KR102590489B1 - Compound, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and display device - Google Patents

Abstract

A phthalocyanine-based compound whose shortest half width to the maximum absorption wavelength is located within the range of 600 nm to 620 nm, a photosensitive resin composition containing the same, a photosensitive resin film manufactured using the photosensitive resin composition, a color filter comprising the photosensitive resin film, and A display device including the color filter is provided.

Description

Compound, photosensitive resin composition containing the same, photosensitive resin film, color filter and display device {COMPOUND, PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME, PHOTOSENSITIVE RESIN LAYER, COLOR FILTER AND DISPLAY DEVICE}

This disclosure relates to compounds, photosensitive resin compositions containing the same, photosensitive resin films, color filters, and display devices.

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, 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. The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels, and a plurality of colors (typically red (R), green (G), and blue (B) to form each pixel. ) has a structure in which the pixel units, in which the three primary colors 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 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, 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 demand for colorants that can be applied to image sensors that require characteristics of high brightness and high contrast ratio along with high color reproduction rate is increasing.

An image sensor refers to an image capture device component that generates an image from a display device such as a mobile phone camera or DSC (Digital Still Camera). Depending on the manufacturing process and application method, it can be broadly classified into a solid-state imaging device (charge coupled device; CCD). They can be classified into image sensors and complementary metal oxide semiconductor (CMOS) image sensors.

Since the photosensitive resin film for color filters used in solid-state imaging devices requires a film thickness of 1.5㎛ or less, a large amount of dye must be added to the photosensitive resin composition, which reduces sensitivity and leads to insufficient adhesion to the substrate. There are problems such as insufficient curing being obtained, dye eluting from exposed areas and color loss, and pattern forming properties being significantly reduced.

Accordingly, efforts are being made to develop photosensitive resin compositions for color filters that can be applied to image sensors that satisfy reliability such as brightness and chemical resistance while simultaneously realizing high colors.

One embodiment is to provide a compound capable of implementing a high-definition color filter.

Another embodiment is to provide a photosensitive resin composition containing the above compound.

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.

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

One embodiment of the present invention provides a phthalocyanine-based compound whose shortest wavelength at half maximum with respect to the maximum absorption wavelength is located within the range of 600 nm to 620 nm.

The phthalocyanine-based compound may be represented by the following formula (1).

[Formula 1]

In Formula 1,

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

R ⁵ to R ⁸ are each independently a hydrogen atom or a halogen atom,

R ⁹ to R ¹⁶ are each independently a halogen atom or represented by the following formula (2),

[Formula 2]

In Formula 2,

R ¹⁷ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

Formula 2 may be represented by any one of the following Formulas 2-1 to 2-4.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²⁰ to R ²² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

Any one of R ⁹ to R ¹⁶ may be represented by Formula 2.

The ‘any one of R ⁹ to R ¹² ’ or the ‘one of R ¹³ to R ¹⁶ ’ may be represented by Formula 2.

The ‘any one of R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ ’ may be represented by Formula 2 above.

The ‘any two of R ⁹ to R ¹⁶ ’ may be represented by Formula 2 above.

The ‘any one of R ⁹ to R ¹² ’ and the ‘one of R ¹³ to R ¹⁶ ’ may be represented by Formula 2.

The ‘any one of R ¹⁰ and R ¹¹ ’ and the ‘one of R ¹⁴ and R ¹⁵ ’ may be represented by Formula 2.

The compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-20.

[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]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

The compound may be a green dye.

Another embodiment provides a photosensitive resin composition containing the above compound.

The compound may be included in an amount of 1% to 40% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further include an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include pigment.

The photosensitive resin composition may further include a compound represented by the following formula (3).

[Formula 3]

In Formula 3 above,

R ²³ and R ²⁴ are each independently a hydroxy group or a substituted or unsubstituted C1 to C20 alkyl group,

n1 and n2 are each independently integers from 0 to 5, but 3 ≤ n1+n2 ≤ 5.

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

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

Another embodiment provides a display device including the color filter.

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

The compound according to one embodiment has excellent green spectral characteristics and a high molar extinction coefficient and has excellent solubility in organic solvents, so it can be used as a dye in the production of a photosensitive resin composition for a green color filter, and a photosensitive resin composition containing the dye. A photosensitive resin film manufactured using and a color filter containing the same can have excellent luminance and contrast ratio.

Figure 1 is a diagram to explain the half width of the maximum absorption wavelength of a compound and the shortest wavelength of the half width.

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 It means substituted with one or more substituents selected from the group consisting of 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.

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

One embodiment provides a phthalocyanine-based compound in which the shortest wavelength at half maximum with respect to the maximum absorption wavelength is located within the range of 600 nm to 620 nm.

In color filters manufactured from photosensitive resin compositions using pigments as colorants, there are limitations in luminance and contrast ratio resulting from the size of the pigment particles. Therefore, the need to improve luminance and contrast ratio is continuously raised, and to achieve this, particles instead of pigments are present. Efforts are continuing to implement color filters with improved luminance and contrast ratio by introducing dyes that do not form a photosensitive resin composition suitable for dyes, and through these efforts, in the case of photosensitive resin compositions that use dyes as the main colorant instead of pigments, , it has shown some effect in improving luminance and contrast ratio.

Meanwhile, in recent years, there has been a rapid increase in the demand for photosensitive resin compositions that can be applied to solid-state imaging device image sensors and complementary metal oxide semiconductor image sensors in addition to display devices such as conventional LCDs. In this case, it is impossible to realize high colors when applied to the image sensor, and a new problem is emerging that it is very difficult to manufacture a high-definition color filter. It is thought that the reason high color realization as described above is impossible is because the pattern size of the color filter mounted on a solid-state imaging device image sensor is very small, about 1/100 to 1/200 times the size of the color filter pattern for a conventional LCD.

Accordingly, after long research, the inventors of the present invention limited the shortest wavelength at half maximum for each maximum absorption wavelength of the phthalocyanine-based compound to a specific wavelength range, thereby creating a pattern that is 100 to 200 times smaller than the size of the conventional color filter pattern for LCD. It can be easily applied to branched patterns, increasing resolution, reducing residue, and ultimately leading to the development of a dye compound used in a photosensitive resin composition for color filters capable of realizing high colors.

The shortest wavelength at half maximum for the maximum absorption wavelength refers to the wavelength (a) with the smallest value among the energy width (Δλ) of the wavelength (maximum absorption wavelength, b) with the maximum absorption value in the absorption spectrum of a specific phthalocyanine compound. (See Figure 1)

Phthalocyanine-based compounds whose shortest half-width to the maximum absorption wavelength is located within the range of 600 nm to 620 nm, such as 610 nm to 620 nm, such as 611 nm to 616 nm, are compared to phthalocyanine-based compounds whose shortest half-width to the maximum absorption wavelength is outside the above range. , not only has excellent solubility in organic solvents, but also improves the brightness and chemical resistance of the photosensitive resin composition containing it as a colorant, and above all, it is possible to achieve high color (reduction of Gx value in CIE color coordinates (Gx, Gy)). In that respect, there is a big difference.

For example, a phthalocyanine-based compound whose shortest half width with respect to the maximum absorption wavelength is located within the range of 600 nm to 620 nm may be represented by the following formula (1).

[Formula 1]

In Formula 1,

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

R ⁵ to R ⁸ are each independently a hydrogen atom or a halogen atom,

R ⁹ to R ¹⁶ are each independently a halogen atom or represented by the following formula (2),

[Formula 2]

In Formula 2,

R ¹⁷ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

The compound represented by Formula 1 has excellent green spectral characteristics and a high molar extinction coefficient. Furthermore, the compound represented by Formula 1 must include at least one substituent represented by Formula 2, and thus can exhibit excellent solubility in organic solvents and excellent brightness and chemical resistance when applied to a color filter.

For example, when the compound represented by Formula 1 does not contain any substituents represented by Formula 2, the solubility, brightness, and chemical resistance in organic solvents are greatly reduced, and thus it is used as a colorant in a photosensitive resin composition for a color filter. Not only is it difficult, but it can also be very difficult to implement with a high-color reproduction image sensor.

The substituent represented by Formula 2 is “an aryloxy group having 1 or 2 alkyl groups as a substituent” or “an alkoxy group having 1 or 2 alkyl groups as a substituent”, and in the aryloxy group, the alkyl group is ortho. By being substituted at the (ortho) and/or para positions, brightness and chemical resistance can be further improved. For example, if the alkyl group is substituted at the meta position, it may be difficult to implement a green pixel for a color filter.

For example, Formula 2 may be represented by any one of the following Formulas 2-1 to 2-4, but is not necessarily limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²⁰ to R ²² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

In Formulas 2-2 and 2-3, at least one of R ¹⁸ and R ¹⁹ is a nonlinear alkyl group such as a tert-butyl group, rather than a linear alkyl group such as a methyl group, ethyl group, or n-butyl group. An alkyl group may be more advantageous in terms of brightness and chemical resistance, and in Formula 2-4, at least one of R ²⁰ to R ²² is a substituted or unsubstituted C1 to C20 alkyl group in terms of brightness and chemical resistance. It may be more advantageous.

For example, when the substituent represented by Formula 2 is represented by Formula 2-4, developability can be further improved.

In addition, the phthalocyanine-based compound represented by Formula 1 contains four hydrogen atoms and at least four halogen atoms, and these structural features can further improve solubility in organic solvents. More specifically, the phthalocyanine-based compound represented by Formula 1 includes i) a benzene ring having a group represented by R ¹ to R ⁴ , ii) a benzene ring having a group represented by R ⁵ to R ⁸ , iii) R ⁹ to R ¹² The core structure includes four benzene rings of a benzene ring having a group represented by and iv) a benzene ring having a group represented by R ¹³ to R ¹⁶ , including a substituent represented by Formula 2 among the four benzene rings. In the benzene ring, other than the substituent represented by Formula 2, all three remaining groups are halogen atoms, and all four groups of the benzene ring that do not contain the substituent represented by Formula 2 may be hydrogen atoms or halogen atoms, and these structural features Due to this, the shortest wavelength of the half width with respect to the maximum absorption wavelength can be easily located within the range of 600 nm to 620 nm, solubility in organic solvents can be further improved, and it can be advantageous in terms of improving brightness and securing process characteristics.

Above all, even if it is a phthalocyanine-based compound whose shortest wavelength at half-width with respect to the maximum absorption wavelength is located within the range of 600 nm to 620 nm, if the compound does not have the structure represented by Formula 1, the photosensitive resin composition containing it as a colorant Brightness and chemical resistance may be greatly reduced or high color may not be realized, so the phthalocyanine-based compound according to one embodiment has the shortest wavelength at half maximum with respect to the maximum absorption wavelength located within the range of 600 nm to 620 nm, and at the same time, it is expressed by Formula 1 above. It may be desirable to have a structure.

For example, one or both of R ⁹ to R ¹⁶ may be represented by Formula 2 above. If one or both of R ⁹ to R ¹⁶ are not represented by Formula 2, a problem of reduced luminance may occur.

For example, ‘one of R ⁹ to R ¹² ’ and/or ‘one of R ¹³ to R ¹⁶ ’ may be represented by Formula 2.

For example, ‘one of R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ ’ may be represented by Formula 2 above.

For example, ‘one of R ¹⁰ and R ¹¹ ’ and ‘one of R ¹⁴ and R ¹⁵ ’ may be represented by Formula 2.

For example, the compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-20, 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]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

For example, since the phthalocyanine-based compound represented by Formula 1 contains one or more substituents represented by Formula 2, it is possible to produce more vivid colors even with a small amount, and when used as a colorant, color characteristics such as brightness and contrast ratio are improved. Manufacturing of this excellent display device is possible. For example, the compound may be a colorant, such as a dye, such as a green dye, such as a dye having a maximum transmittance in the wavelength range of 445 nm to 560 nm.

Generally, dye is the most expensive component used in color filters. Therefore, in order to achieve the desired effect, such as high brightness or high contrast ratio, more expensive dyes must be used, which inevitably increases the production cost. However, when the compound according to one embodiment is used as a dye in a color filter, excellent color characteristics such as high brightness and high contrast ratio can be achieved even with a small amount, making it possible to reduce production costs.

According to another embodiment, a photosensitive resin composition including the phthalocyanine-based compound according to the above embodiment is provided.

For example, the photosensitive resin composition may include a phthalocyanine-based compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent according to the embodiment.

The compound according to one embodiment may act as a colorant, such as a dye, such as a green dye, in the photosensitive resin composition, and may express excellent color characteristics.

The compound according to one embodiment is 1% by weight to 40% by weight, such as 10% by weight to 40% by weight, such as 20% by weight to 40% by weight, such as 1% by weight to 30% by weight, based on the total amount of the photosensitive resin composition, such as It may comprise from 1% to 20% by weight, such as from 1% to 10% by weight. When the compound according to one embodiment is included in the above range, color gamut and contrast ratio become excellent .

The photosensitive resin composition may further include a pigment, such as a yellow pigment, a green pigment, or a combination thereof.

The yellow pigment is classified as C.I. in the color index. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, etc. can be mentioned, and these can be used alone or in a mixture of two or more types.

The green pigment is classified as C.I. in the color index. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59 and the like can be mentioned, and these can be used alone or in a mixture of two or more types.

The 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, 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 pigment dispersion may be included in an amount of 10% to 20% by weight, for example, 12% to 18% 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.

The binder resin may be an acrylic resin.

The acrylic 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 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, late 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. .

For example, the binder resin may further include an epoxy-based resin along with the acrylic resin.

The weight average molecular weight of the binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, an appropriate viscosity, and excellent adhesion to the substrate when manufacturing a color filter.

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

The binder resin may be included in an amount of 1% to 20% by weight, for example, 1% to 15% by weight, for example, 1% 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 property is improved, and excellent surface smoothness can be obtained.

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, novolac 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® , 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 15% by weight, for example, 1% to 10% 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.

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. can be used.

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)-octan-1-oneoxime-O-acetate and 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 0.01 wt% to 10 wt%, for example, 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, 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 there is no damage from unreacted initiators. Deterioration of transmittance can be prevented.

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

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 monomethyl 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, in consideration of compatibility and reactivity, 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; and/or ketones such as cyclohexanone may be used.

The solvent may be included in the remaining amount, for example, 30% by weight to 80% by weight, 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.

The photosensitive resin composition may further include a compound represented by the following formula (3).

[Formula 3]

In Formula 3 above,

R ²³ and R ²⁴ are each independently a hydroxy group or a substituted or unsubstituted C1 to C20 alkyl group,

L ² to L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently integers from 0 to 5, but 3 ≤ n1+n2 ≤ 5.

For example, the compound represented by Formula 3 may function as an antioxidant.

For example, in Formula 3, R ²³ may be a C1 to C20 alkyl group substituted with an alkyl group, R ²⁴ may be a hydroxy group, n1 may be an integer of 2, and n2 may be an integer of 1.

The photosensitive resin composition according to another 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 ^® , 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.

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

The pattern formation process within the color filter is as follows.

A process of applying the photosensitive resin composition on 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.

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.

(Synthesis of compounds)

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

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2-isopropyl-phenol (2.56g), 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, it is purified by column chromatography. After purification and vacuum drying, 4-(2-isopropyl-phenoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2-isopropropyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.73g), phthalonitrile (0.35g) 1,8-Diazabicycloundec in a 100mL flask. Add -7-ene (2.08g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.50g) 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 1-1.

[Formula 1-1]

Maldi-tof MS: 1190.69 m/z

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

4-(2-isopropropyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.91g), phthalonitrile (0.70g) 1,8-Diazabicycloundec in a 100mL flask. Add -7-ene (4.16g) and 1-pentanol (30g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (1.00g) 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 1-2.

[Formula 1-2]

Maldi-tof MS: 1090.96 m/z

Synthesis Example 3: Synthesis of the compound represented by Formula 1-3

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2-tert-Butyl-phenol (2.83g), 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, it is purified by column chromatography. After purification, it is vacuum dried to obtain 4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), phthalonitrile (0.34g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.48g) 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 1-3.

[Formula 1-3]

Maldi-tof MS: 1218.75 m/z

Synthesis Example 4: Synthesis of the compound represented by Formula 1-4

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.80g), phthalonitrile (0.67g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (4.01g) and 1-pentanol (30g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.97g) 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 1-4.

[Formula 1-4]

Maldi-tof MS: 1104.98 m/z

Synthesis Example 5: Synthesis of the compound represented by Formula 1-5

3,4,5,6-tetrachlorophthalonitrile (5g), p-cresol (2.83g), 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, it is purified by column chromatography. After purification and vacuum drying, 4-(2-methyl-phenoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2-methyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.79g), phthalonitrile (0.38g) 1,8-Diazabicycloundec in a 100mL flask. Add -7-ene (2.26g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.54g) 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 1-5.

[Formula 1-5]

Maldi-tof MS: 1134.58 m/z

Synthesis Example 6: Synthesis of the compound represented by Formula 1-6

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dimethylphenol (2.30g), 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, it is purified by column chromatography. After purification and vacuum drying, 4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.76g), phthalonitrile (0.36g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.17g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.52g) 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 1-6.

[Formula 1-6]

Maldi-tof MS: 1162.64 m/z

Synthesis Example 7: Synthesis of the compound represented by Formula 1-7

4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (3.03g), phthalonitrile (0.73g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (4.33g) and 1-pentanol (30g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (1.04g) 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 1-7.

[Formula 1-7]

Maldi-tof MS: 1076.93 m/z

Synthesis Example 8: Synthesis of the compound represented by Formula 1-8

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,4-di-t-butylphenol (3.9g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N) Add -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, it is purified by column chromatography. After purification and vacuum drying, 4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), and phthalonitrile (0.34g) in a 100mL flask. ) Add 1,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.48g) 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 1-8.

[Formula 1-8]

Maldi-tof MS: 1330.96 m/z

Synthesis Example 9: Synthesis of the compound represented by Formula 1-9

4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.80g), and phthalonitrile (0.68g) in a 100mL flask. ) Add 1,8-Diazabicycloundec-7-ene (4.01g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.97g) 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 1-9.

[Formula 1-9]

Maldi-tof MS: 1161.09 m/z

Synthesis Example 10: Synthesis of the compound represented by Formula 1-10

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2-tert-Butyl-4-methylphenol (3.09g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N Add -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, it is purified by column chromatography. After purification and vacuum drying, 4-(2-tert-Butyl-4-methyl phenoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2-tert-Butyl-4-methylphenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.68g), phthalonitrile (0.33g) 1 in a 100mL flask. Add 8-Diazabicycloundec-7-ene (1.9g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.47g) 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 1-10.

[Formula 1-10]

Maldi-tof MS: 1246.80 m/z

Synthesis Example 11: Synthesis of the compound represented by Formula 1-11

In a 100 mL flask, 4-(2-tert-Butyl-4-methylphenoxy)-3,5,6-trichloro-phthalonitrile (2 g), phthalonitrile (0.65 g) 1,8-Diazabicycloundec-7-ene (1.9 g) and 1 -Add pentanol (15g) and heat to 90℃ to dissolve the solid, then add zinc acetate (0.47g) 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 1-11.

[Formula 1-11]

Maldi-tof MS: 1109.03 m/z

Synthesis Example 12: Synthesis of the compound represented by Formula 1-12

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,2-dimethyl-1-propanol (1.66g), Diazabicycloundec-7-ene (4.29g), N,N-dimethylformamide (N, Add 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, it is purified by column chromatography. After purification and vacuum drying, 4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.84g), phthalonitrile (0.40g) 1 in a 100mL flask Add 8-Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.58g) 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 1-12.

[Formula 1-12]

Maldi-tof MS: 1094.60 m/z

Synthesis Example 13: Synthesis of the compound represented by Formula 1-13

4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (1g), 3,4,5,6-tetrachlorophthalonitrile (1.67g), phthalonitrile (0.40g) 1 in a 100mL flask Add 8-Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.58g) 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 1-13.

[Formula 1-13]

Maldi-tof MS: 1042.91 m/z

Synthesis Example 14: Synthesis of the compound represented by Formula 1-14

In a 100 mL flask, 4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (2 g), phthalonitrile (0.81 g) 1,8-Diazabicycloundec-7-ene (2.40 g) and 1 -Add pentanol (15g) and heat to 90℃ to dissolve the solid, then add zinc acetate (0.58g) 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 1-14.

[Formula 1-14]

Maldi-tof MS: 956.84 m/z

Synthesis Example 15: Synthesis of the compound represented by Formula 1-15

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 3-methyl-1-butanol (1.66g), Diazabicycloundec-7-ene (4.29g), N,N-dimethylformamide (N,N- Add 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, it is purified by column chromatography. After purification and vacuum drying, 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.84g), phthalonitrile (0.40g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.58g) 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 1-15.

[Formula 1-15]

Maldi-tof MS: 1094.60 m/z

Synthesis Example 16: Synthesis of the compound represented by Formula 1-16

4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile (1g), 3,4,5,6-tetrachlorophthalonitrile (1.67g), phthalonitrile (0.40g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.58g) 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 1-16.

[Formula 1-16]

Maldi-tof MS: 1042.91 m/z

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

4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile (2 g), phthalonitrile (0.81 g) 1,8-Diazabicycloundec-7-ene (2.40 g) and 1-pentane in a 100 mL flask. Add all (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.58g) 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 1-17.

[Formula 1-17]

Maldi-tof MS: 956.84 m/z

Synthesis Example 18: Synthesis of the compound represented by Formula 1-18

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2-methyl-1-propanol (1.39g), Diazabicycloundec-7-ene (4.29g), N,N-dimethylformamide (N,N- Add 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, it is purified by column chromatography. After purification and vacuum drying, 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile is obtained.

4-(2-methyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.88g), phthalonitrile (0.42g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.52g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.61g) 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 1-18.

[Formula 1-18]

Maldi-tof MS: 1066.55 m/z

Synthesis Example 19: Synthesis of the compound represented by Formula 1-19

4-(2-methyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (1g), 3,4,5,6-tetrachlorophthalonitrile (1.76g), phthalonitrile (0.42g) 1,8 in a 100mL flask. -Add Diazabicycloundec-7-ene (2.52g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.61g) 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 1-19.

[Formula 1-19]

Maldi-tof MS: 1028.89 m/z

Synthesis Example 20: Synthesis of the compound represented by Formula 1-20

4-(2-methyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (2 g), phthalonitrile (0.85 g) 1,8-Diazabicycloundec-7-ene (2.52 g) and 1-pentane in a 100 mL flask. Add all (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.61g) 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 1-20.

[Formula 1-20]

Maldi-tof MS: 928.78 m/z

Synthesis Example 21: Synthesis of the compound represented by Formula 1-21

4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), phthalonitrile (2.03g) and 1,8-Diazabicycloundec-7-ene (4.01g) in a 100mL flask. and 1-pentanol (15 g) were added and heated to 90°C to dissolve the solid. Then, zinc acetate (0.97g) was added and stirred 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 1-21.

[Formula 1-21]

Maldi-tof MS: 885.56 m/z

Comparative Synthesis Example 1: Synthesis of the compound represented by formula C-1

In a 100mL flask, 4-(2-sec-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (0.30g), 1-pentanol (7g), Add zinc acetate (0.12g) and stir while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. After purification, the obtained liquid is concentrated to obtain a solid. The crystallized solid is vacuum dried to obtain a compound represented by the following formula C-1.

[Formula C-1]

Maldi-tof MS: 1584.04 m/z

Comparative Synthesis Example 2: Synthesis of the compound represented by formula C-2

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,4-di-tert-butylphenol (2.75g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N Add -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-(2,4-dimethyl-phenoxy)-phthalonitrile.

3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1 g), 1,8-Diazabicycloundec-7-ene (1.08 g) and 1-pentanol in a 100 mL flask. Add (14g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.26g) 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 C-2.

[Formula C-2]

Maldi-tof MS: 1808.47 m/z

Comparative Synthesis Example 3: Synthesis of the compound represented by formula C-3

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2,4-dimethoxyphenol (3.47g), 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-(2,4-dimethoxy-phenoxy)-phthalonitrile.

3,4,6-Trichloro-5-(2,4-dimethoxy-phenoxy)-phthalonitrile (2g), 1,8-Diazabicycloundec-7-ene (0.99g), and 1-pentanol (14g) were added to a 100mL flask. After the solid is dissolved by heating to 90℃, add zinc acetate (0.24g) 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 C-3.

[Formula C-3]

Maldi-tof MS: 1591.80 m/z

Comparative Synthesis Example 4: Synthesis of the compound represented by formula C-4

4-(2,4-dimethoxy-phenoxy)-3,5,6-trichloro-phthalonitrile (0.7g), 3,4,5,6-Tetrachlorophthalonitrile (1.45g), 1 of Synthesis Example 1-2 in a 100mL flask. Add 8-Diazabicycloundec-7-ene (1.38g) and 1-pentanol (14g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.33g) 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 C-4.

[Formula C-4]

Maldi-tof MS: 1237.54 m/z

Comparative Synthesis Example 5: Synthesis of the compound represented by formula C-5

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), 4,5-dichlorophthalonitrile (0.52g) in a 100mL flask. ) Add 1,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.48g) 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 C-5.

[Formula C-5]

Maldi-tof MS: 1287.63 m/z

Comparative Synthesis Example 6: Synthesis of the compound represented by formula C-6

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), 4-dichlorophthalonitrile (0.43g) 1 in a 100mL flask Add 8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) and heat to 90℃ to dissolve the solid. Then add zinc acetate (0.48g) 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 C-6.

[Formula C-6]

Maldi-tof MS: 1253.19 m/z

Evaluation 1: Measurement of the shortest wavelength at half maximum for the maximum absorption wavelength

The compounds according to Synthesis Examples 1 to 21 and Comparative Synthesis Examples 1 to 6 were prepared at a concentration of 0.005 wt% using a diluting solvent (PGMEA), and prepared in Synthesis Examples 1 to 20 and Comparative Examples. Absorption spectra were obtained for each of the phthalocyanine compounds according to Synthesis Example 1 to Comparative Synthesis Example 6, and the results are shown in Table 1 below. (UV-1800, SHIMADZU)

Shortest wavelength at half maximum for maximum absorption wavelength (nm) Synthesis Example 1 616 Synthesis Example 2 617 Synthesis Example 3 618 Synthesis Example 4 617 Synthesis Example 5 618 Synthesis Example 6 618 Synthesis Example 7 618 Synthesis Example 8 616 Synthesis Example 9 618 Synthesis Example 10 616 Synthesis Example 11 611 Synthesis Example 12 617 Synthesis Example 13 618 Synthesis Example 14 611 Synthesis Example 15 617 Synthesis Example 16 618 Synthesis Example 17 611 Synthesis Example 18 617 Synthesis Example 19 618 Synthesis Example 20 611 Synthesis Example 21 608 Comparative Synthesis Example 1 628 Comparative Synthesis Example 2 624 Comparative Synthesis Example 3 623 Comparative Synthesis Example 4 626 Comparative Synthesis Example 5 625 Comparative Synthesis Example 6 623

Evaluation 2: Solubility measurements

A diluting solvent (PGMEA) was added to 0.5 g of the compounds according to Synthesis Examples 1 to 21 and Comparative Synthesis Examples 1 to 6, respectively, and the solution was mixed with a mix rotor (iuchi Co., Ltd., MIXROTAR VMR-5). After stirring at 25°C rpm for 1 hour, the solubility confirmation results of each compound are shown in Table 2 below.

Solubility evaluation criteria

Dissolution of more than 10% by weight of compound (solute) based on the total amount of diluting solvent: ○

Compound (solute) dissolved in less than 10% by weight based on the total amount of diluting solvent:

(Unit: weight%) Solubility Synthesis Example 1 ○ Synthesis Example 2 ○ Synthesis Example 3 ○ Synthesis Example 4 ○ Synthesis Example 5 ○ Synthesis Example 6 ○ Synthesis Example 7 ○ Synthesis Example 8 ○ Synthesis Example 9 ○ Synthesis Example 10 ○ Synthesis Example 11 ○ Synthesis Example 12 ○ Synthesis Example 13 ○ Synthesis Example 14 ○ Synthesis Example 15 ○ Synthesis Example 16 ○ Synthesis Example 17 ○ Synthesis Example 18 ○ Synthesis Example 19 ○ Synthesis Example 20 ○ Synthesis Example 21 X Comparative Synthesis Example 1 X Comparative Synthesis Example 2 X Comparative Synthesis Example 3 X Comparative Synthesis Example 4 X Comparative Synthesis Example 5 X Comparative Synthesis Example 6 X

From Table 2, the compounds of Synthesis Examples 1 to 20, which are compounds according to one embodiment, have better solubility in organic solvents than the compounds of Synthesis Examples 21 and Comparative Synthesis Examples 1 to 6, resulting in the photosensitive resin composition. It can be confirmed that excellent color characteristics can be shown when used in the back.

(Synthesis of photosensitive resin composition)

Example 1

The photosensitive resin compositions according to Examples 1 to 21 and Comparative Examples 1 to 6 were prepared by mixing the components mentioned below in the compositions shown in Tables 3 to 5.

Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours, then a binder resin and a photopolymerizable monomer were added thereto and stirred at room temperature for 2 hours. Next, the compound (dye) and pigment (in the form of pigment dispersion) prepared in the above synthesis example were added as colorants to the obtained reaction product and stirred at room temperature for 1 hour. Next, an antioxidant and a leveling agent were added, and the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%) Example One 2 3 4 5 6 7 8 9 10 binder resin EHPE-3150
(DAICEL, epoxy series) 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 NPR-5216
(Miwon, acrylic) 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 photopolymerizable monomer GM66G0P
(QPPC) 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 Miramer 2200
(Miwon) 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 photopolymerization initiator SPI-03
(Samyang Corporation) 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 IRG369
(BASF) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 antioxidant AO-80
(ADEKA) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 pigment G58 pigment dispersion (SANYO, AG1623) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Y138 Pigment Dispersion (ENF, EC-1200Y) 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 dyes 30.22 (Synthesis Example 1) 30.22 (Synthesis Example 2) 30.22 (Synthesis Example 3) 30.22 (Synthesis Example 4) 30.22 (Synthesis Example 5) 30.22 (Synthesis Example 6) 30.22 (Synthesis Example 7) 30.22 (Synthesis Example 8) 30.22 (Synthesis Example 9) 30.22 (Synthesis Example 10) menstruum PGMEA(DAICEL) 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 leveling agent F554(DIC) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

(Unit: weight%) Example 11 12 13 14 15 16 17 18 19 20 binder resin EHPE-3150
(DAICEL, epoxy series) 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 NPR-5216
(Miwon, acrylic) 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 photopolymerizable monomer GM66G0P
(QPPC) 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 Miramer 2200
(Miwon) 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 photopolymerization initiator SPI-03
(Samyang Corporation) 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 IRG369
(BASF) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 antioxidant AO-80
(ADEKA) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 pigment G58 pigment dispersion (SANYO, AG1623) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Y138 Pigment Dispersion (ENF, EC-1200Y) 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 dyes 30.22 (Synthesis Example 11) 30.22 (Synthesis Example 12) 30.22 (Synthesis Example 13) 30.22 (Synthesis Example 14) 30.22 (Synthesis Example 15) 30.22 (Synthesis Example 16) 30.22 (Synthesis Example 17) 30.22 (Synthesis Example 18) 30.22 (Synthesis Example 19) 30.22 (Synthesis Example 20) menstruum PGMEA(DAICEL) 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 leveling agent F554(DIC) 0.20 0.20 0.20 Total 100.00 100.00 100.00

(Unit: weight%) Example Comparative example 21 One 2 3 4 5 6 binder resin EHPE-3150
(DAICEL, epoxy series) 0.27 0.27 0.27 0.27 0.27 0.27 0.27 NPR-5216
(Miwon, acrylic) 7.91 7.91 7.91 7.91 7.91 7.91 7.91 photopolymerizable monomer GM66G0P
(QPPC) 4.92 4.92 4.92 4.92 4.92 4.92 4.92 Miramer 2200
(Miwon) 0.37 0.37 0.37 0.37 0.37 0.37 0.37 photopolymerization initiator SPI-03
(Samyang Corporation) 0.78 0.78 0.78 0.78 0.78 0.78 0.78 IRG369
(BASF) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 antioxidant AO-80
(ADEKA) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 pigment G58 pigment dispersion (SANYO, AG1623) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Y138 Pigment Dispersion (ENF, EC-1200Y) 17.79 17.79 17.79 17.79 17.79 17.79 17.79 dyes 30.22 (Synthesis Example 21) 30.22 (Comparative Synthesis Example 1) 30.22 (Comparative Synthesis Example 2) 30.22 (Comparative Synthesis Example 3) 30.22 (Comparative Synthesis Example 4) 30.22 (Comparative Synthesis Example 5) 30.22 (Comparative Synthesis Example 6) menstruum PGMEA(DAICEL) 34.50 34.50 34.50 34.50 34.50 34.50 34.50 leveling agent F554(DIC) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Evaluation 3: Color coordinates, luminance, chemical resistance, developability and surface wrinkles

The photosensitive resin composition prepared in Examples 1 to 21 and Comparative Examples 1 to 6 was applied to a thickness of 1 ㎛ to 3 ㎛ on a degreased and cleaned glass substrate with a thickness of 1 mm, and placed on a hot plate at 90°C. A coating film was obtained by drying on the surface for 2 minutes. Subsequently, the coating film was exposed using a high-pressure mercury lamp with a dominant wavelength of 365 nm. Afterwards, samples were obtained by drying in a hot air circulation drying furnace at 230°C for 20 minutes. The color purity of the pixel layer was evaluated based on the C light source using a spectrophotometer (MCPD3000, Otsuka Electronic), and the luminance (Y) was calculated based on the CIE color coordinates and is listed in Table 6 below.

In addition, after measuring the initial thickness of the sample (photoresist film) obtained through the above exposure and drying, it was left in NMP solvent at 25°C for 10 minutes, washed with ultrapure water for 30 seconds, and then dried by blowing with compressed air. Afterwards, chemical resistance was confirmed by measuring the del(E*) value using the spectrophotometer, and the results are shown in Table 6 below.

After the above coating and exposure processes, developability was confirmed using a developer (SVS, KOH diluted solution), and the results are shown in Table 6 below.

The developed substrate was dried in a hot air circulation drying furnace at 230°C for 20 minutes to obtain a sample, and surface wrinkles were confirmed using a scanning electron microscope. The results are shown in Table 6 below.

Chemical resistance evaluation criteria

del(E*) is less than 3: ○

del(E*) is 3 or more:

Developability evaluation criteria

BP less than 60 seconds: ○

BP over 60 seconds:

Surface wrinkle evaluation criteria

No wrinkles are observed on the pattern surface when observed with a scanning electron microscope: ○

Wrinkles observed on the pattern surface when observed with a scanning electron microscope:

CIE color coordinates (Gx, Gy) Luminance (%) chemical resistance Developability Surface wrinkle evaluation Example 1 0.255, 0.560 61.7 ○ O O Example 2 0.254, 0.560 61.8 ○ O O Example 3 0.255, 0.560 61.4 ○ O O Example 4 0.256, 0.560 61.5 ○ O O Example 5 0.254, 0.560 61.6 ○ O O Example 6 0.253, 0.560 61.7 ○ O O Example 7 0.255, 0.560 61.3 ○ O O Example 8 0.254, 0.560 61.9 ○ O O Example 9 0.252, 0.560 61.8 ○ O O Example 10 0.253, 0.560 61.6 ○ O O Example 11 0.254, 0.560 61.4 ○ O O Example 12 0.255, 0.560 61.2 ○ O O Example 13 0.253, 0.560 61.1 ○ O O Example 14 0.254, 0.560 61.3 ○ O O Example 15 0.255, 0.560 61.4 ○ O O Example 16 0.250, 0.560 61.8 ○ O O Example 17 0.251, 0.560 61.3 ○ O O Example 18 0.254, 0.560 61.2 ○ O O Example 19 0.255, 0.560 61.3 ○ O O Example 20 0.253, 0.560 61.5 ○ O O Example 21 0.253, 0.560 59.7 X X X Comparative Example 1 0.274, 0.560 60.1 X X X Comparative Example 2 0.273, 0.560 60.0 X O X Comparative Example 3 0.272, 0.560 58.8 X X X Comparative Example 4 0.276, 0.560 59.8 X X O Comparative Example 5 0.275, 0.560 59.1 X X X Comparative Example 6 0.275, 0.560 58.1 X X X

From Table 6, the photosensitive resin compositions of Examples 1 to 20 containing the compound according to one embodiment as a dye have a high color compared to the photosensitive resin compositions of Comparative Examples 1 to 6 that do not contain the compound. It can be confirmed that reproduction is possible and at the same time, luminance and chemical resistance are excellent, so it can be easily applied to image sensors, etc., making it possible to manufacture a high-definition display device with excellent color characteristics. Although the photosensitive resin composition of Example 21 is capable of realizing high colors, it can be seen that brightness, chemical resistance, developability, surface wrinkle characteristics, etc. are significantly lower than those of the photosensitive resin compositions of Examples 1 to 20.

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, which are also possible in accordance with the present invention. It is natural that it falls within the scope of the invention.

Claims (19)

A phthalocyanine-based compound represented by the following formula (1), where the shortest wavelength at half maximum with respect to the maximum absorption wavelength is located within the range of 610 nm to 620 nm:
[Formula 1]

In Formula 1,
R ¹ to R ⁴ are each independently a hydrogen atom,
R ⁵ to R ⁸ are each independently a hydrogen atom or a halogen atom,
R ⁹ to R ¹⁶ are each independently a halogen atom or represented by the following formula (2),
[Formula 2]

In Formula 2,
R ¹⁷ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
delete According to paragraph 1,
Formula 2 is a compound represented by any one of the following Formulas 2-1 to 2-4:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,
R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ²⁰ to R ²² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.
According to paragraph 1,
Any one of R ⁹ to R ¹⁶ is a compound represented by Formula 2.
According to paragraph 4,
The ‘any one of R ⁹ to R ¹² ’ or the ‘one of R ¹³ to R ¹⁶ ’ is a compound represented by Formula 2.
According to clause 5,
‘Any one of R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ ’ is a compound represented by Formula 2.
According to paragraph 1,
‘Any two of R ⁹ to R ¹⁶ ’ is a compound represented by Formula 2.
In clause 7,
The ‘any one of R ⁹ to R ¹² ’ and the ‘one of R ¹³ to R ¹⁶ ’ are compounds represented by Formula 2.
According to clause 8,
The ‘any one of R ¹⁰ and R ¹¹ ’ and the ‘one of R ¹⁴ and R ¹⁵ ’ are compounds represented by Formula 2.
According to paragraph 1,
The compound represented by Formula 1 is a compound represented by any one of the following Formulas 1-1 to 1-20.
[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]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

According to paragraph 1,
The compound is a green dye.
A photosensitive resin composition comprising the compound of any one of claims 1 and 3 to 11.
According to clause 12,
The photosensitive resin composition includes the compound in an amount of 1% to 40% by weight based on the total amount of the photosensitive resin composition.
According to clause 12,
The photosensitive resin composition further includes a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
According to clause 14,
The photosensitive resin composition further includes a pigment.
According to clause 14,
The photosensitive resin composition further includes a compound represented by the following formula (3):
[Formula 3]

In Formula 3 above,
R ²³ and R ²⁴ are each independently a hydroxy group or a substituted or unsubstituted C1 to C20 alkyl group,
n1 and n2 are each independently integers from 0 to 5, but 3 ≤ n1+n2 ≤ 5.
A photosensitive resin film manufactured using the photosensitive resin composition of claim 12.
A color filter comprising the photosensitive resin film of claim 17.
A display device comprising the color filter of claim 18.

Images