KR20210028832A - Low dielectric dye type black matrix for color filter on array - Google Patents

Abstract

The present invention relates to a low dielectric dye type black matrix for a color filter array structure and, more specifically, to a tetrabenzocorrolazine dye with high color intensity, a wide absorption range, low dielectric strength, and high durability, to a photosensitive resin composition comprising the dye, to a black matrix comprising the dye, and to a color filter comprising the black matrix.

Description

Low dielectric dye type black matrix for color filter on array

The present invention relates to a low dielectric tetrabenzocorrolazine dye for manufacturing a black matrix for a color filter on array structure, a photosensitive resin composition comprising the same, and a black matrix comprising the dye.

The color filter, which is a key component in an LCD or large OLED panel, is the most important component for improving display quality, and the black matrix is the second largest market among the components of color filters, and in particular, contributes greatly to improving the contrast ratio.

Conventionally, carbon black, which is easy to produce a strong black color and has excellent durability, was used as a black matrix material, but in the Color Filter On Array mode, which can improve the aperture ratio by more than 80% and is advantageous for thinning, the high dielectric constant of the carbon black transmits the electrical signal of TFT It interfered and became a big problem.

Accordingly, low-dielectric organic materials were studied and applied. The pigment type was a problem because the color intensity was not strong enough, and the dye type had low heat resistance and it was difficult to have a wide absorption range close to black.

Accordingly, in the Color Filter On Array mode, a carbon black replacement dye material having a low dielectric constant that does not interfere with the electrical signal of TFT is required.

The present inventors have tried to design a new dye matrix to have a strong and wide absorption range, and thus, a low dielectric tetrabenzocorrolazine dye, and a photosensitive resin composition comprising the same, have a high shielding ability, and a perylene-based dye When mixed with, it has a wide absorption range close to black, has excellent heat resistance, and has a low dielectric constant of 3 to 5, thereby confirming that there is a characteristic representing the function of an insulating film that does not interfere with the electrical signal of the TFT. Completed.

Korean Patent Registration No. 10-1966803 Japanese Patent Publication No. 2017-193689 Japanese Patent Registration No. 6426469

An object of the present invention was to develop a black matrix material using a new matrix that was not used for electronic materials in the past, and the conditions of high color strength, wide absorption range, low dielectric properties, and high durability, which are requirements as a black matrix material. To provide a tetrabenzocorrolazine dye satisfying all of and a black matrix comprising the dye.

In order to achieve the above object, the present invention

It provides a low-dielectric dye for a color filter black matrix comprising a compound represented by the following formula (1).

[Formula 1]

(here,

R ₁ is H, CH ₃ or 4-methylcyclohexyl,

R ₂ is H, OCH ₃ or (4-methylcyclohexyl)oxy[(4-Methylcyclohexyl)oxy]).

In addition, the present invention

It provides a low-dielectric dye for a color filter black matrix comprising a compound represented by a compound represented by any one of Formulas 2 to 4 below.

[Formula 2]

;

;

[Formula 3]

; 및

; And

[Formula 4]

.

.

In addition, the present invention

1) 4-nitrophthalonitrile and 2,5-bis-(1,1-dimethylbutyl)-methoxyphenol were dissolved in anhydrous DMSO, anhydrous K ₂ CO ₃ was added, and the stirred reaction mixture was filtered and purified. Synthesizing 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile;

2) The reaction was stirred after adding Li to the solution of 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile dissolved in anhydrous xylene and ethanol under a nitrogen atmosphere. Extracting and purifying the mixture to synthesize tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine; And

3) After dissolving the tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine in pyridine, PBr ₃ was added, and the resulting solution was heated and stirred. It provides a method of producing a low-dielectric dye for a color filter black matrix comprising the compound represented by Formula 1, including filtering and purifying.

In addition, the present invention

1) 4-nitrophthalonitrile and 2,5-bis-(1,1-dimethylbutyl)-methoxyphenol were dissolved in anhydrous DMSO, anhydrous K ₂ CO ₃ was added, and the stirred reaction mixture was filtered and purified. Synthesizing 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile;

2) The reaction was stirred after adding Li to the solution of 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile dissolved in anhydrous xylene and ethanol under a nitrogen atmosphere. Extracting and purifying the mixture to synthesize tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine; And

3) After dissolving the tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine in pyridine, PBr ₃ was added, and the resulting solution was heated and stirred. from,

a) after evaporating the solvent, pouring it into a water and ice bath, and then filtering the resulting suspension and purifying;

b) After reducing the volume by vacuum distillation, after treatment with a 50:50 solution of _{CH 2} Cl _{2 : MeOH, the resulting green solid was dissolved in CH 2} Cl ₂ and filtered to remove pyridinium bromide, a white crystalline solid. Reduce the volume of the filtrate and purify it under reduced pressure; or

c) After reducing the volume by vacuum distillation, _{the resulting green solid was dissolved in CH 2} Cl _{2 after treatment with a CH 2} Cl ₂ :4-methylcyclohexanol 50:50 solution and filtered to pyridinium as a white crystalline solid. After removing the bromide, the filtrate was reduced in volume and purified under reduced pressure; It provides a method for producing a low-dielectric dye for a color filter black matrix comprising the compound represented by Formula 1, comprising performing any one of the steps.

In addition, the present invention provides a photosensitive resin composition for a color filter black matrix comprising the dye according to the present invention.

In addition, the present invention relates to the dye according to the present invention and N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide ( It provides a photosensitive resin composition for a color filter black matrix including a dye N,N'-Bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide).

In addition, the present invention provides a black matrix comprising the dye according to the present invention.

In addition, the present invention relates to the dye according to the present invention and N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide ( It provides a black matrix including N,N'-Bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide) dye.

In addition, the present invention provides a color filter formed by forming the black matrix according to the present invention.

The present invention is designed to have a strong and wide absorption range using a new dye matrix, and was developed as a dye for manufacturing black mattresses using a new matrix that has not been used for electronic materials.

The present invention satisfies the requirements of a black matrix material such as high color strength, a wide absorption range, low dielectric properties, and high durability, thereby replacing carbon black, which is a black matrix material.

Specifically, the low dielectric tetrabenzocorrolazine dye according to the present invention and the black matrix prepared using the same have strong color intensity and have an optical density of 2 or more at a thickness of 3.0 um, and have a wide absorption range close to black when mixed with perylene-based dyes. As a result of measuring the most important dielectric constant in Color Filter On Array mode, it has a structure that is easy to aggregate between molecules, and has a value of 3 to 5, indicating the function of the insulating film that does not interfere with the electrical signal of the TFT.

1 is a diagram showing a synthesis process of dyes (RC 1 to 3) according to the present invention.
2 is a diagram showing the synthesis process of the dye 3 according to the present invention.
3 is a graph showing absorption spectra of synthesized dyes (RC 1 to 3) according to the present invention.
4 is a graph showing the results of TGA analysis of the synthesized dyes (RC 1 to 3) according to the present invention.
5 is a diagram showing a geometric optimization structure of the synthesized dyes (RC 1 to 3) according to the present invention.
6 is a graph showing the transmittance spectrum of the film produced according to the present invention.

Hereinafter, the present invention will be described in detail.

In describing the present invention, detailed descriptions of related known configurations or functions may be omitted.

Terms or words used in the present specification and claims are not limited to a conventional or dictionary meaning and are not interpreted, but should be interpreted as meanings and concepts consistent with the technical matters of the present invention.

Since the embodiments described in the present specification and the configurations shown in the drawings are preferred embodiments of the present invention, and do not represent all the technical spirit of the present invention, various equivalents and modifications that can replace them at the time of the present application are There may be.

The present invention

It provides a low-dielectric dye for a color filter black matrix comprising a compound represented by the following formula (1).

[Formula 1]

(here,

R ₁ is H, CH ₃ or 4-methylcyclohexyl,

R ₂ is H, OCH ₃ or (4-methylcyclohexyl)oxy[(4-Methylcyclohexyl)oxy]).

In addition, the present invention

It provides a low-dielectric dye for a color filter black matrix comprising a compound represented by a compound represented by any one of Formulas 2 to 4 below.

[Formula 2]

;

;

[Formula 3]

; 및

; And

[Formula 4]

.

.

The compound is

i) Hydroxyphosphorus (V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzocorol hydroxide (Hydroxyphosphorus( V)2(3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole hydroxide);

ii) Dimethoxyphosphorus (V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzocorol (Dimethoxyphosphorus(V)2) (3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole); And

iii) Di(4-methylcyclohexoxy)phosphorus (V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorol (Di(4-methylcyclohexoxy)phosphorus(V)2(3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole).

In addition, the present invention

1) 4-nitrophthalonitrile and 2,5-bis-(1,1-dimethylbutyl)-methoxyphenol were dissolved in anhydrous DMSO, anhydrous K ₂ CO ₃ was added, and the stirred reaction mixture was filtered and purified. Synthesizing 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile;

2) The reaction was stirred after adding Li to the solution of 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile dissolved in anhydrous xylene and ethanol under a nitrogen atmosphere. Extracting and purifying the mixture to synthesize tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine; And

3) After dissolving the tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine in pyridine, PBr ₃ was added, and the resulting solution was heated and stirred. It provides a method of producing a low-dielectric dye for a color filter black matrix comprising the compound represented by Formula 1, including filtering and purifying.

In the manufacturing method, step 3) is preferably performed in any one of the following a) to c).

a) evaporating the solvent of the reaction mixture of step 3), pouring it into a water and ice bath, filtering the resulting suspension, and purifying;

b) After reducing the volume of the reaction mixture of step 3) by vacuum distillation, the resulting green solid was dissolved _{in CH 2} Cl _{2 and filtered to reduce the volume of the reaction mixture with a 50:50 solution of CH 2} Cl _{2 :MeOH.} Reducing the volume of the filtrate under reduced pressure and purifying the filtrate after removing the solid pyridinium bromide; And

c) After reducing the volume of the reaction mixture of step 3) by vacuum distillation, the resulting green solid was dissolved _{in CH 2} Cl _{2 after treatment with a CH 2} Cl ₂ :4-methylcyclohexanol 50:50 solution. After filtering to remove pyridinium bromide as a white crystalline solid, reduce the volume of the filtrate under reduced pressure and purify it.

In addition, the present invention provides a photosensitive resin composition comprising the dye according to the present invention.

The photosensitive resin composition preferably has a dye content of 1 to 20% by weight, and more preferably 4 to 10% by weight.

The photosensitive resin composition is, in addition to the dye according to the present invention, N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide It is preferable to further include a dye (N,N'-Bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide).

The photosensitive resin composition may include another dye, a dye dispersant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent in addition to the dye according to the present invention.

The another dye may include an organic black pigment, a blue pigment, a carbon black, a violet pigment, and a red pigment.

The dispersant is added for deagglomeration and stability of the dye. Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more.

The alkali-soluble resin generally makes the non-exposed portion of the photosensitive resin layer formed using the photosensitive resin composition alkali-soluble, and also acts as a binder resin and dispersion medium for dyes.

The alkali-soluble resin may be used without particular limitation as long as it is a polymer soluble in an alkaline developer used in a developing step for manufacturing a color filter.

The photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator, and may contain 3 to 10 functional monomers and preferably 4 to 8 functional monomers, and these may be used alone or in combination of two or more.

The photopolymerization initiator may be used without limitation as long as it can polymerize the photopolymerizable compound, but preferably, in consideration of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, acetophenone-based compound, benzoin-based compound, benzophene It may be one or more compounds selected from the group consisting of non-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds.

As long as the solvent is effective in dissolving other components included in the photosensitive resin composition, the solvent used in the usual photosensitive resin composition may be used without particular limitation, and in particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols Or esters and the like are preferred, and the solvents may be used alone or in combination of two or more.

In addition to the above components, the photosensitive resin composition may contain other additives according to the needs of those skilled in the art within a range that does not impair the object of the present invention, and the additives are specifically, for example, other polymer compounds, thermal initiators, curing agents, interfacial It may further include one or more additives selected from the group consisting of an activator, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent.

In addition, the present invention provides a black matrix comprising the dye according to the present invention.

In addition to the dye according to the present invention, the black matrix is N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide ( It is preferable to further include N,N'-Bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide) dye.

The thickness of the black matrix is preferably 0.2 µm to 20 µm, more preferably 9.0 µm to 18 µm.

In addition, the present invention provides a color filter formed by forming the black matrix according to the present invention.

The color filter is a conventional patterning process according to a photolithography method.

a) applying a photosensitive resin composition to a substrate;

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

d) performing a developing process of dissolving the unexposed part using an aqueous alkali solution; And

e) It can be prepared including the steps of drying and post-baking.

The substrate may be a glass substrate or a polymer plate.

The coating may be performed by a wet coating method using an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (die coater), or inkjet to obtain a desired thickness.

The prebaking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and heating time in the prebaking may be appropriately selected according to the solvent used, and may be performed at a temperature of, for example, 80 to 150° C. for 1 to 30 minutes.

The exposure is performed by an exposure machine to expose only a portion corresponding to the pattern by exposing through a photo mask. The irradiated light at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

The above development is performed for the purpose of removing the colored photosensitive resin composition in the non-removed portion of the non-exposed portion of the alkali development, and a desired pattern is formed by this phenomenon. As a developer suitable for this alkali development, an aqueous solution of an alkali metal or alkaline earth metal carbonate can be used.

The post-baking is performed to increase the adhesion between the patterned film and the substrate, and may be performed through heat treatment at 100 to 220° C. for 10 to 120 minutes, and the post-baking is the same as the pre-baking, such as an oven or a hot plate. It can be carried out using, for example.

Hereinafter, the present invention will be described in more detail through examples and experimental examples. These Examples and Experimental Examples are only for describing the present invention in more detail, and that the scope of the present invention is not limited by these Examples and Experimental Examples according to the gist of the present invention is one of ordinary skill in the art. It is self-evident to the person.

< Example 1>

<1-1> 4-(2,5- Vis (1,1- Dimethylbutyl )-4- Methoxyphenoxy ) Phthalonitrile (4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile) (1)

4-nitrophthalonitrile (1 g, 5.77 mmol) and 2,5-bis-(1,1-dimethylbutyl)-methoxyphenol (1.68 g, 5.77 mmol) were dissolved in anhydrous DMSO (30 ml) and anhydrous K2CO3 (1.06 g, 7.66 mmol) was added in portions over 4 hours. The mixture was stirred at 40° C. for 24 hours under a nitrogen atmosphere. After filtering the reaction mixture, the residue was extracted with CH2Cl2 and dried by rotary evaporation. The pure product (2.19 g, 5.23 mmol) was collected by column chromatography on silica gel using a mixture of EA/hexane (10:1) as an eluent.

Yield 91%; 1H NMR (CDCl3, ppm): 7.69 (d, 1H), 7.22 (s, 1H), 7.14 (d, 1H), 6.82 (s, 1H), 6.63 (s, 1H), 3.08 (s, 3H, eOeCH3 ), 1.71 (m, 2H), 1.56 (m, 2H), 1.26 (d, 12H), 1.04 (m, 2H), 0.96 (m, 2H), 0.81 (t, 3H), 0.71 (t, 3H) .

<1-2> Tetrakis (2,5- Vis (1,1-dimethyl butyl)-4- Methoxyphenoxy )- Phthalosia Nin (tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-phthalocyanine) (2)

Li (0.13 g, 18.7 mmol) was added to a solution of 1 (0.9 g, 2.38 mmol) dissolved in anhydrous xylene (50 ml) and ethanol (10 ml) under a nitrogen atmosphere. The reaction mixture was stirred at 150° C. for 5 hours. After cooling the solution, the resulting slurry was extracted with CH2Cl2 (100 ml) and washed with saturated NaCl solution. The pure product (0.53 g, 0.31 mmol) was obtained by column chromatography on silica gel using CH2Cl2 as eluent.

Yield 54%; MALDI-TOF MS: m/z 1675.9 (100%, [M+2K]+). FT-IR (KBr, cm-1): 3289 (N-H). Calcd for C108H138N8O8: C, 77.38; H, 8.30; N, 6.68; O, 7.64%. Found: C, 77.36; H, 8.27; N, 6.66; O, 7.69%.

<1-3> Hydroxyphosphorus (V)2(3) - Tetrakis (2,5- Vis (1,1- Dimethylbutyl )-4-methoxyphenoxy)-triazatetrabenzocorol Hydroxide (Hydroxyphosphorus(V)2(3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole hydroxide) (RC1)

The 2 (1.24 g, 0.74 mmol) was placed in a 100 mL flask equipped with a condenser and a gas inlet adapter and dissolved in 20 mL of pyridine. A large amount of PBr3 (9.0 g, 33.0 mmol) was added, and the resulting solution was heated to 120° C. and stirred for 2 hours. After 2 hours, about 3/4 of the solvent was evaporated under a flow of argon. The mixture was then poured into a water/ice bath, and the resulting suspension was then filtered to give a green solid. The solid was purified on a silica gel column using 1/6 ethyl acetate/hexane as eluent. The bright green band was collected and concentrated to give RC1 as a bright green solid (0.45 g, 35%).

MALDI-TOF MS: m/z 1725.0 (100%, [M + OH]&lt;+&gt;); Found: C, 75.07; H, 8.15; N, 5.75. Calc. for C108H138N7O10P: C, 75.19; H, 8.06; N, 5.68.

< Example 2>

Dimethoxyphosphorus (V)2(3) - Tetrakis (2,5- Vis (1,1- Dimethylbutyl )-4- Methoxyphenoxy )-Triazatetrabenzocorol ( Dimethoxyphosphorus(V)2(3) - Tetrakis (2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole) (RC2)

The 2 (1.24 g, 0.74 mmol) was placed in a 100 mL flask equipped with a condenser and a gas inlet adapter and dissolved in 30 mL of pyridine. A large amount of PBr3 (9.0 g, 33.0 mmol) was added, and the resulting solution was heated to 120° C. and stirred for 2 hours. After 2 hours, the volume of the reaction mixture was reduced to 1-2 mL by vacuum distillation, and then treated with a 50/50 solution of CH2Cl2/MeOH for 2 hours. The resulting green solid was dissolved in CH2Cl2 and filtered to remove excess pyridinium bromide as a white crystalline solid. The filtrate was loaded onto a silica gel column to reduce the volume under reduced pressure and purify with 1/7 ethyl acetate/hexane as eluent. The eluting light green band was collected and dried under vacuum to give RC2 as a light green solid (0.75 g, 58%).

MALDI-TOF MS: m/z 1752.4 (100%, [M+]); Found: C, 75.17; H, 8.20; N, 5.65. Calc. for C110H142N7O10P: C, 75.35; H, 8.16; N, 5.59.

< Example 3>

Di(4-methylcyclohexoxy)phosphorus (V)2(3) - Tetrakis (2,5- Vis (1,1- Dimethylbutyl )-4-methoxyphenoxy)-triazatetrabenzcorol ( Di (4- methylcyclohexoxy)phosphorus(V)2(3) -Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole) (RC3)

The 2 (1.24 g, 0.74 mmol) was placed in a 100 mL flask equipped with a condenser and a gas inlet adapter and dissolved in 30 mL of pyridine. A large amount of PBr3 (9.0 g, 33.0 mmol) was added, and the resulting solution was heated to 120° C. and stirred for 2 hours. After 2 hours, the volume of the reaction mixture was reduced to 1-2 mL by vacuum distillation, and then treated with a 50/50 solution of CH2Cl2/4-methylcyclohexanol for 12 hours. The resulting green solid was dissolved in CH2Cl2 and filtered to remove excess pyridinium bromide as a white crystalline solid. The filtrate was loaded onto a silica gel column to reduce the volume under reduced pressure and purify with CH2Cl2 as eluent. The eluting second bright green band was collected and loaded onto a silica gel column for purification again with 3/40 ethyl acetate/hexane as eluent. The first light green band that elutes was collected and dried under vacuum to make RC3 a glossy light green solid (0.78 g, 55%).

MALDI-TOF MS: m/z 1917.8 (100%, [M+]); Found: C, 76.11; H, 8.56; N, 5.13. Calc. for C122H162N7O10P: C, 76.41; H, 8.52; N, 5.11.

< Example 4>

<4-1> N,N '- Vis (2,6- Diisopropylphenyl )-One- Bromoperylene -3,4,9,10- Tetracarboxydiimide ( N,N '- Bis (2,6- diisopropylphenyl )-One- bromoperylene -3,4,9,10-tetracarboxydiimide) (2a)

Perylene-3,4,9,10-tetracarboxylic dianhydride (16.0 g, 40.7 mmol), iodine (0.39 g, 1.52 mmol) and sulfuric acid ( 98%, 225ml) were mixed and stirred at room temperature for 2 hours. The reaction temperature was set to 80° C., and bromine (3.58 ml, 70 mmol) was added dropwise over 2 hours. The mixture was further reacted at 80° C. for 16 hours, cooled to room temperature, and the excess bromine gas was replaced with nitrogen gas. The precipitate obtained after adding ice water to the mixture was collected by suction filtration. The precipitate was washed several times with water until the aqueous layer became neutral to give dibromo dianhydride as a crude product. The crude product was then dried at 100° C. under reduced pressure and used in the next step without further purification.

Crude 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride (8.0 g, 14.5 mmol) , 2,6-diisopropylaniline (8.8 ml, 46.7 mmol) and acetic acid (4.6 ml) were mixed, and N-methyl-2-pyrrolidone (N-Methyl- It was heated at 120° C. for 96 hours in 2-pyrrolidone)(NMP) (100 ml). After adding water to the mixture, the obtained precipitate was collected by suction filtration. The crude product was washed with water, dried and purified by column chromatography on silica gel using CH2Cl2 as eluent. The band containing tribrominated diimide can be separated first. Subsequently, a second band containing a mixture of this brominated isomeric diimide was collected. The mixture was washed with EtOH and toluene and heated in toluene (50 ml) at 80° C. for 12 hours. Pure diimide, red compound 2b was recrystallized from hot toluene solution.

2a can be separated by column chromatography from the same crude product of 2b. After obtaining a mixture of this brominated isomeric diimide, 2a was obtained as the second eluted compound. Product 2a was used in the next step without further purification as there were no isomers.

<4-2> N,N '- Vis (2,6- Diiso Propylphenyl )-One- Phenoxy - Perylene -3,4,9,10- Tetra Carboxydiimide (N,N'-Bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide) (3)

The compound of 2a (1 g, 1.27 mmol) was mixed with anhydrous potassium carbonate (0.7 g), 4-tert-butylphenol (0.23 g, 1.50 mmol) and NMP (70 ml). ) And mixed. The mixture was heated to 120° C. under argon and stirred at this temperature for 24 hours. The reaction mixture was cooled to room temperature and poured into 5% HCl (250 ml). The precipitate was filtered, washed repeatedly with water, and vacuum dried at 70°C. The crude product was purified by column chromatography on silica gel using CH2Cl2 as eluent to give 3 as a red solid.

Yield 86.1%: 1H NMR (CDCl3, ppm): 9.68 (d, 1H), 8.82 (m, 2H), 8.75 (m, 3H), 8.42 (s, 1H), 7.48 (m, 4H), 7.33 (m , 4H), 7.13 (d, 2H), 2.74 (septet, 4H), 1.36 (s, 9H), 1.16 (d, 24H); MALDI-TOF MS: m/z 860.28 (100%, [M+2K]+).

< Example 5>

Manufacturing of Black Matrix

To prepare a dye-type black matrix, an ink was prepared by mixing a total of 0.10 g of synthesized dye, 2.02 g of PGMEA, and 0.38 g of an acrylic binder (Kolon Industry, Inc.). The prepared ink was coated on a transparent glass substrate using a Midas system spin-1200D spin coater. The coating speed at this time was 300 rpm for 20 seconds and 500 rpm for 10 seconds. Thereafter, the black matrix was cured through heat treatment of the coated substrate. The heat treatment conditions at this time were dried at 80° C. for 20 minutes, prebaked at 100° C. for 1 minute, and post-baked at 230° C. for 30 minutes.

< Experimental example 1> Dye properties

<1-1> Analysis of solubility of dyes

The synthesized dyes RC1, RC2, RC3, and 3 were dissolved in PGMEA (Propylene glycol monomethyl ether acetate) at 20° C. and solubility was measured.

Specifically, after the synthesized dye was added to PGMEA at various concentrations, the solution was ultrasonicated for 5 minutes using an ultrasonic cleaner NXP-4020. After allowing the solution to stand at room temperature for 48 hours, precipitation was checked to determine the solubility of the dye.

As a result, it is shown in Table 1. It was confirmed that the synthesized dyes have sufficient process solvent solubility.

Synthesized dye Solubility (g/100 ml) 3 8 RC1 9 RC2 9 RC3 10

<1-2> Analysis of absorption spectrum of dye

The synthesized dyes RC1, RC2, RC3 and 3 were respectively ^{measured in PGMEA (5×10 -6} mol litre ^-1 ) using a Scinco Mega-800 UV-Visible spectrophotometer.

As a result, it is shown in Fig. 3 and Table 2. The synthesized dye showed a very good molar extinction coefficient, and it was confirmed that it has a wide absorption range close to black, and when mixed with Perylene-based dye 3, it was found that it was possible to cover the entire visible light area.

Synthesized dye λmax (nm) ε _max (L mol ^{- 1} cm ^-1 ) RC1 450/662 183,594 / 91,996 RC2 450/662 158,640 / 81,918 RC3 450/662 244,538 / 126,696 3 532 77,434

<1-3> of dye TGA analysis

The synthesized dyes RC1, RC2, RC3 and 3 were measured for thermogravimetric analysis (TGA) by temperature, respectively.

Specifically, the TGA was measured using a TA Instruments thermogravimetric analyzer 2050 while heating up to 400° C. by 10° C. per minute.

As a result, it is shown in FIG. It was confirmed that the synthesized dye has excellent heat resistance with a weight loss of 5 wt% or less in the 220°C isothermal section (30 min), and RC1 has a slight weight loss due to the asymmetrical and somewhat unstable structure of the axial substituent, but the heat resistance of Dye 3 is high. When mixed and applied, it was found that the heat resistance was excellent.

<1-4> Analysis of dye geometry

The geometric structures of the synthesized dyes RC1, RC2, and RC3 were analyzed.

Specifically, the dye geometry was optimized by the Density Functional Theory (DFT) method in B3LYP/6-31G (d, p) performed in the Gaussian 09 program.

As a result, it is shown in FIG. It was found that the synthesized dye contributed to an increase in solubility by lowering the strong π-π interaction of the phthalocyanine matrix due to the steric hindrance effect of the Bulky substituents.

< Experimental example 2> Characteristics of Black Matrix

<2-1> Analysis of transmittance spectrum of black matrix

The transmission spectrum according to the wavelength of the prepared black matrix was measured using a Scinco Mega-800 UV-Visible spectrophotometer.

As a result, it is shown in FIG. In the condition of dye content of 4 wt% and film thickness of 9.0 μm, there was slight transmission around 470 nm and around 570 nm where there may be some light leakage, and the higher the molar extinction coefficient, the lower the transmittance on average. When adjusted to the (J Incl Phenom Macrocycl Chem (2015) 82:187-194) level (18.0 μm), the total transmittance was 0.

<2-2> Optical density analysis of black matrix

The prepared black matrix was analyzed for optical densities at 450, 550 and 650 nm.

Specifically, the intensity and thickness of incident light and transmitted light were calculated using a Scinco Mega-800 UV-Visible spectrophotometer, and the OD value was converted by Equation 1 below.

As a result, it is shown in Table 3. It was found to be a remarkably high value under the condition of 4 wt% dye content and 9.0 μm film thickness, which is the highest level among conventional dye types.

RC1+3 RC2+3 RC3+3 after
prebaking 450 nm 0.516/㎛ 0.494/㎛ 0.597/㎛ 550 nm 0.493/㎛ 0.490/㎛ 0.501/㎛ 650 nm 0.434/㎛ 0.421/㎛ 0.465/㎛ after
postbaking 450 nm 0.520/㎛ 0.498/㎛ 0.605/㎛ 550 nm 0.495/㎛ 0.493/㎛ 0.498/㎛ 650 nm 0.440/㎛ 0.425/㎛ 0.466/㎛

<2-3> Analysis of color change value of black matrix

The prepared black matrix was analyzed for ΔEab value according to the CIE 1931 chromaticity diagram.

According to the black matrix heat treatment conditions in Table 3, the ΔEab value between the pre-baking and post-baking processes was measured with a Scinco color spectrometer.

As a result, it is shown in Table 4. Like the dye TGA analysis, it was found that it has excellent heat resistance.

RC1+3 RC2+3 RC3+3 ΔEab 3.87 2.15 2.75

*Pre-baked at 90°C for 10 minutes and then post baked at 200°C for 30 minutes

<2-4> Analysis of the dielectric constant of the black matrix

The dielectric constant according to the frequency was measured for the prepared black matrix.

Specifically, the dielectric constant was measured using an Edward E306 thermal evaporator and an HP 4294A precision impedance analyzer, and the thickness of the black matrix was measured using a KLA-Tencor Nanospec AFT/200 alpha step. .

As a result, it is shown in Table 5. The low value of 3.54 ~ 4.88 was seen in all areas, compared to the high value of 17.1 ~ 26.39 in the same frequency range (Reference: J Incl Phenom Macrocycl Chem (2015) 82:187-194), remarkably It was confirmed that it has a low dielectric constant. In particular, it showed a particularly low value in the working frequency range (100~500kHz).

Frequency
(kHz) Dielectric constant (εr average) RC1+3 RC2+3 RC3+3 0.1 4.88 3.95 3.89 One 4.81 3.87 3.80 10 4.77 3.79 3.67 100 4.71 3.73 3.64 200 4.69 3.71 3.61 500 4.67 3.72 3.57 700 4.66 3.70 3.56 1,000 4.65 3.68 3.54

The black matrix is positioned between the RGB patterns of the color filter to prevent color mixing, and is also used for the purpose of shielding a portion where a pixel electrode is not formed and a reverse slope formed around a pixel electrode. In addition, the direct light irradiation of the TFT is blocked to prevent an increase in the leakage current of the TFT. The low-dielectric dye or photosensitive resin composition for manufacturing a black matrix of the present invention can be successfully applied to a display panel or an image sensor in which a black matrix is used. Characteristics.

Claims (11)

Low dielectric dye for a color filter black matrix comprising a compound represented by the following formula (1):
[Formula 1]

(here,
R ₁ is H, CH ₃ or 4-methylcyclohexyl,
R ₂ is H, OCH ₃ or (4-methylcyclohexyl)oxy[(4-Methylcyclohexyl)oxy]).
The method of claim 1,
The compound is a low dielectric dye for a color filter black matrix, characterized in that the compound represented by any one of the following formulas 2 to 4:
[Formula 2]

;
[Formula 3]

; And
[Formula 4]

.
The method of claim 1,
The compound is a low dielectric dye for a color filter black matrix, characterized in that any one of the following i) to iii):
i) Hydroxyphosphorus (V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzocorol hydroxide (Hydroxyphosphorus( V)2(3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole hydroxide);
ii) Dimethoxyphosphorus(V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzocorol (Dimethoxyphosphorus(V)2) (3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole); And
iii) Di(4-methylcyclohexoxy)phosphorus (V)2(3)-tetrakis(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorol (Di(4-methylcyclohexoxy)phosphorus(V)2(3)-Tetrakis(2,5-Bis(1,1-dimethylbutyl)-4-methoxyphenoxy)-triazatetrabenzcorrole).
1) 4-nitrophthalonitrile and 2,5-bis-(1,1-dimethylbutyl)-methoxyphenol were dissolved in anhydrous DMSO, anhydrous K ₂ CO ₃ was added, and the stirred reaction mixture was filtered and purified. Synthesizing 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile;
2) The reaction was stirred after adding Li to the solution of 4-(2,5-bis(1,1-dimethylbutyl)-4-methoxyphenoxy)phthalonitrile dissolved in anhydrous xylene and ethanol under a nitrogen atmosphere. Extracting and purifying the mixture to synthesize tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine; And
3) After dissolving the tetrakis(2,5-bis(1,1-dimethyl butyl)-4-methoxyphenoxy)-phthalocyanine in pyridine, PBr ₃ was added, and the resulting solution was heated and stirred. Including; filtering and purifying
A method for producing a low-dielectric dye for a color filter black matrix comprising a compound represented by the following formula (1):
[Formula 1]

(here,
R ₁ is H, CH ₃ or 4-methylcyclohexyl,
R ₂ is H, OCH ₃ or (4-methylcyclohexyl)oxy[(4-Methylcyclohexyl)oxy]).
The method of claim 4,
The step 3) is a method of producing a low-dielectric dye for a color filter black matrix, characterized in that any one of the following a) to c) is performed:
a) evaporating the solvent of the reaction mixture of step 3), pouring it into a water and ice bath, filtering the resulting suspension, and purifying;
b) After reducing the volume of the reaction mixture of step 3) by vacuum distillation, the resulting green solid was dissolved _{in CH 2} Cl _{2 and filtered to reduce the volume of the reaction mixture with a 50:50 solution of CH 2} Cl _{2 :MeOH.} Reducing the volume of the filtrate under reduced pressure and purifying the filtrate after removing the solid pyridinium bromide; And
c) After reducing the volume of the reaction mixture of step 3) by vacuum distillation, the resulting green solid was dissolved _{in CH 2} Cl _{2 after treatment with a CH 2} Cl ₂ :4-methylcyclohexanol 50:50 solution. After filtering to remove pyridinium bromide as a white crystalline solid, reduce the volume of the filtrate under reduced pressure and purify it.
A photosensitive resin composition for a color filter black matrix comprising the dye according to claim 1.
The method of claim 6,
A photosensitive resin composition for a color filter black matrix, characterized in that the content of the dye is 1 to 20% by weight.
The method of claim 6,
N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide (N,N'-Bis(2,6-diisopropylphenyl) )-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide) A photosensitive resin composition for a color filter black matrix, characterized in that it further comprises a dye.
A black matrix comprising the dye according to claim 1.
The method of claim 9,
N,N'-bis(2,6-diisopropylphenyl)-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide (N,N'-Bis(2,6-diisopropylphenyl) )-1-phenoxy-perylene-3,4,9,10-tetracarboxydiimide) Black matrix, characterized in that it further comprises a dye.
A color filter formed by forming the black matrix according to claim 9 or 10.

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