin compositions were determined using the area obtained from the graph according to Comparative Example 1 (area of the area under the graph corresponding to 400 nm to 450 nm) as a standard (100%). The transmittance results are shown in Table 3 and Figure 1 below.

heat resistance chemical resistance Transmittance at 400nm to 450nm (relative comparison) (%) Example 1 3.20 4.31 55 Example 2 2.87 3.50 56 Example 3 2.54 2.68 57 Example 4 2.69 2.90 64 Example 5 2.67 2.79 61 Example 6 2.68 2.82 63 Example 7 2.77 2.91 65 Comparative Example 1 0.61 0.77 100 Comparative Example 2 4.49 10.89 53 Comparative Example 3 1.64 1.35 73 Comparative Example 4 2.68 2.71 88 Comparative Example 5 2.95 3.67 89

From Table 2, Table 3, and Figure 1, it can be seen that the photosensitive resin composition according to one embodiment maintains low transmittance at 400 nm to 450 nm, realizes high color coordinates, and has excellent heat resistance and chemical resistance. Specifically, it can be confirmed that the photosensitive resin composition of Comparative Example 1 is excellent in brightness, contrast ratio, durability, etc., but the transmittance at 400 nm to 450 nm is too high and high color coordinates cannot be realized at all. In addition, it can be confirmed that the photosensitive resin compositions of Comparative Examples 2 to 5 can implement high color coordinates, but the transmittance at 400 nm to 450 nm is too high or the brightness, contrast ratio, durability, etc. are not excellent.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and this also applies to the present invention. It is natural that it falls within the scope of the invention.

Claims (19)

(A) a colorant containing a blue pigment, a dye represented by the following formula (1), and a phthalocyanine-based dye;
(B) binder resin;
(C) photopolymerizable compound;
(D) photopolymerization initiator; and
(E) Solvent
Including,
The compound represented by Formula 1 is contained in an amount of 10% by weight or less based on the total amount of the photosensitive resin composition,
A photosensitive resin composition in which the phthalocyanine-based dye is contained in an amount of 5% to 25% by weight based on the total amount of the photosensitive resin composition:
[Formula 1]

In Formula 1,
M is Cu, Co, VO, Zn, Pt or In,
L ¹ to L ⁴ are each independently *-C(=O)O-* or *-S(=O) ₂ NH-*,
R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R ⁵ to R ¹² are each independently a hydrogen atom or a halogen atom.
According to paragraph 1,
A photosensitive resin composition in which the dye represented by Formula 1 is contained in a smaller amount than the phthalocyanine-based dye.
According to paragraph 2,
A photosensitive resin composition comprising the dye represented by Formula 1 and the phthalocyanine-based dye in a weight ratio of 1:1.1 to 1:2.
According to paragraph 1,
The L ¹ to L ⁴ are each independently *-C(=O)O-*,
The photosensitive resin composition wherein R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group.
According to paragraph 1,
The dye represented by Formula 1 is a photosensitive resin composition having maximum absorption in the wavelength range of 400 nm to 435 nm.
According to paragraph 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by any one of the following Formulas 1-1 to 1-14:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

In Formula 1-1 or Formula 1-14,
M is Cu, Co, VO, Zn, Pt or In.
According to paragraph 1,
The phthalocyanine-based dye is a photosensitive resin composition represented by the following formula (2):
[Formula 2]

In Formula 2,
R ¹³ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group.
In clause 7,
In Formula 2,
A photosensitive resin composition wherein at least one of R ¹³ to R ¹⁶ and at least one of R ²¹ to R ²⁴ are a C6 to C20 aryloxy group substituted with a halogen atom.
According to clause 8,
In Formula 2,
A photosensitive resin composition wherein any one of R ¹⁴ and R ¹⁵ and any one of R ²² and R ²³ are a C6 to C20 aryloxy group substituted with a halogen atom.
According to clause 8,
In Formula 2,
A photosensitive resin composition wherein at least one of R ¹⁷ to R ²⁰ and at least one of R ²⁵ to R ²⁸ are a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group.
According to clause 10,
In Formula 2,
A photosensitive resin composition wherein any one of R ¹⁸ and R ¹⁹ and any one of R ²⁶ and R ²⁷ are a C6 to C20 aryloxy group substituted with a C6 to C10 aryl group.
According to paragraph 1,
The binder resin is a photosensitive resin composition including an acrylic binder resin, a cardo-based binder resin, or a combination thereof.
According to clause 12,
The binder resin is an acrylic binder resin, and the acrylic binder resin has a weight average molecular weight of 5000 g/mol to 15000 g/mol.
According to clause 12,
The binder resin is an acrylic binder resin, and the acrylic binder resin has an acid value of 80 mgKOH/g to 130 mgKOH/g.
According to paragraph 1,
The photosensitive resin composition is based on the total amount of the photosensitive resin composition,
30% to 50% by weight of the colorant;
1% to 10% by weight of the binder resin;
1% to 10% by weight of the photopolymerizable compound;
0.1% to 5% by weight of the photopolymerization initiator and
The remaining amount of the solvent
A photosensitive resin composition containing a.
According to paragraph 1,
The photosensitive resin composition further includes an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.
According to paragraph 1,
The photosensitive resin composition has a Bx value of 0.152 or less when the By value is 0.0600 in CIE color coordinates.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 17.
A color filter comprising the photosensitive resin film of claim 18.

Images