KR20210052193A - Compound, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and display device - Google Patents

Abstract

Provided are a phthalocyanine-based compound having the shortest wavelength at half maximum with respect to the maximum absorption wavelength within the range of 600 to 620 nm, a photosensitive resin composition comprising the same, a photosensitive resin film manufactured by using the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter.

Description

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

The present description relates to a compound, a photosensitive resin composition comprising the same, a photosensitive resin film, a color filter, and a display device.

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

In the pigment dispersion method, one of the methods of implementing a color filter, a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, and the pattern of the shape to be formed is exposed, and then the unexposed part is removed with a solvent. This is a method in which a colored thin film is formed by repeating a series of thermal curing processes. The photosensitive resin composition used to manufacture the color filter according to the pigment dispersion method is generally composed 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 has been actively applied to manufacturing LCDs such as mobile phones, notebook computers, monitors, and TVs. However, in recent years, a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, as well as excellent pattern characteristics, has been demanded for further improved performance. In particular, the demand for a colorant that can be applied to an image sensor that requires high luminance and high contrast ratio along with high color reproducibility is increasingly being demanded.

An image sensor refers to an image pickup device component that generates an image in a display device such as a mobile phone camera or DSC (Digital Still Camera), and is largely a charge coupled device (CCD) depending on the manufacturing process and application method. It can be classified as an image sensor and a complementary metal oxide semiconductor (CMOS) image sensor.

Since the photosensitive resin film for color filters used in the solid-state image sensor is required to have a film thickness of 1.5 μm or less, a large amount of pigment must be added to the photosensitive resin composition, and the sensitivity decreases accordingly, resulting in insufficient adhesion to the substrate, or There is a problem in that sufficient curing is not obtained, or the pattern formation property is remarkably deteriorated, such as dye elution from the exposed portion and color loss.

Accordingly, efforts have been made to develop a photosensitive resin composition for a color filter applicable to an image sensor that satisfies reliability such as luminance and chemical resistance while simultaneously implementing high colors.

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

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

Another embodiment is to provide a photosensitive resin film prepared by 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 in which the shortest wavelength of the half width for the maximum absorption wavelength is located within the range of 600nm to 620nm.

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 represented by a halogen atom or the following formula (2),

[Formula 2]

In Chemical 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 Formulas 2-1 to 2-4 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formula 2-1 to Formula 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'any one of R ¹³ to R ¹⁶ ' may be represented by Formula 2.

The'R ¹⁰ , R ¹¹ , ^{any one of R 14} and R ¹⁵ 'may be represented by Chemical Formula 2.

The'any two of R ⁹ to R ¹⁶ ' may be represented by Formula 2.

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

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

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

[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 comprising the 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 a pigment.

The photosensitive resin composition may further include a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

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 an integer of 0 to 5, but 3≦n1+n2≦5.

Another embodiment provides a photosensitive resin film prepared by 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.

Other specifics of aspects of the present invention are included in the detailed description below.

The compound according to an embodiment has excellent green spectral properties and a high molar absorption coefficient, and has excellent solubility in organic solvents, so that it can be used as a dye when preparing a photosensitive resin composition for a green color filter, and a photosensitive resin composition comprising the dye The photosensitive resin film manufactured by using and a color filter including the same may have excellent luminance and contrast ratio.

1 is a diagram for explaining the half-value width of the maximum absorption wavelength of the compound and the shortest wavelength of the half-value 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 in the specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and It means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, “alkyl group” refers to a C1 to C20 alkyl group, specifically C1 to C15 alkyl group, and “cycloalkyl group” refers to a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" refers to a C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, and "aryl group" refers to a C6 to C20 aryl group, specifically C6 to It means a C18 aryl group, "alkenyl group" means a C2 to C20 alkenyl group, specifically C2 to C18 alkenyl group, and "alkylene group" means a C1 to C20 alkylene group, specifically C1 It means a to C18 alkylene group, "arylene group" means a C6 to C20 arylene group, and specifically, it means a C6 to C16 arylene group.

Unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid" It means both are possible.

In the present specification, unless otherwise defined, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formula in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

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

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

In a color filter made of a photosensitive resin composition using a pigment as a colorant, there is a limit on the luminance and contrast ratio resulting from the pigment particle size, so the need for improving the luminance and contrast ratio is continuously raised. Efforts to implement a color filter with improved luminance and contrast ratio by preparing a photosensitive resin composition suitable for a dye by introducing a dye that does not form a dye are continuing, and by such efforts, in the case of a photosensitive resin composition using a dye as a main colorant instead of a pigment. However, it has been shown to have some effect on improving the luminance and contrast ratio.

Meanwhile, in recent years, there is a rapid increase in demand for photosensitive resin compositions that can be applied to solid state image sensors or complementary metal oxide semiconductor image sensors in addition to display devices such as conventional LCDs. In this case, when applied to the image sensor, it is impossible to implement a high color, and thus a problem that it is very difficult to manufacture a high-definition color filter is emerging. As described above, it is believed that the reason why high color is not implemented is because the pattern size of a color filter mounted on an image sensor of a solid-state image sensor is very small, about 1/100 to 1/200 times that of a conventional color filter pattern for LCD.

Accordingly, after a long study, the inventors of the present invention limited the shortest wavelength of the half-width for each maximum absorption wavelength of the phthalocyanine compound to a specific wavelength range, thereby reducing the size of 100 to 200 times smaller than the conventional color filter pattern size for LCD. Branches can be easily applied to patterns, increase resolution, reduce residues, and ultimately develop dye compounds used in photosensitive resin compositions for color filters capable of realizing high colors.

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

Phthalocyanine-based compounds located in the range of 600nm to 620nm, such as 610nm to 620nm, such as 611nm to 616nm, the shortest wavelength of the half width for the maximum absorption wavelength, compared to the phthalocyanine-based compound in which the shortest wavelength of the half width for the maximum absorption wavelength is outside the above range , Not only has excellent solubility in organic solvents, but also improves the luminance and chemical resistance of a photosensitive resin composition containing it as a colorant, and above all, it is possible to realize high color (decrease of Gx value on CIE color coordinates (Gx, Gy)). In that regard, there is a big difference.

For example, a phthalocyanine-based compound in which the shortest wavelength of the 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 represented by a halogen atom or the following formula (2),

[Formula 2]

In Chemical 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 properties and a high molar extinction coefficient. Furthermore, since the compound represented by Formula 1 necessarily contains at least one substituent represented by Formula 2, it may exhibit excellent solubility in an organic solvent and excellent luminance 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, luminance, and chemical resistance of the organic solvent are largely deteriorated, so that it can be used as a colorant in the photosensitive resin composition for color filters. In addition to being unreasonable, it can be very difficult to implement as a high-color reproduction image sensor.

The substituent represented by Formula 2 is “an aryloxy group having one or two alkyl groups as a substituent” or “an alkoxy group having one or two alkyl groups as a substituent”, and in the aryloxy group, the alkyl group is ortho Since it is substituted at the (ortho) and/or para position, brightness and chemical resistance can be further improved. For example, when 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 Formulas 2-1 to 2-4 below, but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formula 2-1 to Formula 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 branch such as a tert-butyl group than in the case of a linear alkyl group such as a methyl group, an ethyl group, or an n-butyl group. The alkyl group may be more advantageous in terms of luminance 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 luminance and chemical resistance. It can be more advantageous.

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

In addition, the phthalocyanine-based compound represented by Formula 1 includes 4 hydrogen atoms and at least 4 halogen atoms, and due to such structural characteristics, solubility in an organic solvent may be further improved. More specifically, the phthalocyanine-based compound represented by Formula 1 is 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 A benzene ring having a group represented by and iv) ^{four benzene rings of a benzene ring having a group represented by R 13} to R ¹⁶ are included in the core structure, including a substituent represented by Formula 2 among the four benzene rings. In the benzene ring, all three groups other than the substituent represented by Formula 2 are halogen atoms, and all four groups of the benzene ring not including the substituent represented by Formula 2 may be hydrogen atoms or halogen atoms, and such structural characteristics Therefore, the shortest wavelength of the half width for the maximum absorption wavelength can be easily located within the range of 600nm to 620nm, the solubility in the organic solvent can be further improved, and it can be advantageous in terms of improving brightness and securing process characteristics.

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

For example, ^{one or two of R 9} to R ¹⁶ may be represented by Formula 2. When ^{one or two of R 9} to R ¹⁶ are not represented by Formula 2, a problem of lowering the luminance may occur.

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

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

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

For example, the compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-20, but is not 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 express more vivid colors even in a small amount.When used as a colorant, color characteristics such as brightness and contrast ratio This excellent display device can be manufactured. 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.

In general, dyes are the most expensive constituents among the constituents used in color filters. Therefore, in order to achieve a desired effect, such as high luminance or high contrast ratio, more expensive dyes must be used, resulting in an increase in production cost. However, when the compound according to an embodiment is used as a dye in a color filter, excellent color characteristics such as high luminance and high contrast ratio can be achieved even with a small amount, thereby reducing production cost.

According to another embodiment, a photosensitive resin composition including the phthalocyanine-based compound according to the 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 an embodiment may serve as a colorant, such as a dye, such as a green dye, in the photosensitive resin composition, and thus may exhibit excellent color characteristics.

The compound according to an embodiment is 1% to 40% by weight, such as 10% to 40% by weight, such as 20% to 40% by weight, such as 1% to 30% by weight, for example, based on the total amount of the photosensitive resin composition. It may be included in an amount of 1% to 20% by weight, for example, 1% to 10% by weight. When the compound according to the embodiment is included in the above range, color reproduction and contrast ratio are 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 C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment yellow 150, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

The green pigment is C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment green 59, etc. are mentioned, and these can be used individually or in mixture of 2 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 in the solvent.

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

Nonionic dispersants, anionic dispersants, cationic dispersants, and the like may be used as the dispersant. Specific examples of the dispersant include polyalkylene glycol and esters thereof, 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, and the like, and these may be used alone or in combination of two or more.

Examples of commercially available products of the above dispersant are 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 Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are PB711 and PB821 of Ajinomoto.

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, it is possible to maintain an appropriate viscosity, and thus the dispersibility of the photosensitive resin composition is excellent, and thus the optical, physical and chemical quality can be maintained when the product is applied.

As a solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like may be used.

The pigment dispersion may be included in an amount of 10% to 20% by weight, such as 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 a process margin, and color reproduction 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 including at least one acrylic repeating unit.

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

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; And the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Rate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, etc., but are not limited thereto, and these may be used alone or in combination of two or more. .

For example, the binder resin may further include an epoxy resin together 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, has an appropriate viscosity, and has excellent adhesion to a 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, such as 1% to 15% by weight, such as 1% to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, developability is excellent and crosslinking property is improved when manufacturing a color filter, so that excellent surface smoothness can be obtained.

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

Since the photopolymerizable compound has the ethylenically unsaturated double bond, it is possible to form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern 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, 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( Meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

Commercially available products of the photopolymerizable compound are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^{®; KAYARAD TC-110S ®} of Nihon Kayaku Co., Ltd., TC-120S ^®, etc.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^{®; KAYARAD HDDA ®} , HX-220 ^® , R-604 ^{® of} Nihon Kayaku Co., Ltd.; Osaka Yuki Kagaku High School Co., Ltd.'s V-260 ^® , V-312 ^® , and V-335 HP ^® are listed. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -710 ^® , M-8030 ^® , M-8060 ^®, etc.; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka Yuki Kayaku High School Co., Ltd.'s V-295 ^® , East-300 ^® , East-360 ^® , East-GPT ^® , East-3PA ^® , and East-400 ^® are listed. The above products can be used alone or in combination of two or more.

The photopolymerizable compound may be used after treatment with an acid anhydride in order to impart better developability.

The photopolymerizable compound may be included in an amount of 1% to 15% by weight, such as 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, hardening occurs sufficiently during exposure in the pattern formation process, thereby providing excellent reliability and excellent developability in an alkaline developer.

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or a combination thereof Can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt -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, and the like.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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. are mentioned.

Examples of the oxime-based compound 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-based compound 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)-butan-1-oneoxime-O- Acetate, etc. are mentioned.

In addition to the above compounds, the photopolymerization initiator may be a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, or a fluorene-based compound.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and becoming excited and then transferring the energy.

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% to 10% by weight, such as 0.1% to 5% 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 in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to unreacted initiators. It is possible to prevent a decrease in transmittance.

The solvent may have compatibility with a compound, a pigment, a binder resin, a photopolymerizable compound, and a photopolymerization initiator according to an embodiment, but materials that do not react may be used.

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; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl 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 3-oxy methyl propionate and 3-oxy ethyl propionate; 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 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionate propyl; 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 propionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid And high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, ?butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

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 balance, for example, 30% to 80% by weight based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus processability is excellent in manufacturing a color filter.

The photosensitive resin composition may further include a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

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 an integer of 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 is a C1 to C20 alkyl group substituted with an alkyl group, R ²⁴ is a hydroxy group, n1 is 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 with 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 parts by weight to 20 parts by weight, for example, 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an 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, γ glycidoxy propyl tri Methoxysilane, βepoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 parts by weight 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 and storage properties are excellent.

In addition, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defects from being generated, if necessary.

Examples of the surfactants include, BM Chemie BM-1000 ^® of社, BM-1100 ^®, and the like; ^{Mecha Pack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^®, etc. of Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

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

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

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

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

Applying the photosensitive resin composition onto a supporting substrate by spin coating, slit coating, inkjet printing, or the like; Drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film to light; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to prepare a photosensitive resin film; And a step of heat treating the photosensitive resin film. Since the above process conditions are widely known in the art, detailed descriptions thereof will be omitted herein.

Hereinafter, the present invention will be described in more detail with reference to examples, but 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 a compound represented by Formula 1-1

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), 2-isopropropyl-phenol (2.56g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N-dimethylformamide) ( 25ml) was added and stirred while heating to 70°C. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2-isopropropyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2-isopropropyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.73g), phthalonitrile (0.35g) 1,8-Diazabicycloundec 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, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-1 below.

[Formula 1-1]

Maldi-tof MS: 1190.69 m/z

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

In a 100 mL flask, 4-(2-isopropropyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.91g), phthalonitrile (0.70g) 1,8-Diazabicycloundec 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, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-2 below.

[Formula 1-2]

Maldi-tof MS: 1090.96 m/z

Synthesis Example 3: Synthesis of a 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 (N,N-dimethylformamide) )(25ml) was added and stirred while heating to 70℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction, concentration, and purification by column chromatography, purification and vacuum drying to obtain 4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), phthalonitrile (0.34g) 1,8 -Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.48g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-3 below.

[Formula 1-3]

Maldi-tof MS: 1218.75 m/z

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

In a 100 mL flask, 4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.80g), phthalonitrile (0.67g) 1,8 -Diazabicycloundec-7-ene (4.01g) and 1-pentanol (30g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.97g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-4 below.

[Formula 1-4]

Maldi-tof MS: 1104.98 m/z

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

In a 100ml flask, 3,4,5,6-tetrachlorophthalonitrile (5g), p-cresol (2.83g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (25ml) Put and stir while heating to 70 ℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2-methyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2-methyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.79g), phthalonitrile (0.38g) 1,8-Diazabicycloundec 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, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-5 below.

[Formula 1-5]

Maldi-tof MS: 1134.58 m/z

Synthesis Example 6: Synthesis of a 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 (N,N-dimethylformamide) )(25ml) was added and stirred while heating to 70℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.76g), phthalonitrile (0.36g) 1,8 -Diazabicycloundec-7-ene (2.17g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.52g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-6 below.

[Formula 1-6]

Maldi-tof MS: 1162.64 m/z

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

In a 100 mL flask, 4-(2,6-dimethyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (3.03g), phthalonitrile (0.73g) 1,8 -Diazabicycloundec-7-ene (4.33g) and 1-pentanol (30g) are added and heated to 90°C to dissolve the solid, then zinc acetate (1.04g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-7 below.

[Formula 1-7]

Maldi-tof MS: 1076.93 m/z

Synthesis Example 8: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), phthalonitrile (0.34g) ) Add 1,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g), heat to 90℃ to dissolve the solid, add zinc acetate (0.48g), and stir while heating to 140℃. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-8 below.

[Formula 1-8]

Maldi-tof MS: 1330.96 m/z

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

In a 100 mL flask, 4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (2.80g), phthalonitrile (0.68g) ) Add 1,8-Diazabicycloundec-7-ene (4.01g) and 1-pentanol (15g), heat to 90℃ to dissolve the solid, add zinc acetate (0.97g), and stir while heating to 140℃. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-9 below.

[Formula 1-9]

Maldi-tof MS: 1161.09 m/z

Synthesis Example 10: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2-tert-Butyl-4-methyl phenoxy)-3,5,6-trichloro-phthalonitrile.

4-(2-tert-Butyl-4-methylphenoxy)-3,5,6-trichloro-phthalonitrile (2 g), 3,4,5,6-tetrachlorophthalonitrile (0.68 g), phthalonitrile (0.33 g) 1 in a 100 mL flask ,8-Diazabicycloundec-7-ene (1.9g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.47g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-10 below.

[Formula 1-10]

Maldi-tof MS: 1246.80 m/z

Synthesis Example 11: Synthesis of a 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 -Pentanol (15g) is added and heated to 90℃ to dissolve the solid, then zinc acetate (0.47g) is added and heated to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-11 below.

[Formula 1-11]

Maldi-tof MS: 1109.03 m/z

Synthesis Example 12: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile.

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 heat to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-12 below.

[Formula 1-12]

Maldi-tof MS: 1094.60 m/z

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

4-(2,2-dimethyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (1 g), 3,4,5,6-tetrachlorophthalonitrile (1.67 g), phthalonitrile (0.40 g) 1 in a 100 mL 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 heat to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, filtered, and dried under vacuum. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-13 below.

[Formula 1-13]

Maldi-tof MS: 1042.91 m/z

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

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 in a 100 mL flask -Pentanol (15g) is added and heated to 90℃ to dissolve the solid, then zinc acetate (0.58g) is added and heated to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, filtered, and dried under vacuum. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-14 below.

[Formula 1-14]

Maldi-tof MS: 956.84 m/z

Synthesis Example 15: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.84g), phthalonitrile (0.40g) 1,8 -Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.58g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-15 below.

[Formula 1-15]

Maldi-tof MS: 1094.60 m/z

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

In a 100 mL flask, 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile (1 g), 3,4,5,6-tetrachlorophthalonitrile (1.67 g), phthalonitrile (0.40 g) 1,8 -Diazabicycloundec-7-ene (2.40g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.58g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-16 below.

[Formula 1-16]

Maldi-tof MS: 1042.91 m/z

Synthesis Example 17: Synthesis of a compound represented by Chemical Formula 1-17

In a 100 mL flask, 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 Add alcohol (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, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-17 below.

[Formula 1-17]

Maldi-tof MS: 956.84 m/z

Synthesis Example 18: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). After extraction and concentration, it is purified by column chromatography. After purification, it is vacuum-dried to obtain 4-(3-methyl-1-butoxy)-3,5,6-trichloro-phthalonitrile.

In a 100 mL flask, 4-(2-methyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.88g), phthalonitrile (0.42g) 1,8 -Diazabicycloundec-7-ene (2.52g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.61g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-18 below.

[Formula 1-18]

Maldi-tof MS: 1066.55 m/z

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

In a 100 mL flask, 4-(2-methyl-1-propoxy)-3,5,6-trichloro-phthalonitrile (1 g), 3,4,5,6-tetrachlorophthalonitrile (1.76 g), phthalonitrile (0.42 g) 1,8 -Diazabicycloundec-7-ene (2.52g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.61g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-19 below.

[Formula 1-19]

Maldi-tof MS: 1028.89 m/z

Synthesis Example 20: Synthesis of a 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 ol (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, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is appropriately added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 1-20 below.

[Formula 1-20]

Maldi-tof MS: 928.78 m/z

Synthesis Example 21: Synthesis of a compound represented by Chemical Formula 1-21

4-(2,4-di-t-butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2 g), phthalonitrile (2.03 g) 1,8-Diazabicycloundec-7-ene (4.01 g) in a 100 mL flask And 1-pentanol (15g) is added and heated to 90°C to dissolve the solid, then zinc acetate (0.97g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo 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 a compound represented by Chemical Formula C-1

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

[Chemical Formula C-1]

Maldi-tof MS: 1584.04 m/z

Comparative Synthesis Example 2: Synthesis of a 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℃. After completion of the reaction, extraction was performed with ethyl acetate (EA). A solid can be obtained by concentration after extraction. The obtained solid was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo 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 (14g) is added and heated to 90℃ to dissolve the solid, then zinc acetate (0.26g) is added and heated to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (C-2).

[Chemical Formula C-2]

Maldi-tof MS: 1808.47 m/z

Comparative Synthesis Example 3: Synthesis of a compound represented by Chemical 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 (N,N-dimethylformamide) ( 25ml) was added and stirred while heating to 70°C. After completion of the reaction, extraction was performed with ethyl acetate (EA). A solid can be obtained by concentration after extraction. The obtained solid was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to obtain 3,4,6-Trichloro-5-(2,4-dimethoxy-phenoxy)-phthalonitrile.

In a 100 mL flask, add 3,4,6-Trichloro-5-(2,4-dimethoxy-phenoxy)-phthalonitrile (2 g), 1,8-Diazabicycloundec-7-ene (0.99 g) and 1-pentanol (14 g). The mixture is heated to 90℃ to dissolve the solid, and then zinc acetate (0.24g) is added and heated to 140℃ while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (C-3).

[Chemical Formula C-3]

Maldi-tof MS: 1591.80 m/z

Comparative Synthesis Example 4: Synthesis of a compound represented by Chemical Formula C-4

In a 100 mL flask, 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 ,8-Diazabicycloundec-7-ene (1.38g) and 1-pentanol (14g) were added and heated to 90°C to dissolve the solid, then zinc acetate (0.33g) was added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (C-4).

[Chemical Formula C-4]

Maldi-tof MS: 1237.54 m/z

Comparative Synthesis Example 5: Synthesis of a compound represented by Chemical Formula C-5

In a 100 mL flask, 4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), 4,5-dichlorophthalonitrile (0.52g) ) Add 1,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g), heat to 90℃ to dissolve the solid, add zinc acetate (0.48g), and stir while heating to 140℃. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (C-5).

[Chemical Formula C-5]

Maldi-tof MS: 1287.63 m/z

Comparative Synthesis Example 6: Synthesis of a compound represented by Chemical Formula C-6

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2 g), 3,4,5,6-tetrachlorophthalonitrile (0.70 g), 4-dichlorophthalonitrile (0.43 g) 1 in a 100 mL flask ,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) are added and heated to 90°C to dissolve the solid, then zinc acetate (0.48g) is added and heated to 140°C while stirring. After completion of the reaction, the precipitation was confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. After purification, the obtained solid edichloromethane is appropriately added to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (C-6).

[Chemical Formula C-6]

Maldi-tof MS: 1253.19 m/z

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

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 compared with Synthesis Examples 1 to 20 The absorption spectrum for each of the phthalocyanine-based compounds according to Synthesis Examples 1 to 6 was obtained, and the results are shown in Table 1 below. (UV-1800, SHIMADZU)

Shortest wavelength at half width 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 measurement

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

Solubility evaluation criteria

Compound (solvent) is dissolved in 10% by weight or more based on the total amount of the diluted solvent: ○

Dissolution of less than 10% by weight of compound (solute) based on the total amount of diluent: X

(Unit: wt%) 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 an embodiment, have better solubility in an organic solvent than the compounds of Synthesis Example 21 and Comparative Synthesis Examples 1 to 6, and the photosensitive resin composition It can be seen that it can exhibit excellent color characteristics when used on the back.

(Synthesis of photosensitive resin composition)

Example 1

The components mentioned below were mixed in the composition shown in Tables 3 to 5 below to prepare a photosensitive resin composition according to Examples 1 to 21 and Comparative Examples 1 to 6.

Specifically, after dissolving a photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 2 hours, and then a binder resin and a photopolymerizable monomer were added thereto, followed by stirring at room temperature for 2 hours. Subsequently, the compound (dye) and pigment (pigment dispersion type) prepared in Synthesis Example were added as a colorant to the obtained reactant and stirred at room temperature for 1 hour. Then, 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: wt%) Example One 2 3 4 5 6 7 8 9 10 Binder resin EHPE-3150
(DAICEL, epoxy system) 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: wt%) Example 11 12 13 14 15 16 17 18 19 20 Binder resin EHPE-3150
(DAICEL, epoxy system) 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: wt%) Example Comparative example 21 One 2 3 4 5 6 Binder resin EHPE-3150
(DAICEL, epoxy system) 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 coordinate, luminance, chemical resistance, developability and surface wrinkle

The photosensitive resin composition prepared in Examples 1 to 21 and Comparative Examples 1 to 6 was applied to a thickness of 1 µm to 3 µm on a degreasing and washed glass substrate, and a hot plate at 90°C It was dried on the bed for 2 minutes to obtain a coating film. Subsequently, the coating film was exposed using a high-pressure mercury lamp having a dominant wavelength of 365 nm. Thereafter, a sample was obtained by drying for 20 minutes in a hot air circulation drying furnace at 230°C. The pixel layer was evaluated for color purity 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 shown in Table 6 below.

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

Through the coating and exposure process, developability was confirmed using a developer (SVS company, KOH diluent), 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 with a scanning electron microscope, and the results are shown in Table 6 below.

Criteria for evaluation of chemical resistance

del(E*) is less than 3: ○

del(E*) is 3 or greater: X

Developability evaluation criteria

BP less than 60 seconds: ○

BP over 60 seconds: X

Surface wrinkle evaluation criteria

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

When observed with a scanning electron microscope, wrinkles were observed on the pattern surface: X

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 including the compound according to an embodiment as a dye were compared with the photosensitive resin compositions of Comparative Examples 1 to 6 not including the compound, and high color It can be seen that the reproducibility is possible and at the same time excellent in luminance and chemical resistance, it is easily applied to an image sensor, etc., so that it is possible to manufacture a high-definition display device having excellent color characteristics. The photosensitive resin composition of Example 21 is capable of implementing a high color, but it can also be seen that brightness, chemical resistance, developability, and surface wrinkle characteristics are significantly lower than those 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 it is possible to implement various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It is natural to fall within the scope of the invention.

Claims (19)

Phthalocyanine-based compounds in which the shortest wavelength of the half width for the maximum absorption wavelength is located within the range of 600nm to 620nm.
The method of claim 1,
The phthalocyanine-based compound is a compound 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 represented by a halogen atom or the following formula (2),
[Formula 2]

In Chemical 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 method of claim 2,
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 Formula 2-1 to Formula 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.
The method of claim 1,
Any one of R ⁹ to R ¹⁶ is a compound represented by Formula 2.
The method of claim 4,
The'any one of R ⁹ to R ¹² ' or the'any one of R ¹³ to R ¹⁶ ' is a compound represented by Formula 2.
The method of claim 5,
The'R ¹⁰ , R ¹¹ , ^{any one of R 14} and R ^15'is a compound represented by Formula 2.
The method of claim 1,
The'any two of R ⁹ to R ¹⁶ ' is a compound represented by the formula (2).
The method of claim 7,
The'any one of R ⁹ to R ¹² ' and the'any one of R ¹³ to R ¹⁶ ' is a compound represented by Formula 2 above.
The method of claim 8,
The'any one of R ¹⁰ and R ¹¹ ' and the'any one of R ¹⁴ and R ¹⁵ ' is a compound represented by Formula 2 above.
The method of claim 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]

The method of claim 1,
The compound is a green dye.
A photosensitive resin composition containing the compound of any one of Claims 1-11.
The method of claim 12,
The compound is a photosensitive resin composition contained in an amount of 1% to 40% by weight based on the total amount of the photosensitive resin composition.
The method of claim 12,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The method of claim 14,
The photosensitive resin composition is a photosensitive resin composition further comprising a pigment.
The method of claim 14,
The photosensitive resin composition further comprises a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
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 an integer of 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.

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