KR101312660B1 - Black pigment and resin composition for light blocking member including the same - Google Patents

Abstract

상기 화학식 1에서 Ar₁ 및 Ar₂는 명세서에 기재한 바와 같다.The present invention relates to a black pigment for a light shielding member comprising a compound having a moiety represented by Formula 1 and a resin composition comprising the black pigment.
[Formula 1]

Ar ₁ and Ar ₂ in Formula 1 are as described in the specification.

Description

Black pigment and resin composition for light-blocking member containing the same {BLACK PIGMENT AND RESIN COMPOSITION FOR LIGHT BLOCKING MEMBER INCLUDING THE SAME}

The present invention relates to a black pigment and a resin composition for light blocking members including the same.

The liquid crystal display is one of the most widely used flat panel display devices. The liquid crystal display includes two substrates on which electrodes are formed and a liquid crystal layer interposed therebetween to rearrange the liquid crystal molecules of the liquid crystal layer by applying a voltage to the electrode. The display device controls the amount of light transmitted.

Among the liquid crystal display devices, a structure which is mainly used at present is a structure in which electric field generating electrodes are provided on two display panels. Among them, a plurality of thin film transistors and pixel electrodes are arranged in a matrix form on one display panel, and red, green, and blue color filters and light blocking members are formed on another display panel, and the common electrode covers the entire surface thereof. Is the mainstream.

Among these, the light blocking member is positioned between neighboring pixels to prevent light leakage and thus has an important influence on display characteristics.

One aspect of the present invention provides a black pigment having excellent light blocking properties and thermal stability.

Another aspect of the present invention provides a resin composition for light blocking members including the black pigment.

According to an aspect of the present invention, there is provided a black pigment for a light blocking member including a compound having a moiety represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, a C2 to C20 heteroaryl group or a combination thereof.

The black pigment for the light blocking member may include at least one of the compounds represented by the following Chemical Formulas 1a to 1f.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1a to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C2 to C20 heteroaryl group or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.

The moiety represented by Chemical Formula 1 may be linked to at least one of * moieties of the following Chemical Formula 2.

(2)

In Formula 2, R ₁ and R ₂ are each independently hydrogen, C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocyclo An alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C10 alkoxy group, a halogen group or a combination thereof.

Ar ₁ and Ar ₂ in Formula 1 may each independently include a benzene group, a naphthalene group, a thiazole group, a benzothiazole group, or a combination thereof.

Formula 1 may be represented by the formula 1A.

≪ EMI ID =

The compound having a moiety represented by Chemical Formula 1 may be in the form of a single molecule.

The compound having a moiety represented by Chemical Formula 1 may absorb light in the entire visible ray range of about 400 to 700 nm.

According to another aspect of the invention, there is provided a light-shielding member resin composition comprising a black pigment, a polymerizable compound, and a binder comprising a compound having a moiety represented by the following formula (1).

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, a C2 to C20 heteroaryl group or a combination thereof.

The black pigment may include at least one of the compounds represented by the following Chemical Formulas 1a to 1f.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1a to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C2 to C20 heteroaryl group or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.

Ar ₁ and Ar ₂ in Formula 1 may each independently include a benzene group, a naphthalene group, a thiazole group, a benzothiazole group, or a combination thereof.

Formula 1 may be represented by the formula 1A.

≪ EMI ID =

The black pigment may be in the form of a single molecule.

The black pigment, the polymerizable compound and the binder may be included in about 20 to 70% by weight, about 20 to 70% by weight and about 10 to 30% by weight based on the total content of the resin composition.

Absorption of light in the entire visible light area prevents light leakage and increases the contrast ratio, and excellent thermal stability prevents deformation or alteration by heat during the process.

1 is a graph showing the UV spectrum according to the wavelength of the black pigment according to Synthesis Examples 1 and 2,
2 is a graph showing UV absorbance according to the wavelength of the black pigment according to Synthesis Examples 1 and 2,
3 is a graph showing thermal characteristic curves of black pigments according to Synthesis Examples 1 and 2. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The black pigment according to an embodiment of the present invention includes a compound having a moiety represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group and a C2 to C20 heteroaryl group or a combination thereof.

In Formula 1, Ar ₁ and Ar ₂ may each independently include a benzene group, a naphthalene group, a thiazole group, a benzothiazole group, or a combination thereof.

Formula 1 may be, for example represented by Formula 1A.

 ≪ EMI ID =

The moiety represented by Formula 1 may be bound to a side chain of the cyclic compound, and '*' is a part connected to the cyclic compound.

The moiety represented by Chemical Formula 1 may be linked to at least one of * moieties of the following Chemical Formula 2.

(2)

In Formula 2, R ₁ and R ₂ are each independently hydrogen, C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocyclo An alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C10 alkoxy group, a halogen group or a combination thereof.

The compound may include at least one of the compounds represented by Formula 1a to Formula 1f.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1a to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C2 to C20 heteroaryl group or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.

The compound represented by Chemical Formula 1a may be, for example, a compound represented by Chemical Formula 1aa.

(1aa)

The compound represented by Chemical Formula 1b may be, for example, a compound represented by Chemical Formula 1ba.

[Formula 1ba]

The compound having a moiety represented by Chemical Formula 1 may be in the form of a single molecule.

The compound may absorb light in the full visible range of about 400 to 700 nm. In addition, the compound has a uniform degree of light absorption for each wavelength band, thereby preventing light from leaking at a specific wavelength and degrading display characteristics, and maintaining a high contrast ratio.

Thus, according to the present embodiment, by using the organic compound in the monomolecular form as a black pigment, when an inorganic pigment such as carbon black is used as the black pigment, it is possible to solve the problem that the residue is adsorbed in the adjacent layer. have. In addition, as a black pigment, light leakage can be reduced and the manufacturing process can be simplified as compared with a mixture of various kinds of organic pigments absorbing light of a specific wavelength.

 Another embodiment of the present invention provides a resin composition for a light blocking member including the black pigment, the polymerizable compound, and a binder as described above.

The black pigment described above may be a monomolecular compound having a moiety represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group and a C2 to C20 heteroaryl group or a combination thereof.

In Formula 1, Ar ₁ and Ar ₂ may each independently include a benzene group, a naphthalene group, a thiazole group, a benzothiazole group, or a combination thereof.

Formula 1 may be, for example represented by Formula 1A.

≪ EMI ID =

The moiety represented by Chemical Formula 1 may be bonded to the side chain of the cyclic compound, and '*' is a part connected to the cyclic compound.

The moiety represented by Chemical Formula 1 may be linked to at least one of * moieties of the following Chemical Formula 2.

(2)

In Formula 2, R ₁ and R ₂ are each independently hydrogen, C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocyclo An alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C10 alkoxy group, a halogen group or a combination thereof.

The compound may include at least one of the compounds represented by Formula 1a to Formula 1f.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1a to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C2 to C20 heteroaryl group or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.

The compound represented by Chemical Formula 1a may be, for example, a compound represented by Chemical Formula 1aa.

(1aa)

The compound represented by Chemical Formula 1b may be, for example, a compound represented by Chemical Formula 1ba.

[Formula 1ba]

The black pigment may be included in about 20 to 70% by weight based on the total content of the resin composition.

The polymerizable compound is a compound such as a monomer or oligomer which can be polymerized by light or heat, and has a carbon-carbon unsaturated bond and / or a carbon-carbon cyclic bond, such as an unsaturated carboxylic acid. A compound, an acrylamide type compound, an allyl ester type compound, a vinyl type compound, etc. are contained.

The polymerizable compound may be included in about 20 to 70% by weight based on the total content of the resin composition. By including the polymerizable compound in the above range, it is excellent in developability and may be formed in a good pattern and at the same time excellent in coatability.

The binder may be, for example, an alkali soluble resin such as an acrylic or methacrylic polymer.

The binder may be included in about 10 to 30% by weight based on the total content of the resin composition. By including the binder in the above range it may be excellent in coating properties and developability.

The resin composition may further include additives such as a photo initiator, a surfactant, and an adhesion improving agent in addition to the above components.

The black pigment, the polymerizable compound, the binder, and various additives may be dissolved in a solvent to prepare a solution.

The resin composition solution may be coated on a substrate and patterned to form a light blocking member called a black matrix.

The present invention will be described in more detail with reference to the following Examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Black pigment

Synthetic example  One

As shown in Reaction Scheme 1, 2.5 g (10.12 mmol) of 1,4-phenylazo-1-naphthylamine in 100 ml of toluene, and 2.9 g (12.14 mmol) of 1-chloroanthraquinone ), Tris (dibenzylideneacetone) dipalladium (Tris (dibenzylideneacetone) dipalladium, Pd ₂ (dba) ₃ ) 0.28 g (0.30 mmol) [2,2'-bis (diphenylphosphine-1,1'-by Naphthyl] ([2,2'-bis (diphenylphosphine) -1,1'-binaphthyl], BINAP) 0.75g (1.20 mmol) and cesium carbonate 9.89g (30.35 mmol) were added and refluxed.

[Reaction Scheme 1]

After the reaction was extracted using chloroform and water. Subsequently, the organic solvent was distilled under reduced pressure, and then chromatographed with chloroform, followed by reprecipitation to obtain 1- (4-phenylazo-naphthalen-1-yl amino) -anthraquinone (1- (4-) as a compound represented by Chemical Formula 1a. phenylazo-naphthalen-1-yl amino) -anthraquinone, AAQ).

The molecular structure of the compound represented by Chemical Formula 1a was confirmed by using NMR. The NMR results are as follows:

¹ H NMR (500 MHz, CDCl ₃ ) δ (ppm): 11.96 (s, 1H), 9.07-9.06 (d, 1H), 8.40-8.39 (d, 1H), 8.33-8.31 (d, 1H), 8.28- 8.26 (d, 1H), 8.07-8.06 (d, 2H), 7.93-7.92 (d, 1H), 7.84-7.79 (m, 3H), 7.73 (t, 1H), 7.69-7.66 (m, 2H), 7.59-7.56 (t, 2H) 7.53-7.51 (m, 3H)

Synthetic example  2

As shown in Scheme 2, 5.6 g (22.6 mmol) of 1,4-phenylazo-1-naphthylamine was added to 100 ml of toluene, and 2.5 g of 1,4-dichloroanthraquinone ( 9.0 mmol), tris (dibenzylideneacetone) dipalladium, Pd ₂ (dba) ₃ ) 0.219 g (0.24 mmol), [2,2'-bis (diphenylphosphine-1,1 4.37 g (0.70 mmol) of cesium carbonate and 11.58 g (35.54 mmol) of '-binaphthyl] ([2,2'-bis (diphenylphosphine) -1,1'-binaphthyl], BINAP) It was refluxed.

[Reaction Scheme 2]

After the reaction was extracted using chloroform and water. Subsequently, the organic solvent was distilled under reduced pressure, and then chromatographed with chloroform, followed by reprecipitation to obtain 1,4-bis- (4-phenylazo-naphthalen-1-yl amino) -anthraquinone (1). , 4-bis- (4-phenylazo-naphthalen-1-yl amino) -anthraquinone, DAAQ) was obtained.

The molecular structure of the compound represented by Chemical Formula 1b was confirmed using NMR. The NMR results are as follows:

¹ H NMR (500 MHz, CDCl ₃ ) δ (ppm): 12.88 (s, 2H), 9.07-9.05 (d, 2H), 8.48-8.47 (m, 2H), 8.36-8.34 (d, 2H), 8.05- 8.04 (d, 4H), 7.92-7.91 (d, 2H), 7.84-7.83 (m, 2H), 7.75-7.67 (m, 4H), 7.60-7.55 (m, 8H), 7.51-7.46 (t, 2H )

Absorbance Measurement-1

Absorption according to the wavelength range of the black pigment according to Synthesis Examples 1 and 2 was measured.

Absorbance was measured by dissolving the black pigment in a tetrahydrofuran (THF) solution at a concentration of 1 * 10 ^-4 M and placing it in a UV cell.

The result will be described with reference to FIG. 1.

1 is a graph showing the UV spectrum according to the wavelength of the black pigment according to Synthesis Examples 1 and 2.

Referring to FIG. 1, it can be seen that the black pigments according to Synthesis Examples 1 and 2 uniformly absorb light in the visible light wavelength range of about 400 to 700 nm.

Absorbance Measurement-2

Absorbance over the wavelength range was measured using the black pigments according to Synthesis Examples 1 and 2.

Absorbance was measured by dissolving the black pigment in 0.5% by weight in chloroform and spin coating at 1000 rpm for 60 seconds on a glass plate to form a thin film.

The result will be described with reference to FIG.

2 is a graph showing UV absorbance according to the wavelength of the black pigment according to Synthesis Examples 1 and 2.

Referring to FIG. 2, it can be seen that the black pigments according to Synthesis Examples 1 and 2 have high absorbances of about 0.1 au or more in the visible wavelength range of about 400 to 700 nm. It can also be seen that the absorbance is uniform in each wavelength range.

Pyrolysis characteristics

Referring to FIG. 3, the thermal stability of the black pigments according to Synthesis Examples 1 and 2 was confirmed by thermogravimetric analysis (TGA).

3 is a graph showing thermal characteristic curves of black pigments according to Synthesis Examples 1 and 2. FIG.

The thermogravimetric method measured the weight change rate of the black pigment prepared according to Synthesis Examples 1 and 2 while increasing the temperature from room temperature (about 25 ℃) to 600 ℃.

Referring to FIG. 3, the temperature at which the weight of the black pigment according to Synthesis Example 1 is reduced to 90% compared to the initial (100%) is about 380 ° C., and the weight of the black pigment according to Synthesis Example 2 is compared to the initial (100%). It can be seen that the temperature decreasing to 90% is about 400 ℃.

This shows that the black pigment according to Synthesis Examples 1 and 2 has excellent thermal stability up to about 400 ° C., which is generally thermally stable at about 250 ° C., which is a process temperature of a liquid crystal display device, so that it is not decomposed by heat or changed in properties. It means not to.

As described above, the black pigments according to Synthesis Examples 1 and 2 not only absorb light in the visible wavelength range uniformly, thereby exhibiting excellent performance as a light shielding member, but also have excellent thermal stability and are applied to display devices such as liquid crystal displays. It can be seen that.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of right.

Claims (14)

A black pigment for a light shielding member comprising at least one of the compounds represented by the following Chemical Formulas 1c to 1f:
[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1c to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C2 to C20 heteroaryl group or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.
delete delete In claim 1,
In Formulas 1c to 1f, Ar ₁ and Ar ₂ are each independently a black pigment for a light blocking member including a benzene group, a naphthalene group, a thiazole group, a benzothiazole group, or a combination thereof.

delete In claim 1,
The compound represented by Chemical Formulas 1c to 1f is a black pigment for a light blocking member in the form of a single molecule.
In claim 1,
The compound represented by Chemical Formulas 1c to 1f is a black pigment for a light blocking member that absorbs light in the visible light region of 400nm to 700nm.
Black pigment containing at least one of the compounds represented by the formula 1c to 1f,
Polymerizable compounds, and
bookbinder
Resin composition for a light shielding member comprising:
[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

In Formulas 1c to 1f, Ar ₁ and Ar ₂ are each independently a C6 to C20 aryl group, a C7 to C20 arylalkyl group, a C2 to C20 heteroaryl group, or a combination thereof, and R ₁ and R ₂ are each independently hydrogen , C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C20 heterocycloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 To C10 alkoxy group, halogen group or a combination thereof.
delete delete 9. The method of claim 8,
Ar ₁ and Ar ₂ in the formula 1c to 1f are each independently a benzene group, naphthalene group, thiazole group, benzothiazole group resin composition for a light shielding member.

delete 9. The method of claim 8,
The black pigment is a resin composition for a light blocking member in the form of a single molecule.
9. The method of claim 8,
The black pigment, the polymerizable compound and the binder are 20 to 70% by weight, 20 to 70% by weight and 10 to 30% by weight, respectively, with respect to the total content of the resin composition.

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