KR102697047B1 - Diketopyrrolopyrrole compound, manufacturing method thereof, colored photosensitive resin composition comprising same, and color filter employing same - Google Patents

Abstract

The present invention provides a diketopyrrolopyrrole compound as a pigment synergist, which is a key material for improving pigment dispersibility and dispersion stability, and a color filter employing the same can exhibit excellent performance in terms of brightness and tinting power, which are key performances.

Description

Diketopyrrolopyrrole compound, manufacturing method thereof, colored photosensitive resin composition comprising same, and color filter employing same

The present invention relates to a diketopyrrolopyrrole compound, a method for producing the same, a colored photosensitive resin composition comprising the same, and a color filter employing the same.

In the display industry, the role of color filters is the most important among the various core components of LCDs in order to obtain colors closer to nature by implementing more vivid colors, distinct contrast and brightness, etc.

The core components of a color filter are mainly composed of matrix resin, color paste, photoinitiator, and various additives. Among these, the color paste is a state in which pigments are dispersed, so it can be said to be a key material that determines the core performance of the color filter, namely brightness and tinting power.

In particular, as consumers' demands for display devices such as TVs and smartphones become increasingly demanding, it is very important to maximize transmittance by reducing light scattering through atomization and dispersion of pigment particles in color paste to implement brighter and more distinct colors. In this way, atomization and dispersion can improve the brightness of the color filter, thereby improving the contrast ratio of the display.

The key material that can atomize pigments in color paste is a pigment synergist, which exists between pigments and dispersants, and therefore, as a key material for improving pigment atomization and dispersion stability, development of a pigment synergist with improved performance is necessary.

Korean Patent Publication No. 10-2017-0077460 A Japanese Publication Patent 2009-092924 A

The purpose of the present invention is to provide a pigment synergist, which is a key material for improving pigment dispersibility and dispersion stability, and to provide a color filter employing the pigment synergist, which has improved brightness and tinting power, which are key performances of the color filter.

The present invention provides a diketopyrrolopyrrole compound represented by the following chemical formula 1.

[Chemical Formula 1]

[In the above chemical formula 1,

R ₁ to R ₅ are independently hydrogen, halogen, cyano, (C1-C10)alkyl or (C6-C12)aryl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C20)alkyl or (C7-C20)arylalkyl;

m and n are independently 1 or 2.]

In the above chemical formula 1, R ₁ to R ₅ are each independently hydrogen, halogen, cyano, (C1-C7)alkyl or (C6-C10)aryl; R ₆ is hydrogen or -COOR ₁₁ ; R ₁₁ is (C1-C10)alkyl or (C7-C10)arylalkyl; m and n may each independently be 1 or 2.

In addition, according to one embodiment of the present invention, R ₁ to R ₅ of the chemical formula 1 are each independently hydrogen, halogen, cyano, (C1-C5)alkyl or (C6-C10)aryl; R ₆ is hydrogen or -COOR ₁₁ ; R ₁₁ is (C1-C6)alkyl; and m and n may each independently be 1 or 2.

A diketopyrrolopyrrole compound according to one embodiment of the present invention can be represented by the following chemical formula 2 or chemical formula 3.

[Chemical formula 2]

[Chemical Formula 3]

[In the above chemical formulas 2 and 3,

R ₃ is hydrogen, halogen, (C1-C3)alkyl or phenyl;

R ₄ is hydrogen, cyano or (C1-C3)alkyl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C3) alkyl.]

According to one embodiment of the present invention, the diketopyrrolopyrrole compound may be selected from the following compounds.

In addition, the present invention provides a method for producing a diketopyrrolopyrrole compound, and the diketopyrrolopyrrole compound represented by the following chemical formula 1 can be produced by reacting a compound of chemical formula 4 and a compound of chemical formula 5.

[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the above chemical formulas 1, 4 and 5,

R ₁ to R ₅ are independently hydrogen, halogen, cyano, (C1-C10)alkyl or (C6-C12)aryl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C20)alkyl or (C7-C20)arylalkyl;

m and n are independently 1 or 2.]

According to one embodiment of the present invention, a colored photosensitive resin composition comprising a diketopyrrolopyrrole compound is provided, which may include a pigment; and a diketopyrrolopyrrole compound according to one embodiment of the present invention as a pigment-synergist; and the pigment is characterized in that it contains a diketopyrrolopyrrole red pigment.

Additionally, the above-mentioned colored photosensitive resin composition can be used for a color filter.

According to one embodiment of the present invention, the diketopyrrolopyrrole compound may be included in an amount of 0.01 to 2.0 wt% based on the total weight of the colored photosensitive resin composition.

In addition, in one embodiment of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of a dispersant, a binder resin, an organic solvent, a photoinitiator, a crosslinking agent, and a surfactant.

The present invention provides a color filter formed by a colored photosensitive resin composition according to one embodiment of the present invention.

Additionally, the present invention provides a display device including a color filter according to one embodiment of the present invention.

The diketopyrrolopyrrole compound according to one embodiment of the present invention is a material that can improve the dispersibility and dispersion stability of pigments by being included as a pigment-synergist in a colored photosensitive resin composition, and a color filter employing the compound can exhibit excellent performance in terms of core performances such as brightness and coloring power.

The present invention provides a diketopyrrolopyrrole compound, a method for producing the same, a colored photosensitive resin composition comprising the same, and a color filter employing the same.

The singular form used in the present invention is intended to include the plural form as well, unless the context specifically indicates otherwise.

As used herein, the term “comprises” is an open-ended description having the equivalent meaning of “comprises,” “contains,” “has,” or “characterized by,” and does not exclude additional elements, materials, or processes not listed.

The “alkyl” described in the present invention includes both straight-chain and branched forms and may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In another embodiment, the alkyl may have 1 to 6 carbon atoms.

The “aryl” described in the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and includes a single or fused ring system having suitably 4 to 7, preferably 5 or 6 ring atoms in each ring, and includes even a form in which a plurality of aryls are connected by single bonds. The fused ring system may include an aliphatic ring such as a saturated or partially saturated ring, and necessarily includes at least one aromatic ring. In addition, the aliphatic ring may contain nitrogen, oxygen, sulfur, carbonyl, etc. in the ring. Specific examples of the aryl radical include, but are not limited to, phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, 9,10-dihydroanthracenyl, and the like.

The term “arylalkyl” as used herein refers to an alkyl group in which at least one hydrogen atom is substituted with aryl. Here, aryl and alkyl are as defined above. For example, arylalkyl includes, but is not limited to, benzyl, phenethyl, phenylvinyl, and the like.

“Halogen” as described in the present invention means fluorine, chlorine, bromine or iodine.

The carbon number described in alkyl, etc. described in the present invention does not include the carbon number of the substituent. For example, (C1-C10) alkyl means alkyl having 1 to 10 carbon atoms that does not include the carbon number of the substituent of the alkyl.

Hereinafter, the present invention will be described in detail. In this case, if there is no other definition for the technical and scientific terms used, they have the meaning commonly understood by a person with ordinary knowledge in the technical field to which this invention belongs, and in the following description, a description of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

The present invention provides a diketopyrrolopyrrole compound represented by the following chemical formula 1.

[Chemical Formula 1]

[In the above chemical formula 1,

R ₁ to R ₅ are independently hydrogen, halogen, cyano, (C1-C10)alkyl or (C6-C12)aryl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C20)alkyl or (C7-C20)arylalkyl;

m and n are independently 1 or 2.]

A color paste employing a colored photosensitive resin composition containing the above diketopyrrolopyrrole compound enables fine particle formation of pigment particles, increases dispersibility, reduces light scattering, maximizes transmittance, and a color filter employing the same can exhibit excellent contrast ratio due to improved brightness.

In the above chemical formula 1, R ₁ to R ₅ are each independently hydrogen, halogen, cyano, (C1-C7)alkyl or (C6-C10)aryl; R ₆ is hydrogen or -COOR ₁₁ ; R ₁₁ is (C1-C10)alkyl or (C7-C10)arylalkyl; m and n may each independently be 1 or 2.

According to one embodiment of the present invention, R ₁ to R ₅ of the chemical formula 1 are each independently hydrogen, halogen, cyano, (C1-C5)alkyl or (C6-C10)aryl; R ₆ is hydrogen or -COOR ₁₁ ; R ₁₁ is (C1-C6)alkyl; m and n may each independently be 1 or 2.

In addition, according to one embodiment of the present invention, R ₁ to R ₅ of the chemical formula 1 are each independently hydrogen, halogen, cyano, (C1-C5)alkyl or (C6-C10)aryl; R ₆ is hydrogen or -COOR ₁₁ ; R ₁₁ is (C1-C3)alkyl; and m and n may each independently be 1 or 2.

A diketopyrrolopyrrole compound according to one embodiment of the present invention can be represented by the following chemical formula 2 or chemical formula 3.

[Chemical formula 2]

[Chemical Formula 3]

[In the above chemical formulas 2 and 3,

R ₃ is hydrogen, halogen, (C1-C3) alkyl or phenyl;

R ₄ is hydrogen, cyano or (C1-C3)alkyl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C3) alkyl.]

According to one embodiment of the present invention, the diketopyrrolopyrrole compound may be selected from the following compounds.

In addition, the present invention provides a method for producing a diketopyrrolopyrrole compound, and the diketopyrrolopyrrole compound represented by the following chemical formula 1 can be produced by reacting a compound of chemical formula 4 and a compound of chemical formula 5.

[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the above chemical formulas 1, 4 and 5,

R ₁ to R ₅ are independently hydrogen, halogen, cyano, (C1-C10)alkyl or (C6-C12)aryl;

R ₆ is hydrogen or -COOR ₁₁ ;

R ₁₁ is (C1-C20)alkyl or (C7-C20)arylalkyl;

m and n are independently 1 or 2.]

A method for producing a diketopyrrolopyrrole compound according to one embodiment of the present invention can be easily mass-produced through a simple process.

The reaction temperature of the manufacturing method according to one embodiment may be used at a temperature commonly used in organic synthesis, but may vary depending on the quality of the reactants and the amount of the starting materials, and may preferably be performed at 60°C to 140°C, specifically at 80°C to 120°C, and more specifically at 90°C to 110°C.

The reaction is terminated after confirming that the starting material is completely consumed using NMR, etc. Afterwards, a process of separating and purifying the target product may be performed using conventional methods such as an extraction process, a process of distilling the solvent under reduced pressure, and column chromatography.

According to one embodiment of the present invention, a colored photosensitive resin composition comprising a diketopyrrolopyrrole compound is provided, which may include a pigment; and a diketopyrrolopyrrole compound according to one embodiment of the present invention as a pigment-synergist; and the pigment is characterized in that it contains a diketopyrrolopyrrole red pigment.

The colored photosensitive resin composition of the present invention may contain a colorant other than the diketopyrrolopyrrole red pigment. There is no particular limitation on the other colorant, and the color or material may be appropriately selected depending on the intended use. Among them, organic pigments and organic dyes are preferable in the sense of obtaining pixels with high brightness and color purity.

A colored photosensitive resin composition according to one embodiment of the present invention can be used for a color filter.

According to one embodiment of the present invention, the diketopyrrolopyrrole compound may be included in an amount of 0.01 to 2.0 wt%, preferably 0.1 to 1.5 wt%, and more preferably 0.2 to 1.0 wt%, based on the total weight of the colored photosensitive resin composition.

In addition, in one embodiment of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of a dispersant, a binder resin, an organic solvent, a photoinitiator, a crosslinking agent, and a surfactant.

The above dispersant may be a commercially available one as long as it has a nitrogen atom, and for example, as a (meth)acrylic dispersant, Disperbyk-2000, Disperbyk-2001, Disperbyk-21116 (all manufactured by BYK Chemie), etc., as a urethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (all manufactured by BYK Chemie), Solspers 76500 (manufactured by Lubrizol Co., Ltd.), etc., as a polyethyleneimine dispersant, Solspers 24000 (manufactured by Lubrizol Co., Ltd.), etc., as a polyester dispersant, Azisper PB821 (nonvolatile component 100 mass%), Azisper PB822, In addition to Ajisper PB880 and Ajisper PB881 (both manufactured by Ajinomoto Finetechno Co., Ltd.), BYK-LPN 21324 (non-volatile component 40 mass%) (manufactured by BYK) can be mentioned, and the dispersant can be used alone or in combination of two or more types.

In addition, the present invention provides a method for manufacturing a film by a coating method using a spin coater by employing a colored photosensitive resin composition according to the present invention, but is not limited thereto, and any film manufacturing method that can be recognized by a person skilled in the art is possible.

The present invention provides a color filter formed by a colored photosensitive resin composition according to one embodiment of the present invention, and the color filter thus manufactured can exhibit improved brightness and thus exhibit an excellent contrast ratio.

Additionally, the present invention provides a display device including a color filter according to one embodiment of the present invention.

Hereinafter, a method for producing a diketopyrrolopyrrole compound according to the present invention, a colored photosensitive resin composition comprising the same, and a method for producing a color filter employing the same will be described in more detail through specific examples.

[Manufacturing Example 1] Synthesis of Compound 1

Sodium metal (0.6 g, 28.8 mmol) and FeCl ₃ (0.05 g) were added to tert-amyl alcohol (20 ml), and refluxed until the sodium metal was completely dissolved. Compound (11) (0.45 g, 2.52 mmol) and compound (21) (0.42 g, 1.86 mmol) were sequentially added, and refluxed for 12 hours. After completion of the reaction, methanol was added at room temperature, the pH was adjusted to acid using acetic acid, and the resulting solid was filtered after stirring for 30 minutes. Methanol was used during filtration. The filtered solid was hot filtered in EtOH:H2O = 1:1 (50 ml) solvent to obtain compound (1).

¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 8.0 (d, 2H), 7.7 (d, 2H), 7.5 (m, 5H), 7.1 (s, 2H)

[Manufacturing examples 2 and 3]

Except that compounds (12) and (13) in Table 1 below were used instead of compound (11) in Manufacturing Example 1, the same procedure as Manufacturing Example 1 was performed to obtain the following compounds (2) and (3).

Preparation Example 2: ¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 8.0 (d, 2H), 7.4-7.5 (m, 4H), 7.2 (s, 4H)

Preparation Example 3: ¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 8.0 (d, 2H), 7.4-7.5 (m, 4H), 7.2 (s, 4H)

[Manufacturing Example 4]

Compound (4) below was obtained in the same manner as in Manufacturing Example 1, except that compound (22) of Table 1 below was used instead of compound (21) in Manufacturing Example 1.

¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 7.8 (d, 2H), 7.7 (d, 2H), 7.5 (m, 5H), 7.2 (s, 2H)

[Manufacturing examples 5 and 6]

Except that compounds (12) and (13) in Table 1 below were used instead of compound (11) in Manufacturing Example 1, and that compound (22) in Table 1 below was used instead of compound (21) in Manufacturing Example 1, the same procedure as Manufacturing Example 1 was carried out to obtain the following compounds (5) and (6).

Preparation Example 5: ¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 7.8 (d, 2H), 7.4-7.5 (m, 4H), 7.5 (m, 4H)

Preparation Example 6: ¹ H NMR (400 MHz, C6D6) δ12.7 (s, 1H), 7.8 (d, 2H), 7.4-7.5 (m, 4H), 7.5 (m, 4H)

Manufacturing compound Reactive compound Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Manufacturing example 6

Table 2 below shows the molecular weight ( m/e ) and maximum absorption wavelength (λ _max ) analysis data of UV-VIS spectrum of Manufacturing Examples 1 to 6.

EA λ _max (nm) transference number (%) Manufacturing example 1 C,67.48; H,3.79; N,8.05 509 28 Manufacturing example 2 C,61.89; H,3.27; N,7.18 513 69 Manufacturing example 3 C,55.58; H,2.92; N,6.57 514 57 Manufacturing example 4 C,68.87; H,4.33; N,7.65 521 48 Manufacturing example 5 C,60.70; H,3.11; N,7.37 524 49 Manufacturing example 6 C,55.23; H,3.80; N,5.75 526 62

[Example 1] Preparation of a colored photosensitive resin composition 4.0 wt% of Pigment Red No. 254, 0.5 wt% of Preparation Example 1, 2.0 wt% based on solid content of Disperbyk-21116 (BYK-Chemie) as an acrylic dispersant, 3.0 wt% based on solid content of SPCG-19X (Showa Denko) (acid value 110 KOH mg/g, Mw=10,000) as a binder resin, and 30.0 wt% of propylene glycol monomethyl ether acetate (PGMEA) and 15 wt% of diacetone alcohol as a solvent were mixed and stirred, dispersed using a vertical bead mill, and then 1.0 wt% of binder resin SPCG-19X (Showa Denko) (acid value 110 KOH mg/g, Mw=10,000) was additionally added, and 1.0 wt% of photoinitiator was added. After sequentially adding 1.5 wt% of Irgacure-369 (BASF), 7.0 wt% of dipentaerythritol hexaacrylate as a crosslinker, and 0.01 wt% of Megapak F477 (Dainippon Ink and Chemicals) as a surfactant, 24.49 wt% of PGMEA and 10.0 wt% of diacetone alcohol were additionally added and stirred to obtain a red-colored photosensitive resin composition.

[Examples 2 to 6] Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was obtained in the same manner as in Example 1, except that Manufacturing Examples 2 to 6 were used instead of Manufacturing Example 1 in the above Example 1.

[Comparative Example 1] Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was obtained in the same manner as in Example 1, except that Manufacturing Example 1 was not used in the above Example 1.

[Experimental Example 1] Color characteristic evaluation test of colored photosensitive resin composition

Each of the colored photosensitive resin compositions obtained in Examples 1 to 6 and Comparative Example 1 was formed into a film using a spin coater, and then dried in an 80° C. oven for 10 minutes to obtain a coating film. The coating film was exposed to light at a light amount of 40 mJ/cm ² using an ultra-high pressure mercury lamp (pre-baked), developed for 60 seconds by spraying using a 0.04% KOH developer (containing 0.12% surfactant), and then washed with ultrapure water. The developed coating film was heat-cured in an oven at 230° C. for 20 minutes (post-baked) to manufacture a film substrate having a pattern for a color filter formed thereon.

- Color evaluation

The above film substrate was spectral measured using an MCPD-3000 chromaticity meter (manufactured by Otsuka Corporation), and the XY chromaticity coordinates (x, y) and Y in the XYZ colorimetric system of CIE were measured using the characteristic function of the C illuminant, and the results are shown in Table 3 below.

- Contrast evaluation

The contrast value (maximum brightness value/minimum brightness value, blank value = 20,000) of the above film substrate was measured using a contrast meter CT-1 (manufactured by Tsubosaka Denki Co., Ltd.), and the results are shown in Table 3 below.

Pre-bake Post-bake Pre-bake Post-bake color Brightness Conversion
Brightness color Brightness Conversion
Brightness Contrast Contrast Example 1 0.64,
0.3301 22.04 22.02 0.64,
0.3297 21.73 21.79 5132 3296 Example 2 0.64,0.3300 22.04 22.03 0.64,
0.3296 21.71 21.80 5398 3662 Example 3 0.64,0.3306 22.14 22.02 0.64,
0.3303 21.82 21.76 6182 4425 Example 4 0.64,0.3305 22.12 22.02 0.64,
0.3303 21.82 21.76 5314 3648 Example 5 0.64,0.3304 22.09 22.01 0.64,
0.3302 21.78 21.74 5467 3417 Example 6 0.64,0.3295 21.97 22.07 0.64,
0.3292 21.67 21.83 5312 3915 Comparative Example 1 0.64,0.3290 21.87 22.07 0.64,
0.3284 21.48 21.81 4566 3125

As shown in Table 3 above, the films of Examples 1 to 6 manufactured with the compositions including the diketopyrrolopyrrole compounds according to one embodiment of the present invention exhibited contrasts improved by 12.4 to 35.4% in the pre-bake and by 5.5 to 41.6% in the post-bake compared to Comparative Example 1. Therefore, it can be seen that the diketopyrrolopyrrole compounds of the present invention function as pigment synergists and enable the particle formation of pigments to increase dispersibility, and with the increased dispersibility, the scattering of light is reduced and the transmittance is maximized, so that the contrast ratio of the color filter employing the same can be greatly improved.

Although the present invention has been described through specific matters and limited examples and comparative examples, these have been provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations from this description.

Therefore, the idea of the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the same are included in the scope of the idea of the present invention.

Claims (13)

A colored photosensitive resin composition comprising a diketopyrrolopyrrole compound represented by the following chemical formula 2 or 3 and a diketopyrrolopyrrole red pigment.
[Chemical formula 2]

[Chemical Formula 3]

[In the above chemical formulas 2 and 3,
R ₃ is halogen;
R ₄ is hydrogen, cyano or (C1-C3)alkyl;
R ₆ is hydrogen or -COOR ₁₁ ;
R ₁₁ is (C1-C3) alkyl.] delete delete delete In the first paragraph,
A colored photosensitive resin composition, wherein the diketopyrrolopyrrole compound is selected from the following compounds.


A method for producing a diketopyrrolopyrrole compound represented by the following chemical formula 1, which is produced by reacting a compound of the following chemical formula 4 with a compound of the following chemical formula 5.
[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the above chemical formulas 1, 4 and 5,
R ₁ to R ₅ are independently hydrogen, halogen, cyano, (C1-C10)alkyl or (C6-C12)aryl;
R ₆ is hydrogen or -COOR ₁₁ ;
R ₁₁ is (C1-C20)alkyl or (C7-C20)arylalkyl;
m and n are independently 1 or 2.] delete delete In the first paragraph,
The above colored photosensitive resin composition is a colored photosensitive resin composition for use as a color filter. In the first paragraph,
A colored photosensitive resin composition, wherein the diketopyrrolopyrrole compound is contained in an amount of 0.01 to 2.0 wt% based on the total weight of the colored photosensitive resin composition. In the first paragraph,
The above colored photosensitive resin composition further comprises one or more selected from the group consisting of a dispersant, a binder resin, an organic solvent, a photoinitiator, a crosslinking agent, and a surfactant. A color filter formed by the colored photosensitive resin composition of claim 1. A display device including a color filter of claim 12.