KR101793681B1 - Pigments for light shield layer and photo-curable resin composition using the same - Google Patents

Abstract

상기 식에서, R¹, R²는 각각 독립적으로 시아노기, 히드록시기, 에테르기, 아민기또는 아민 유도체기, 치환 또는 비치환된 C1~C20의 알콕시기, 치환 또는 비치환된 C1~C20의 알킬기, 치환 또는 비치환된 C2~C20의 알케닐기, 치환 또는 비치환된 C2~C20의 알키닐기, 치환 또는 비치환된 C3~C20의 사이클로알킬기, 치환 또는 비치환된 C3~C20의 사이클로알케닐기, 치환 또는 비치환된 C3~C20의 사이클로알키닐기, 치환 또는 비치환된 C2~C20의 헤테로사이클로알킬기, 치환 또는 비치환된 C2~C20의 헤테로사이클로알케닐기, 치환 또는 비치환된 C2~C20의 헤테로사이클로알키닐기, 치환 또는 비치환된 C6~C30의 아릴기, 또는 치환 또는 비치환된 C6~C30의 아릴옥시기이다.
본 발명에 따르는 광차단막용 안료는 종래의 페릴렌 블랙에 비하여 내열성 및 분산성이 우수하다.The present invention provides a pigment for a light-blocking film comprising a compound represented by the following formula (1)
[Chemical Formula 1]

Wherein each of R ¹ and R ² independently represents a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, A substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2-C20 cycloalkynyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkenyl group, a substituted or unsubstituted C2-C20 heterocyclo An alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.
The pigment for a light-shielding film according to the present invention is superior in heat resistance and dispersibility to conventional perylene black.

Description

TECHNICAL FIELD [0001] The present invention relates to a pigment for a light-shielding film of a perylene type and a photo-curable composition using the same. BACKGROUND ART [0002]

The present invention relates to a pigment for a light-shielding film and a photo-curing composition using the same, and more particularly to a photo-curing composition for a light-shielding film, which comprises conjugation to a perylene-based compound, And a photo-curable composition using the same. BACKGROUND ART

In recent years, in order to reduce the power consumption and manufacturing cost in the LCD industry, a demand for a high-luminance color filter has been increased, and thus a structure of a color filter on array has been studied. In this structure, since the step of joining the upper and lower substrates is not required, the line width of the black matrix existing in the color filter can be narrowed, and the aperture ratio and the luminance can be improved. However, since the color filter is formed on the TFT array, It is necessary to use a black colorant having low conductivity as a material of the black matrix. The existing carbon black has a high permittivity and a risk of malfunction of the TFT. Therefore, dyes and pigments made of organic materials have been studied as substitute materials.

In addition, a black column spacer having a function of absorbing polarization including a black colorant instead of a transparent column spacer widely used for improving image quality in the LCD industry is under study. It is required to have a very low electrical conductivity so as to minimize the influence of such an electric field. In addition, when manufactured by applying photolithography, it is necessary to have a relatively high transmittance in the ultraviolet region. Therefore, organic and inorganic pigments are suitable as materials that meet these requirements. For example, titanium black and carbon black are used as inorganic pigments used for this purpose, and rhammet black, aniline black, perylene black, and RGB mixed black are known as organic pigments.

Specifically, KR2014-0071725A, KR2015-0037125A, KR2015-0037127A, and the like discloses a photocurable resin composition comprising a pigment, a binder resin, a photopolymerizable monomer, and a plurality of photoinitiators, and a method of forming a black matrix pattern of a color filter using the same. However, the photo-curing resin composition disclosed in these documents uses a colored dispersion in which two or more color pigments are mixed and milled on the basis of black pigment carbon black or carbon black, which has a problem in dispersibility.

On the other hand, KR2013-0079165A, US2007-0151478A1, US5,508,137A, JP2013-134263A, etc. have proposed a method in which a perylene derivative as an organic pigment is dispersed in a black pigment And a method for producing a black column spacer using the same. However, even in the case of the disclosed organic pigments, the improvement of poor dispersibility is still insufficient, and above all, there is a typical problem of organic pigments that heat resistance is poor.

Thus, the inventors of the present invention have confirmed that the conjugation of a double bond in the form of an imidazole is extended to a compound of a pseudo-rylene series, and at the same time, when a specific substituent is introduced into the bay-position, heat resistance and dispersibility can be simultaneously achieved And completed the present invention.

An object of the present invention is to provide a pigment for a light-shielding film having a low heat conductivity and a high absorbance and high heat resistance and dispersibility.

Another object of the present invention is to provide a photocurable composition comprising the pigment.

It is still another object of the present invention to provide an electronic component device using the composition.

The present invention provides a pigment for a light-shading coating film comprising a compound represented by the following general formula (1)

[Chemical Formula 1]

Wherein each of R ¹ and R ² independently represents a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, A substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2-C20 cycloalkynyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkenyl group, a substituted or unsubstituted C2-C20 heterocyclo An alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.

Preferably, R ¹ and R ² are independently the following substituents:

Wherein R ³ to R ⁷ are each independently selected from the group consisting of hydrogen, C 1 to C 10 linear or branched alkyl, and C 1 to C 10 linear or branched alkoxy.

More preferably, R ³ to R ⁷ are each independently a substituent selected from the group consisting of hydrogen, a C 1 to C 5 straight-chain or branched alkyl, and a C 1 to C 5 straight-chain or branched alkoxy.

The light-blocking film-forming pigment may be one of the following compounds:

   [1-1] [1-2] [1-3] [1-4]

   [1-5] [1-6] [1-7] [1-8]

   [1-9] [1-10] [1-11] [1-12]

The present invention also provides a photocurable composition comprising the above-described pigment for a light-shielding film.

In addition, the present invention provides a light-shielding film formed by applying the above composition to a substrate.

The light blocking film may be a color filter black matrix, a black column spacer, a black bezel or an OLED black insulating film.

The pigment for a light-blocking film according to the present invention has a benzimidazole structure conjugated to a perylene structure and excellent in heat resistance at a level of 1 wt% or less in mass reduction measured by setting an isothermal section at 230 ° C for 1 hour .

In addition, since the perylene has a substituent at the bay-position, the solubility in solvents such as propylene glycol methyl ether acetate (PGMEA) and cyclohexanone is preferably 3-6 g / 100 ml, the solubility is excellent and high dispersibility can be expected.

FIG. 1 is a graph showing the absorbance of each of the pigments for a light-shielding film synthesized according to the present invention. FIG.
2 is a result of thermal analysis of the pigment for a light-blocking film synthesized in the example of the present invention.
3 is a SEM photograph of a black matrix produced in the practice of the present invention.

In the present invention, 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (3,4,9,10-tetraazacyclododecane) having a substituent introduced at the bay-position (carbon position 1, 6, 7 or 12 of perylene) , 10-Perylenetetracarboxylic Bisbenzimidazole, PTCBI).

Preferably, the PTCBI compound may be represented by the following Formula 1:

[Chemical Formula 1]

Wherein each of R ¹ and R ² independently represents a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, A substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2-C20 cycloalkynyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkenyl group, a substituted or unsubstituted C2-C20 heterocyclo An alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.

Wherein R < ¹ > and R < ² > are preferably the following substituents:

Wherein R ³ to R ⁷ are each independently selected from the group consisting of hydrogen, C 1 to C 10 linear or branched alkyl, and C 1 to C 10 linear or branched alkoxy. More preferably, R ³ to R ⁷ can each independently be selected from the group consisting of hydrogen, C 1 to C 5 linear or branched alkyl, and C 1 to C 5 linear or branched alkoxy.

For example, C1-C5 straight chain or branched alkyl; Or alkyl forming a straight or branched alkoxy of C1 to C5 may be a substituent such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- butyl, isobutyl, , 1-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, neopentyl and the like.

Most preferably, the pigment for a light-shielding film may be any one selected from the following:

   [1-1] [1-2] [1-3] [1-4]

   [1-5] [1-6] [1-7] [1-8]

   [1-9] [1-10] [1-11] [1-12]

The present invention also provides a photocurable composition comprising the above-mentioned pigment for a light-shielding film and at least one polymer. The composition includes, for example, 1 to 20% by weight of a pigment for a light-shielding film, 1 to 20% by weight of a photopolymerizable binder resin, 0.1 to 20 parts by weight of a photopolymerization initiator, and a residual solvent.

The photopolymerizable binder resin is preferably an acrylic resin. More specifically, an acrylic binder resin soluble in alkali which is used as a developer can be used. Preferably, the acrylic binder resin uses a copolymer of a monomer having an acid functional group and another monomer copolymerizable with the monomer.

Examples of the acrylic resin used for this purpose include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used singly or in combination of two or more kinds.

The photo-curable composition may contain a known functional monomer having an ethylenically unsaturated double bond such as ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, phenoxy Monofunctional monomers such as ethyl acrylate, and phenoxyethyl methacrylate; Or ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol di And a multifunctional monomer having a methacrylate ethylenically unsaturated double bond. When the composition contains a functional monomer having an ethylenically unsaturated double bond, the content thereof is 20% by weight or less.

The photopolymerization initiator is a photopolymerization initiator generally used in a photocurable resin composition. Examples of the photopolymerization initiator include an acetophenone based compound, a benzophenone based compound, a thioxanthone based compound, a benzoin based compound, a triazine based compound, A combination of these can be used.

The solvent used in the composition is not particularly limited and includes, for example, known alcohols, ethers, glycol ethers, cellosolve acetates, carvitol, propylene glycol alkyl ether acetates, aromatic hydrocarbons, Carboxylic acid alkyl esters, amides, and the like.

In addition, additional components known in the photocurable composition according to the present invention may be included. Such additional components include, for example, viscosity modifiers, dispersants, surfactants, coupling agents, antioxidants, curing accelerators, ultraviolet absorbers, thermal polymerization inhibitors, leveling agents and the like.

In addition, the present invention provides a light shielding film to which the photo-curing composition is applied. The light shielding film is, for example, a black matrix of a color filter, a black column spacer, a black bezel or an OLED black insulating film.

As a typical method for forming a light shielding film, a photolithography technique is used. For example, the above composition may be applied to a substrate, followed by sequentially performing exposure and development to form a light-shielding film having a specific pattern. If desired, pre-baking may be performed before the exposure process, post-baking after development, and the like, which are well known in the art.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples illustrate the present invention, but the scope of the present invention is not limited to the following examples.

Example 1: Synthesis of Compound 1-4

Step 1:

(1-4a)

First, 32 g of perylenetetracarboxylic anhydride and 1 g of iodine (I ₂ ) were placed in 450 ml of sulfuric acid and stirred at room temperature for 2 hours. Next, the reaction mixture was heated to 80 ℃ using a dropping funnel, bromine (Br ₂₎ was dropwise added over a period of 9.5ml of 3 hours and reacted at reflux conditions for 17 hours.

After completion of the reaction, nitrogen gas was blown to remove the residual bromine gas, and the reaction mixture was cooled to room temperature and slowly poured into 3 L of ice water to form a precipitate. Thereafter, the precipitate was filtered and washed several times with distilled water, and the filtered material was oven-dried to obtain a compound 1-4a in which bromine atom was substituted at the bay-position (1, 7-position of perylene) in a yield of 42.8% Respectively.

Step 2:

      (1-4a) (1-4b)

1.5 g of the compound 1-4a obtained in the first step and 1.476 g of 1,2-diaminobenzene were placed in 150 ml of 1-propanoic acid and reacted at 150 ° C under reflux for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, distilled water was added, stirred for 30 minutes, filtered and washed, and then dried in an oven to obtain Compound 1-4b, in which perylene and benzimidazole rings were conjugated, in 67.4% Respectively.

Step 3:

       (1-4b) (1-4)

1 g of the compound 1-4b obtained in the second step and 1.038 g of 4-hydroxy-3-t-butyl anisole were placed in 80 ml of NMP, the temperature was raised to 120 ° C and 0.7 g of K ₂ CO _{3 was} added. Lt; / RTI >

Thereafter, the mixture was cooled to room temperature, and a precipitate was formed while dropping the reaction mixture into 500 ml of a 1 M aqueous solution of HCl. The precipitate was filtered and washed with distilled water, and the filtrate was dried in an oven. The dried product was refluxed with MC for 24 hours, filtered, washed again with MC, and the filtrate was evaporated to dryness. The residue was purified by column chromatography using MC as a starting material and the MeOH ratio was increased very little by little (final ratio: MC: MeOH = 200: 1) to obtain Compound 1-4 in a yield of 38.9%.

Example 2: Synthesis of Compound 1-5

In the same manner as in Example 1 except that 4-hydroxy-3-t-butyl anisole was used in place of 4-hydroxy-3-t-butyl anisole in the third step, Were synthesized.

Example 3: Synthesis of Compound 1-6

In the third step, Compound 1-6 was synthesized in the same manner as in Example 1, except that 2,4-di-tert-pentylphenol was used in place of 4-hydroxy-3-t- .

FIG. 1 is a graph showing the absorbance of each of the synthesized compounds measured by wavelength. The absorbance was measured using a device of the UV-1650PC model of Shimatsu Co., and spectral data analyzed by dissolving the dye in MC (methylene chloride) showed that almost all of the absorbed light was absorbed at 400-700 nm in the visible light region In particular, it showed strong absorption at about 580 nm and a dark red color.

Figure 2 shows the results of thermal analysis (TGA) on the synthesized compounds. Thermal analysis was carried out using a thermogravimetric analyzer Model 20050 from TA Instruments. The isothermal section was set at 230 ° C for 1 hour in accordance with the LCD process conditions. From Fig. 2, the reduction of mass in the case of the compound 1-4 showed excellent heat resistance property at about 1 wt.% At an isothermal temperature of 230.degree.

The solubility of the synthesized compounds was measured at room temperature (25 ℃) for PGMEA (propylene glycol methyl ether acetate) solvent. The following table summarizes the solubilities of the synthesized compounds.

compound Solubility (g / 100 ml) 1-4 4-6 1-5 3-5 1-6 3-4

From Table 1, the light-scattering pigments according to the present invention have a solubility level of 3 to 6 g / 100 ml and a remarkable increase in solubility compared with conventional perylene pigments which are almost insoluble.

As the perylene black, the products and used products in the existing literature are almost in the form of pigments and have no solubility in the process solvent. Therefore, after the physical pressure is applied to make the particles very small and small (milling process), the dispersant or surfactant Is used to maximize the dispersibility without aggregation. On the other hand, the dyed product of the present invention has its own solubility in the process solvent by changing the dye structure so that this process can be reduced or omitted. In addition, there is a general tendency that the heat resistance of the dye is lowered when the structural modification for increasing the solubility (dyeing) is usually performed, and the present invention exhibits a property satisfying the heat resistance.

Example 4: Preparation of Black Matrix

A first polymer (weight average molecular weight (Mw): 15,000 (weight average molecular weight (Mw)) contained in a polymer at a molar ratio of 1: 0.5: 0.5 of octyl methacrylate, methacrylic acid and 3-acryloyloxy- ) Containing 4.03 g (solid content concentration of 40 wt%) of styrene, cyclohexylmaleimide, methacrylic acid and glycidyl methacrylate units in a molar ratio of 1: 1: 1: 1 (weight average , 4.92 g of dipentaerythritol hexaacrylate, 1.43 g of an oxime ester initiator (commercial product OXE-02 from Ciba Co., Ltd.) as a pigment for a light-shielding film 29.3 g of the compound 1-4 synthesized in Example 1, 0.08 g of 3-glycidoxypropyltrimethoxysilane, 0.08 g of a surfactant FZ 2122 (Dow Corning Toray Co., Ltd.) and 26.1 g of propylene glycol methyl ether acetate were mixed and 2 Lt; 0 > C for a period of time to prepare a photocurable resin composition.

The resulting solution was sprayed with 4cc on a 6 inch glass substrate using an SUSS microtec GAMMA device and then applied by spin coating.

The coated glass substrate was cooled on a hot plate of 85 캜 for 130 seconds through a drying process, and then formed into a layer having a thickness of 3.5 탆.

The glass substrate coated with the photo-curable resin composition was placed on a substrate of an SUSS microtec MA-6 exposure apparatus equipped with a patterned mask and exposed at a wavelength of ghi-line for a specific exposure energy in a gap of 25 μm in a gapped state. The exposed glass substrate was developed using a KOH developer containing a surfactant such as CD-150CR. In this case, the developer was exposed to the developer for 100 seconds in a spray type developing machine programmed at a water pressure of 500 mm / min and a temperature of 23 ° C., The DI was washed for 20 seconds and the spin drying was completed for 20 seconds. After completion of the development, the glass substrate was subjected to a heat curing process in a convention oven at 220 ° C for 1 hour, and finally a black matrix pattern to be finally realized was completed.

3 is a SEM photograph of the black matrix pattern prepared above. The photographs were obtained using an FE-SEM JSM-6700F instrument from JEOL. The black matrix pattern prepared by mixing 1-4 of the above dyes with carbon black was confirmed by SEM as shown in the table below. As a result, the dispersibility and the optical density were comparable to those of commercialized organic pigments, and the pattern was good. Also, when the dielectric constant was measured, the electrical characteristics were found to be satisfactory to the LCD standards requiring low dielectric constant.

Claims (9)

1. A pigment for a light-blocking film comprising a compound represented by the following Formula 1:
Formula 1

Wherein R ¹ and R ² are independently the following substituents,

Wherein R ³ to R ⁷ are each independently selected from the group consisting of hydrogen, C _{1 to} C ₁₀ linear or branched alkyl, and C _{1 to} C ₁₀ straight chain or branched alkoxy. delete A compound according to claim 1, wherein R ³ to R ⁷ are each independently selected from the group consisting of hydrogen, C ₁ -C ₅ linear or branched alkyl and C ₁ -C ₅ linear or branched alkoxy Pigment for light blocking film. The light-blocking film of claim 1, wherein the compound is one selected from the group consisting of the following compounds [1-1] to [1-12]:

[1-1] [1-2] [1-3] [1-4]

[1-5] [1-6] [1-7] [1-8]

[1-9] [1-10] [1-11] [1-12]
The pigment for a light-blocking film according to claim 1, wherein a weight loss measured by setting an isothermal section at 230 ° C for 1 hour is 1 wt% or less. The pigment for a light-blocking film according to claim 1, wherein the solubility in PGMEA solvent is 3-6 g / 100 ml at 25 ° C. 7. A photocurable composition comprising the pigment for a light-blocking film according to any one of claims 1 to 6. An electronic device element comprising a light shielding film formed by applying the composition of claim 7 to a substrate. The electronic device element according to claim 8, wherein the light blocking film is a color filter black matrix, a black column spacer, a black bezel, or an OLED black insulating film.

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