KR102425173B1 - Light-shielding pigment composition and light-shielding member for display - Google Patents

Abstract

(식(1) 중, R¹∼R⁶은 각각 독립적으로, 수소 원자, 할로겐 원자, 니트로기, 치환기를 갖고 있어도 되는 알콕시기, 치환기를 갖고 있어도 되는 아미노기, 치환기를 갖고 있어도 되는 설포닐기, 치환기를 갖고 있어도 되는 카르복시기, 또는 치환기를 갖고 있어도 되는 1가의 탄화수소기임)으로 표시되는 유기 안료(A)를 함유하는 것을 특징으로 하는 차광성 안료 조성물을 제공함으로써, 상기 과제를 해결한다.The problem to be solved by the present invention is to provide a light-shielding pigment composition having high optical density and high exposure sensitivity. Moreover, it is providing the light-shielding member for displays containing the said light-shielding pigment composition. A light-shielding pigment composition comprising two or more organic pigments, at least as an organic pigment, the following general formula (1):

(in formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a sulfonyl group which may have a substituent, a substituent By providing the light-shielding pigment composition characterized by containing the organic pigment (A) represented by the carboxy group which may have or the monovalent hydrocarbon group which may have a substituent, the said subject is solved.

Description

Light-shielding pigment composition and light-shielding member for display

The present invention relates to a light-shielding pigment composition capable of realizing a high optical density, and a light-shielding member for a display using the light-shielding pigment composition.

In recent years, in the field of a liquid crystal display device, a liquid crystal panel incorporating a color filter on array (COA) in which a color filter substrate and a TFT (Thin Film Transistor) array substrate are integrated is attracting attention. The use of COA eliminates the need for precise alignment performed when the two substrates are used, and allows each pixel of red, blue, and green of the color filter to be miniaturized to the limit.高精細化) becomes possible.

Since high light-shielding property is required for such a resin black matrix for COA, thickness formation is calculated|required. However, as the film thickness of the resin black matrix increases, the difference in crosslinking density with respect to the film thickness direction in the exposed portion widens. Therefore, it becomes difficult to achieve high sensitivity and obtain a black pattern of a good shape. . Moreover, when carbon black with high light-shielding property was used as a means of increasing light-shielding property, similarly, there existed a problem that exposure sensitivity fell.

In order to solve these drawbacks, instead of carbon black, attempts to use a black organic pigment composition (organic black matrix) obtained by mixing a plurality of organic pigments to become black in a light-shielding material have been actively conducted in recent years (for example, Patent Document 1).

Here, a blue pigment such as phthalocyanine or indanthrene is mainly used for light blocking in a long wavelength region (550 nm to 780 nm). However, conventionally known blue pigments have a small absorption intensity around 555 nm, which greatly contributes to an OD value showing light-shielding properties (a numerical value indicating optical density and light-shielding performance, and a larger number indicates a higher light-shielding performance), Since the absorption intensity of 365 nm used for curing the ultraviolet curable resin is large, when it is made black in combination with a short-wavelength absorption pigment and a medium-wavelength absorption pigment, there is a problem that the light-shielding is insufficient and the exposure sensitivity is lowered.

Among these, a blue pigment having a large absorption intensity at 555 nm, which greatly contributes to the optical density, and a small absorption intensity at 365 nm, has been demanded.

Japanese Patent Application Laid-Open No. 9-302265

The problem to be solved by the present invention is to provide a light-shielding pigment composition having high optical density and high exposure sensitivity. Moreover, it is providing the light-shielding member for displays containing the said light-shielding pigment composition.

The present inventors paid attention to the blue pigment which has a large influence on the performance of the light-shielding composition containing a some organic pigment in view of the said actual situation. While many blue pigments are known, the present inventors discovered that the said subject was solvable by using the specific organic pigment mentioned later as a blue pigment, and came to complete this invention.

That is, the present invention is a light-shielding pigment composition comprising two or more organic pigments,

As an organic pigment, at least the following general formula (1):

(wherein, R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a sulfonyl group which may have a substituent, or a substituent It relates to a light-shielding pigment composition comprising an organic pigment (A) represented by a carboxy group or a monovalent hydrocarbon group which may have a substituent (for convenience, it is referred to as an organic pigment (A)).

Moreover, as another aspect of this invention, the said organic pigment (A) is C.I. pigment 25 or 26, It is related with the light-shielding pigment composition characterized by the above-mentioned.

Further, as another aspect of the present invention, the organic pigment (A) has a maximum absorbance at a wavelength of 580 nm to 780 nm under the following conditions (condition: visible light region (380 nm to 780 nm), and 365 nm It relates to a light-shielding pigment composition characterized in that it is an organic pigment (A) that satisfies the absorbance at 50% or less of the maximum absorbance, and the absorbance at 555 nm and 700 nm is 50% or more of the maximum absorbance.

As another aspect of the present invention, the light-shielding pigment composition of the present invention further comprises a benzimidazolone pigment comprising a chemical structure represented by the following general formulas (2) and (3), the following general formula (4) ) It relates to a light-shielding pigment composition, characterized in that it further contains one or both of the benzimidazolonedioxazine pigments having a chemical structure represented by .

(Wherein, R ¹ to R ³ each represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent)

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represents a hydrogen atom or a halogen atom; one or more of X ³ , X ⁴ , X ⁵ , X ⁶ is a halogen atom; R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent)

Moreover, as another aspect of this invention, it is related with the light-shielding member for displays containing the light-shielding pigment composition of this invention mentioned above.

The light-shielding pigment composition of this invention has high optical density and since exposure sensitivity is high, it can be used suitably for the light-shielding member for displays.

The light-shielding pigment composition of this invention contains a specific organic pigment (the said organic pigment (A)) as an essential component, By using together organic pigments, such as orange, yellow, purple, and red, a black light-shielding pigment to make up the composition. The light-shielding member for displays containing such a light-shielding pigment composition of this invention has high optical density, and has the outstanding performance that exposure sensitivity is high.

The organic pigment (A) has the following general formula (1):

(Wherein, each of R ¹ to R ⁶ represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a sulfonyl group which may have a substituent, and a carboxy group which may have a substituent. , or a monovalent hydrocarbon group which may have a substituent).

Such an organic pigment is a blue pigment with a large absorption intensity at 555 nm that greatly contributes to the optical density and a small absorption strength at 365 nm, and when used as a light-shielding composition, an excellent optical density can be obtained.

Here, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples of the alkyl moiety of the alkoxy group include those having 1 to 6 carbon atoms.

Among these, it is preferable to use C.I. Pigment Blue 25 (which may also be expressed as PB25) or C.I. Pigment Blue 26 (which may also be expressed as PB26). Both PB25 and PB26 are organic pigments known from ancient times, but their use was limited to use as a colorant (use in which blue coloration is expected).

Here, a 365 nm ultraviolet-ray is generally used abundantly for hardening of an ultraviolet curable resin. Ultraviolet light refers to light having a wavelength of 100 nm to 400 nm, and the shorter the wavelength, the greater the energy. However, at a wavelength of 200 nm or less, energy is consumed for decomposition of oxygen or easily absorbed by oxygen, so light sources of 254 nm and 365 nm are mainly used for UV curing. The energy contained in the same amount of light is 254 nm light: 365 nm light = about 3:2, whereas 254 nm light reaches only 40% of the resin with a thickness of 2 μm, whereas 365 nm light is Even with a thickness of 12 µm, 90% or more reaches the inside. In addition, since a high-pressure mercury lamp emitting 365 nm light can be 20 times as long as a low-pressure mercury lamp emitting 254 nm light and a wattage, a high-pressure mercury lamp emitting 365 nm ultraviolet ray is used for UV curing. it is preferable

The OD value used as a parameter|index of light-shielding property can be calculated|required from the following formula in accordance with JIS Z 8701.

Y: Luminance (brightness)

k: constant

T: transmittance

S: light intensity

y: isochromatic function (the sensitivity of the human eye)

OD = log10 (maximum luminance/Y) = log10 (100/Y)

Here, the color matching function y may use the one described in JIS Z 8701, and the light source intensity S may use the C light source (auxiliary illuminant C for colorimetry) described in JIS Z 8720. The light absorption intensity at 555 nm at which the constant calculated the intensity of the y × C light source at each wavelength becomes the maximum value has a large contribution to the OD value. can be used as an indicator.

Further, in JIS Z 8722, a method of measuring the range of 400 nm to 700 nm with a type 2 spectrophotometer is included as a method for measuring color. By measuring the light in the above-mentioned wavelength range, practical color expression becomes possible. 700 nm is close to the limit at which the human eye perceives color, and light with a wavelength longer than 700 nm has a very small contribution to the external color and OD value. Moreover, when mixing an organic pigment and setting it as black, it is known that external blackness can be improved by having absorption uniformly in 400 nm - 700 nm. Therefore, in order to obtain the blackness of appearance suitable as a black light-shielding composition, and a high OD value, about the pigment which has absorption in the long wavelength range used for mixing, it is preferable to have high absorbance in 700 nm.

It is preferable from the point which can obtain the outstanding optical density to select what satisfy|fills the following conditions among the said organic pigment (A).

Conditions: Absorbance in the visible region (380 nm to 780 nm) is maximum at a wavelength of 580 nm to 780 nm, and the absorbance at 365 nm is 50% or less of the maximum absorbance at 555 nm and 700 nm. The absorbance is 50% or more of the maximum absorbance.

Whether or not the above conditions are satisfied can be determined by dispersing the target organic pigment in PMA (propylene glycol monomethyl ether acetate), diluting the dispersion using PMA, and using a spectrophotometer (U3900, Hitachi High-Tech Sciences, Ltd.) It can be easily specified by measuring the absorbance spectrum in the first) and confirming the position of the peak top, the maximum absorbance, the absorbance at 365 nm, the absorbance at 555 nm, and the absorbance at 700 nm.

In the present invention, the organic pigment (organic pigment (A)) represented by the formula (1) may be used as it is, but in order to satisfy the above conditions, adjustment of the average primary particle diameter and adjustment of the crystal structure , it can be used while satisfying the above conditions by adjusting the dispersibility to a solvent or the like.

Here, when an organic pigment represented by the formula (1) is used as the organic pigment (A), the organic pigment has an average primary particle diameter in the small-angle X-ray scattering method in the range of 30 nm to 190 nm. It is preferable, and it is more preferable to exist in the range of 50 nm - 160 nm. By adjusting the average primary particle diameter within this range, the absorbance at 555 nm and 700 nm can be increased, and the optical density can be made higher.

The light-shielding pigment composition of the present invention is compared with the case where conventional copper phthalocyanine or C.I. Pigment Blue 60 is used as a blue pigment in the mixed color organic pigment, as shown in Examples (Table 2) to be described later, optical density and A light-shielding member for a display which is remarkably excellent in exposure sensitivity can be obtained.

Here, a display is a device which displays the image signal of a still image or a moving image output from apparatuses, such as a computer and a television. Also called monitor, there are plasma display (PDP), liquid crystal display (LCD), EL display (ELD), field emission display (FED), crystal LED display (CLED), and the like.

In addition, the light-shielding member for displays of this invention is a material for shielding light emission from a light emitting member like a visible light region or the backlight in a display. Specific examples include a black matrix, a TFT light-shielding film, a black mask, a black seal, a black column spacer, and an electric field limiting layer in ELD.

You may mix other organic pigments, inorganic pigments, coloring agents, such as dye, with the light-shielding pigment composition of this invention so that the balance of the permeability|transmittance of a visible region may not be impaired. Examples of the colorant to be mixed include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, tren pigments, perylene pigments, perinone pigments, Insulative organic pigments such as quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, benzimidazolone pigments and indanthrene pigments are preferable, and in particular, at least one organic pigment selected from yellow, orange, red, and purple. It is advantageous to contain a pigment.

If the combination of colors to be mixed is to be described in detail, for example, a combination of blue and orange, a combination of blue and orange and purple, a combination of blue and yellow and purple, and a combination of blue and yellow and red may be mentioned. Of course, two or more types of blue pigments may be used in combination of the same color, or the pigment of another color may be combined in addition to the combination of the color of the same color. Moreover, you may use together blue pigments other than an above-described organic pigment (A) further, and you may use multiple types of pigments applicable to an above-described organic pigment (A). As for the organic pigment to be used and its combination, the blackness calculated|required for the black matrix etc. made into the objective should just be obtained. For example, making black by subtractive color mixing of the three primary colors of blue, yellow, and red belongs to those skilled in the art, and the mixing ratio thereof is not particularly limited. Hereinafter, the example of each color pigment is shown.

As a blue pigment which may be further added, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16 , 17, 19, 27, 28, 29, 33, 35, 36, 56, 56:1, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 , 78, 79, 80, and the like.

As a yellow pigment, For example, C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34 , 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75 , 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129 , 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 , 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196 , 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 213, 214, 229 and the like. Among these, preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is mentioned, More preferably, C.I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

As the orange pigment, for example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 , 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 81, and the like. Among these, preferably, C.I. pigment orange 36, 38, 60, 62, 64, 72 is mentioned.

As a brown pigment, C.I. Pigment Brown 23, 25, 41 etc. are mentioned, for example.

As a red pigment, For example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32 , 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53 , 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81 , 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123 , 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194 , 200, 202, 206, 207, 208, 209, 210, 213, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245 , 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274 , 275, 276, 279, and the like. Among these, preferably C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is mentioned, More preferably, C.I. Pigment Red 177, 209, 224 and 254 are mentioned.

As the purple pigment, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23 , 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, Preferably C.I. Pigment Violet 19, 23, 29 is mentioned, More preferably, C.I. Pigment Violet 23 is mentioned.

As a green pigment, For example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 , 55, 58, 59. Among these, preferably C.I. Pigment Green 7 and 36 are mentioned.

As an organic pigment further used in combination with the light-shielding pigment composition of the present invention, benzimi containing a chemical structure represented by the following general formulas (2) and (3) from the viewpoint of obtaining more suitable light-shielding properties It is preferable to use one or both of a dazolone type pigment and the benzimidazolonedioxazine type pigment containing the chemical structure represented by the following general formula (4).

(Wherein, R ¹ to R ³ each represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent)

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represents a hydrogen atom or a halogen atom; one or more of X ³ , X ⁴ , X ⁵ , X ⁶ is a halogen atom; R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent)

In addition, the compound of the said Formula (4) is not restrict|limited in particular, A conventionally well-known method can be used suitably and can be manufactured. Hereinafter, one aspect of the manufacturing method of the compound of the said Formula (4) is described.

The compound of the formula (4) can be produced, for example, by synthesizing a compound of the formula (V) described later by the method described in Japanese Patent Application Laid-Open No. 11-335575, and halogenating it by a halogenation reaction described later. Details are given below.

<Condensation Reaction>

1 mole of a base such as sodium acetate, sodium hydrogen carbonate, and triethylamine and 2 moles of a p-benzoquinone compound of the following formula (II) are suspended in a solvent such as ethanol or dimethylacetamide, and the suspension is placed at 40°C to 70°C. heated to °C. 1 mole of the amine compound of the following formula (III) is added over 1 hour, and the mixture is continuously heated under reflux for 1 hour to 10 hours. Then, 1 mol of a base such as sodium acetate, sodium hydrogen carbonate, and triethylamine is further added, followed by addition of 1 mol of the amine compound of the following formula (IV). The mixture is stirred under reflux for 1 hour to 10 hours, then the solid product is filtered off while hot, and washed with a solvent such as ethanol or dimethylacetamide at 60° C. to 100° C., and then wash with boiling water. The product is suspended in a solvent such as dimethylformamide or dimethylacetamide, the suspension is heated at 80°C to 150°C for 1 hour to 10 hours, filtered while hot, and the solid product is ethanol at 60°C to 100°C , washing with a solvent such as dimethylacetamide, followed by washing with boiling water, and drying at 90°C to 120°C.

(In formula (II), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and X ⁷ and X ⁸ each independently represent a leaving group such as a halogen atom or an alkoxy group)

(In formula (III), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent)

(In formula (IV), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent)

<Circulation Reaction>

The product obtained in the condensation reaction is added to concentrated sulfuric acid at 10°C or lower over 1 hour. Then, 2 moles to 4 moles of manganese dioxide are added over 3 hours, and the mixture is continuously stirred at room temperature for 18 hours to 48 hours. This mixture is diluted to a sulfuric acid concentration of 80% by adding water while cooling. Excess manganese dioxide is destroyed using hydrogen peroxide (30%). The mixture is filtered through a polypropylene filter, and the solid product is washed with sulfuric acid (80%), then with sulfuric acid (50%), followed by washing with water. It dries at 90 degreeC - 120 degreeC, and the compound represented by following formula (V) is obtained.

(In formula (V), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom; R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a monovalent optionally having a substituent. represents a hydrocarbon group)

<Halogen addition reaction>

1 mol to 32 mol of a halogenating reagent such as bromine, N-bromosuccinimide, trichloroisocyanuric acid, or N-iodosuccinimide is added to concentrated sulfuric acid having a temperature of 10° C. or less, followed by the ring closure reaction 1 mol of the compound represented by the formula (V) obtained in above is added, and the mixture is stirred at room temperature for 2 hours to 48 hours. Then it is poured into ice, the resulting precipitate is filtered, washed with water until no acid is detected, then with ethanol, dried at 90°C to 120°C, and the benzene ring is converted to a halogen atom. It is obtained as a mixture of 1-4 substituted compounds. When obtained as a single compound through this method, the obtained mixture is added to a solvent such as N,N-dimethylformamide, and then a base such as 4-dimethylaminopyridine, di-tert-butyldicarbonate (“ tert") is added, and the mixture is stirred at room temperature for 2 hours to 48 hours. Then, this is poured into water, extracted with a solvent such as chloroform, and the solvent layer is concentrated under reduced pressure to obtain a mixture. The obtained mixture is separated by silica gel column chromatography, and each solution having a single compound obtained is concentrated, a solvent such as N,N-dimethylacetamide and an acid such as toluene-4-sulfonic acid monohydrate are added thereto, and 100° C. A precipitate is obtained by stirring at -200°C for 2 hours to 24 hours. The precipitate is filtered, washed with a solvent such as N,N-dimethylacetamide, and dried at 90°C to 120°C to obtain the compound of formula (4).

The light-shielding pigment composition of this invention may refine|miniaturize and mix each organic pigment independently according to the specification of the light-shielding member for displays, and it does not matter even if it refines|miniaturizes after mixing.

The method of refinement|miniaturization of a pigment can be performed by a well-known common method, and is not specifically limited. Generally, a solvent salt milling method, a sulfuric acid dissolution method, a dry grinding method, a pigmentation method by atmospheric pressure and pressure using an organic solvent and water, or a method by a combination thereof, etc. can be employed.

An organic dye derivative may be mixed with the composition of this invention, and an organic dye derivative may have what kind of chemical structure as long as it has a sulfonic acid group, a phthalimide group, or is an organic dye derivative which is a sulfonate. An organic pigment derivative having a sulfonic acid group, a phthalimide group, or a sulfonic acid salt is often added to an organic pigment in order to improve dispersibility in a binder and a solvent system, and the effect is well known. The number of substituents in the sulfonic acid group is 1 to 4 per molecule, preferably 1 to 2. Since the pigment composition of this invention is black type, any organic pigment derivative can be used. Specifically, there are an azo structure, a benzimidazolone structure, a quinacridone structure, a diketopyrrolopyrrole structure, a phthalocyanine structure, a dioxazine violet structure, and the like. Among them, copper phthalocyanine sulfonic acid or a salt thereof, phthalimide is preferable. methyl copper phthalocyanine, quinacridone sulfonic acid or its salt, and phthalimide methyl quinacridone. The metal which forms a salt with a sulfonic acid is a monovalent|monohydric or divalent metal, such as Ca, Na, K, Mg, Fe, Co, Ni, Cu, and Zn. In addition, as those that form salts other than metal salts, there are organic amine salts such as aliphatic amines (NHR ₂ , NH ₂ R, [NR ₄ ] ⁺ (R: alkyl group having 1 to 20 carbon atoms)).

The organic dye derivative is contained in the range of 1 to 20 parts per 100 parts of the organic pigment. When a hue and productivity are considered, it is preferable to contain in the range of 1-15 parts. The timing of adding the organic dye derivative may be added in the step of refining the organic pigment carried out in the present invention, or may be added after the step of refining and washing and refining the organic pigment. However, it is preferable to treat with an organic pigment after refinement|miniaturization in consideration of provision of the dispersibility effect by the organic pigment derivative which has a sulfonic acid group or its salt.

As a treatment method of the organic dye derivative, there is a method of dyeing with a solid or alkali and adsorbing on the surface of the organic pigment in an acidic state. In the case of a solid, it is added to a wet cake containing a micronized organic pigment and a solvent such as water. Dyeing of the organic dye derivative with alkali is usually carried out at pH 8 to 12, and then mixing with the refined organic pigment in a slurry, and then adjusting the inside of the system to acidity, usually pH 3 to 5, and applying to the surface of the organic pigment. An organic dye derivative is precipitated. Moreover, in manufacturing the light-shielding pigment composition of this invention, you may add various additives other than an organic dye derivative. Specific examples thereof include light or thermosetting resins, surfactants, dispersants, and rosin.

A coloring composition is produced from the pigment composition of this invention, and a resin-type dispersing agent and an organic solvent as needed. As a method of preparing a coloring composition, the coloring composition which disperse|distributed each color organic pigment, organic solvent, and a dispersing agent separately may be mixed, and an all organic pigment may be disperse|distributed with an organic solvent and a dispersing agent at once.

When dispersing these pigment compositions in an organic solvent, a resin-based dispersing agent is used in combination for the purpose of improving dispersibility and improving dispersion stability. This resin-based dispersant binds to an organic pigment and an anchor moiety, and the compatible moiety extends to the dispersion medium to form a dispersion, and alkali-soluble used for preparation of a photosensitive composition described later It is a thing different from resin and a photopolymerizable monomer.

As a resin type dispersing agent, what has a polymer chain, for example, a polyurethane resin, polyethyleneimine, polyoxyethylene glycol diester, an acrylic resin, a polyester resin, etc. are mentioned. Especially, a polyester resin type dispersing agent and/or an acrylic resin type dispersing agent are preferable at the point of dispersibility, heat resistance, and light resistance.

Specific examples of the various resin-based dispersants include, as trade names, Ajisu wave (manufactured by Ajinomoto Fine Techno Corporation), EFKA (manufactured by BASF Corporation), DISPERBYK (manufactured by Bikchemi Corporation), DISPERON (manufactured by Kusumoto Chemical Corporation), and SOLSPERSE (manufactured by Lubrizol Corporation). , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical), and the like. These dispersants may use 1 type, and can use 2 or more types together by arbitrary combinations and a ratio.

A resin-type dispersing agent is 30-60 parts normally per 100 parts by mass conversion of the sum total of the organic pigment of each color, Preferably it is 38-50 parts.

Examples of the organic solvent used herein include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate. , n-octane, Barsol #2, Abco #18 solvent, diisobutylene, amyl acetate, butyl acetate, abco thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methylnonyl ketone, propyl ether , dodecane, socarsolvent No. 1 and No. 2, amyl formate, dihexyl ether, diisopropyl ketone, sorbetso #150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, Butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate , methyl cellosolve acetate, methyl isoamyl ketone, n-amyl methyl ketone (2-heptanone), methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether Acetate, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cello Solve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxypropionic acid methyl, 3-ethoxypropionate ethyl, 3-methoxy Methyl propionate, 3-methoxyethyl propionate, 3-methoxypropyl propionate, 3-methoxybutyl propionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t- Butyl ether, 3-methoxybutanol, 3 -Methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. are mentioned.

When using the coloring composition to prepare a photosensitive composition for forming a black matrix by a photolithography method, in order to have a low viscosity and excellent coatability, workability, and ejection properties, at least to be contained in the coloring composition It is preferable to use n-amylmethyl ketone (2-heptanone) as an organic solvent.

In order to prepare a coloring composition, an organic solvent may be used individually by 1 type, and can use 2 or more types together by arbitrary combinations and a ratio. However, the coloring composition of this invention WHEREIN: It is 300-800 parts normally per 100 parts of mass conversion of the sum total of the organic pigment of each color, It is preferable to use an organic solvent, Preferably it is 400-600 parts.

In preparation of a coloring composition, various pigment derivatives etc. can be used together as needed, for example. As a substituent of the pigment derivative, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group, etc. are added directly to the pigment skeleton or an alkyl group, an aryl group, a heterocyclic group. and those combined with the back interposed therebetween.

A coloring composition can be prepared by stirring and mixing the organic pigment composition of each above-mentioned color, a resin type dispersing agent, and an organic solvent. If necessary, it can also be prepared by shaking and dispersing the mixture over a required time in the presence of various grinding media such as beads and rods, and removing the media by filtration or the like.

The coloring composition requires a black matrix or black mask of a color filter that is a constituent member of a display, a column spacer or black seal of a liquid crystal layer, a TFT light-shielding film, a field-limiting layer in ELD, and other display light-shielding methods by a conventionally known method. It can be used for members with

A typical manufacturing method of a color filter is a photolithography method, after a black matrix apply|coats the below-mentioned photosensitive composition prepared from the coloring composition of this invention on the transparent substrate for color filters, and heat-dries (prebaking) , pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure a photocurable compound in a portion corresponding to the black matrix portion, then the unexposed portion is developed with a developer, and the non-pixel portion is removed This is a method of fixing the pixel portion to the transparent substrate. In this way, a black matrix portion made of a cured colored film of the photosensitive composition is formed on the transparent substrate. Each pixel part of RGB can also be similarly prepared from the photosensitive composition prepared from the organic pigment of each color with a larger specific surface area as mentioned above.

As a method of apply|coating the photosensitive composition mentioned later on transparent substrates, such as glass, the spin coating method, the roll coating method, the slit coating method, the inkjet method etc. are mentioned, for example.

Although the drying conditions of the coating film of the photosensitive composition apply|coated to the transparent substrate also change with the kind of each component, a compounding ratio, etc., it is 50-150 degreeC normally, and it is about 1 to 15 minutes. This heat treatment is generally called "pre-baking". Moreover, as light used for photocuring of the photosensitive composition, it is preferable to use the ultraviolet-ray or visible light which is a wavelength range of 200-500 nm. Various light sources emitting light in this wavelength range can be used.

As a developing method, the liquid method, the dipping method, the spray method etc. are mentioned, for example. After exposure and development of the photosensitive composition, the transparent substrate on which the black matrix or pixel portion of the required color is formed is washed with water and dried. The color filter obtained in this way is heat-processed (post-baking) for a predetermined time at 100-280 degreeC with heating apparatuses, such as a hot plate and oven, while removing the volatile component in a colored coating film, the cured coloring film of a photosensitive composition. The unreacted photocurable compound remaining in the inside is thermosetted, and a color filter is completed.

The photosensitive composition for forming the black matrix part of a color filter uses the coloring composition of this invention, alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator as essential components, It can prepare by mixing these.

In the case where the color resin film forming the black matrix portion is required to have toughness to withstand baking etc. performed in real production of color filters, in the preparation of the photosensitive composition, not only the photopolymerizable monomer but also this alkali It is indispensable to use a soluble resin together. When using alkali-soluble resin together, it is preferable to use what melt|dissolves it as an organic solvent.

As a manufacturing method of the said photosensitive composition, after preparing the coloring composition of this invention in advance, the method of adding alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator thereto, and setting it as the said photosensitive composition is common.

As alkali-soluble resin used for preparation of the photosensitive composition, resin containing a carboxy group or a hydroxyl group which shows acidity, for example, a novolak-type phenol resin, (meth)acrylic acid alkylester-(meth)acrylic acid copolymer, styrene-( A meth)acrylic acid copolymer, a styrene-maleic acid copolymer, etc. are mentioned. In addition, in this invention, the base material with (meth)acryl is a generic term which combined acryl and methacryl.

Especially, in order to improve the heat resistance of a cured film more, it is preferable to use alkali-soluble resin containing each polymerization unit of an imide structure, styrene, and (meth)acrylic acid.

This alkali-soluble resin binds to the above-described organic pigment and anchor moiety, and does not have the function of compatibility moieties extending to the dispersion medium to form a dispersion, but on the other hand, taking advantage of the feature of dissolving in contact with alkali, It is used solely for the purpose of removing the unexposed portion of the photosensitive composition.

Examples of the photopolymerizable monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. Bifunctional monomers such as , bis[(meth)acryloxyethoxy]bisphenol A, 3-methylpentanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) ) polyfunctional monomers having a relatively small molecular weight, such as acrylate, and polyfunctional monomers having a relatively large molecular weight, such as polyester acrylate, polyurethane acrylate, and polyether acrylate. As described above, the term (meth)acrylate is a generic term for acrylate and methacrylate.

Especially, in order to improve the heat resistance of a cured film more, it is preferable to use the (meth)acrylate of tetrafunctional - hexafunctionality.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethyl ketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis(4'-azidebenzal)-2-propane, 1,3 -Bis(4-azidebenzal)-2-propane-2'-sulfonic acid, 4,4'-diazidestilbene-2,2'-disulfonic acid, ethanone, 1- [9-ethyl-6- [2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9.H.-carbazol-3-yl]-,1-(O-acetyloxime), etc. can be heard

Since the photosensitive composition of this invention is black, it is preferable to use the photoinitiator excellent in sclerosis|hardenability.

In the photosensitive composition of the present invention having such characteristics, the total amount of the alkali-soluble resin and the photopolymerizable monomer per 100 parts of the coloring composition of the present invention is 3 to 20 parts, and 0.05 to 3 parts of the photopolymerization initiator per 1 part of the photopolymerizable monomer; Furthermore, the organic solvent used for preparation of said coloring composition is added, it stirs and disperses so that it may become uniform, and the photosensitive composition for forming a black-matrix part can be obtained.

In order to form a black matrix by a photolithography method, in order to make the photosensitive composition of the present invention low-viscosity and excellent in coatability and workability, it is preferable to prepare at least 5 to 20% of non-volatile content in terms of mass. .

As a developing solution, a well-known and usual aqueous alkali solution can be used. In particular, since alkali-soluble resin is contained in the said photosensitive composition, washing|cleaning in aqueous alkali solution is effective in formation of a black matrix part. The excellent heat resistance of the photosensitive composition of this invention is exhibited in the manufacturing method of the color filter which bakes after such alkaline washing.

Among the pigment dispersion methods, although the manufacturing method of the black-matrix part by the photolithographic method was described in detail, the black-matrix part prepared using the photosensitive composition of this invention is another electrodeposition method, a transfer method, a micellar electrolysis method, PVED (Photo It may form by methods, such as a Voltaic Electro Deposition method, and may manufacture a color filter.

The color filter uses a red organic pigment, a green organic pigment, a blue organic pigment, and a photosensitive composition of each color obtained by using the coloring composition of the present invention, a liquid crystal material is enclosed between a pair of parallel transparent electrodes, and a transparent electrode is divided into discontinuous fine sections, and in each of the fine sections divided into a lattice shape by a black matrix on the transparent electrode, any of red (R), green (G) and blue (B) It can obtain by the method of providing the color filter colored pixel part selected from one color in pattern shape alternately, or by making it provide a transparent electrode after forming a color filter colored pixel part on a board|substrate.

The black matrix part obtained from the photosensitive composition of this invention is contained so that each color organic pigment mentioned above may become black, and at a glance, the same black as when the photosensitive composition of each color is mixed and the black photosensitive composition is prepared. Although it is thought that a matrix is obtained, in the present invention, at the time of preparation of the coloring composition which is a step before setting it as a photosensitive composition, as a result of mixing the organic pigments of each color in advance, more uniform mixing is achieved, and more excellent properties of the black matrix can be obtained.

(Example)

Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by this. In addition, in an Example and a comparative example, when there is no notice in particular, "part" and "%" are based on mass.

[Assessment Methods]

The main evaluation methods used in this specification will be described in detail.

(1) Peak top position, etc.

After the pigment to be evaluated is dispersed in PMA (propylene glycol monomethyl ether acetate), the dispersion is diluted using PMA, and the absorption spectrum is measured with a spectrophotometer (U3900, manufactured by Hitachi High-Tech Sciences, Ltd.), and peak top The position, the maximum absorbance, the absorbance at 365 nm, the absorbance at 555 nm, and the absorbance at 700 nm were confirmed.

(2) Measurement of optical density (OD value)

The black matrix was produced, and the absorbance in 365 nm, the light absorbency in 700 nm, and the transmittance|permeability (I ₀ /I) in each wavelength were measured with the spectrophotometer (U-3900). According to JIS Z 8701, the OD value of the black matrix was calculated|required from the following formula.

Y: Luminance (brightness)

k: constant

T: transmittance

S: light intensity

y: isochromatic function (the sensitivity of the human eye)

OD = log10 (maximum luminance/Y) = log10 (100/Y)

<Pigment manufacturing process>

C.I. Pigment Blue 25 (synthesized based on Japanese Patent Application Laid-Open No. 51-97633) is mixed with sodium chloride and diethylene glycol, and wet grinding is performed with a stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.). Pigments A-1 to A-5 were prepared. The average primary particle diameters of pigments A-1 to A-5 were measured using the USAXS method of SmartLab (manufactured by Rigaku Corporation) (36 nm for pigment A-1, 53 nm for pigment A-2, and 53 nm for pigment A-3 Silver was 94 nm, Pigment A-4 was 155 nm, and Pigment A-5 was 189 nm).

(Example 1)

0.4 parts of the obtained pigment A-1, 0.5 parts of LPN-21116 (manufactured by BYK Corporation, a resin dispersant), and 7.4 parts of propylene glycol monomethyl ether acetate are mixed, 0.2 to 0.3 mm phi zirconia beads are added, and a paint conditioner (Toyo) It disperse|distributed for 2 hours by Seiki Corporation make, and the coloring composition (B-1) was obtained. 99.9 parts of propylene glycol monomethyl ether acetate were added to 0.1 part of coloring composition (B-1), and the composition (C-1) for evaluation was prepared.

(Example 2)

Except having changed the pigment A-1 into the pigment A-2, operation similar to the said Example 1 was performed, and the composition (C-2) for evaluation was obtained.

(Example 3)

Except having changed the pigment A-1 into the pigment A-3, operation similar to the said Example 1 was performed, and the composition (C-3) for evaluation was obtained.

(Example 4)

Except having changed the pigment A-1 into the pigment A-4, operation similar to the said Example 1 was performed, and the composition (C-4) for evaluation was obtained.

(Example 5)

Except having changed the pigment A-1 into the pigment A-5, operation similar to the said Example 1 was performed, and the composition (C-5) for evaluation was obtained.

(Comparative Example 1)

Except having changed the pigment A-1 into Paliogen Blue L6360 (BASF Corporation C.I. Pigment Blue 60), operation similar to the said Example 1 was performed, and the composition (C-6) for evaluation was obtained.

(Comparative Example 2)

A composition for evaluation (C-7) was obtained in the same manner as in Example 1 except that the pigment A-1 was replaced with Fastogen Blue EP-CF (C.I. Pigment Blue 15:6 manufactured by DIC Corporation).

<Confirmation of the peak top position>

The absorbance spectra of the compositions for evaluation obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were measured with a spectrophotometer (U3900, manufactured by Hitachi High-Tech Sciences, Ltd.). A result is shown in Table 1.

[Table 1]

<Production process of coloring composition>

(Example 6)

Pigment A-3 (C.I. Pigment Blue 25, Colorant 1) 12.0 parts, Cromophtal Orange K 2960 (BASF Corporation, C.I. Pigment Orange 64, Colorant 2) 1.5 parts, Paliogen Red Violet K 5411 (BASF Corporation) Agent, C.I. Pigment Violet 29, Colorant 3) 1.5 parts, LPN-21116 (manufactured by BYK, Inc., resin-based dispersant) 4.5 parts, and propylene glycol monomethyl ether acetate 73.8 parts 0.2 to 0.3 mmφ zirconia beads are added to a mixture, , it disperse|distributed with the paint conditioner for 2 hours, and obtained the coloring composition (D-1).

<Production process of photosensitive resin composition>

Coloring composition (D-1) 100 parts, as alkali-soluble resin, methacrylic acid/succinic acid mono(2-methacryloyloxyethyl)/N-phenylmaleimide/styrene/benzyl methacrylate copolymer (copolymerization mass ratio=25 /10/30/20/15, Mw=12,000, Mn=6,500) 5 parts, dipentaerythritol hexaacrylate 10 parts as a photopolymerizable monomer, ethanone as a photoinitiator, 1- [9-ethyl-6-[ 2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9.H.-carbazol-3-yl]-,1-(O-acetyloxime) 1 As parts and an organic solvent, 25 parts of dipropylene glycol dimethyl ether, 25 parts of propylene glycol monomethyl ether acetate, 75 parts of 3-methoxybutyl acetate, and 50 parts of cyclohexanone are mixed, and the photosensitive resin composition (E-1) is prepared did.

<Production process of black matrix>

A 10 cm square glass substrate (a glass plate "OA-10" for color filters manufactured by Nippon Denki Glass) was immersed in a 1% dilution solution of a silane coupling agent "KBM-603" manufactured by Shin-Etsu Chemical for 3 minutes, washed with water for 10 seconds, After draining the water with an air gun, it was dried in an oven at 110°C for 5 minutes. On this glass substrate, the photosensitive resin composition (E-1) prepared above was apply|coated using the spin coater. After vacuum drying for 1 minute, it was dried by heating at 90°C for 90 seconds on a hot plate to obtain a coating film having a dry film thickness of about 3.5 µm. Then, from the coating film side, performing image exposure through a 15-micrometer-wide thin wire pattern mask (pattern 1), and exposing the whole surface without interposing a mask (pattern 2) ) was subjected to two exposures. Exposure conditions were 50 mJ/cm<2> (based on i line|wire) using a 3 kW high-pressure mercury-vapor lamp, respectively. Next, using a developer consisting of an aqueous solution containing 0.05% potassium hydroxide and 0.08% nonionic surfactant (Kao Corporation "A-60"), shower development with a water pressure of 0.15 MPa at 23 ° C. , pure water stopped image development, it wash|cleaned with water spray, and obtained the black matrix (F-1). In addition, shower development time was adjusted between 10 to 120 second, and it was set as 1.5 times the time for which an unexposed coating film is dissolved and removed.

(Example 7)

The same procedure as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-3, the colorant 2 was changed to 2960 parts of Cromophtal Orange K 2960, and the colorant 3 was changed to 3.75 parts of Paliogen Red Violet K 5411. A black matrix (F-2) was obtained.

(Example 8)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 3.0 parts of Pigment A-3, the colorant 2 was changed to Cromophtal Orange K 2960 6.0 parts, and the colorant 3 was changed to Paliogen Red Violet K 5411 6.0 parts. A black matrix (F-3) was obtained.

(Example 9)

Colorant 1 of Example 6 is 12.0 parts of Pigment A-3, Colorant 2 is PV Fast Orange H4GL01 (manufactured by Clariant, C.I. Pigment Orange 72) 1.5 parts, Colorant 3 is Paliogen Red Violet K 5411 1.5 parts Operation similar to Example 6 was performed, and the black matrix (F-4) was obtained.

(Example 10)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-3, the colorant 2 was changed to PV Fast Orange H4GL 01 3.75 parts, and the colorant 3 was changed to Paliogen Red Violet K 5411 3.75 parts. , a black matrix (F-5) was obtained.

(Example 11)

The same procedure as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 3.0 parts of Pigment A-3, the colorant 2 was changed to PV Fast Orange H4GL 01 6.0 parts, and the colorant 3 was changed to Paliogen Red Violet K 5411 6.0 parts. , a black matrix (F-6) was obtained.

(Example 12)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 12.0 parts of Pigment A-3, the colorant 2 was changed to 1.5 parts of Compound G, and the colorant 3 was changed to 1.5 parts of Cromophtal Orange K 2960, and a black matrix ( F-7) was obtained.

Compound G was produced by performing the following operations.

53 parts of N-bromosuccinimide are added to 52500 parts of concentrated sulfuric acid having a temperature of 10°C or less, followed by addition of 350 parts of Compound H (the following structure) synthesized by the method described in Japanese Unexamined Patent Application Publication No. Hei 11-335575, and room temperature was stirred for 20 hours. Then, this was poured into 525000 parts of ice to obtain a precipitate. The resulting precipitate was filtered, washed with water until no acid was detected, then with 30000 parts of ethanol and dried at 90° C. to obtain 390 parts of product I.

390 parts of the obtained product I is added to 2000 parts of N,N-dimethylformamide, followed by 100 parts of 4-dimethylaminopyridine and 800 parts of di-tert-butyldicarbonate ("tert" is described in the meaning of tertiary, ) was added, and the mixture was stirred at room temperature for 16 hours. Then, this was poured into 8000 parts of water, extracted with 8000 parts of chloroform, and the chloroform layer was concentrated under reduced pressure to obtain a product J.

The resulting product C was separated by silica gel column chromatography (developing solvent: chloroform/methanol/dimethylsulfoxide), and a solution containing compound G obtained was concentrated, N,N-dimethylacetamide 500 parts and toluene-4-sulfoxide 50 parts of phonic acid monohydrate was added, and it stirred at 130 degreeC for 4 hours, and obtained the precipitate. The precipitate was filtered, washed with 200 parts of N,N-dimethylacetamide and 800 parts of methanol, and dried at 90°C to obtain compound G (3.4 parts, yield 0.6%).

(Example 13)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-3, the colorant 2 was changed to 3.75 parts of Compound G, and the colorant 3 was changed to 3.75 parts of Cromophtal Orange K 2960, and a black matrix ( F-8) was obtained.

(Example 14)

The same operation as in Example 6 was carried out except that the colorant 1 of Example 6 was changed to 3.0 parts of Pigment A-3, the colorant 2 was changed to 6.0 parts of Compound G, and the colorant 3 was changed to 6.0 parts of Cromophtal Orange K 2960, and a black matrix ( F-9) was obtained.

(Example 15)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 1.5 parts of Pigment A-3, the colorant 2 was changed to 10.5 parts of Compound G, and the colorant 3 was changed to 3.0 parts of Cromophtal Orange K 2960, and a black matrix ( F-10) was obtained.

(Example 16)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-1, the colorant 2 was changed to 3.75 parts of Compound G, and the colorant 3 was changed to 3.75 parts of Cromophtal Orange K 2960, and a black matrix ( F-11) was obtained.

(Example 17)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-2, the colorant 2 was changed to 3.75 parts of Compound G, and the colorant 3 was changed to Cromophtal Orange K 2960 3.75 parts, and a black matrix ( F-12) was obtained.

(Example 18)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-4, the colorant 2 was changed to 3.75 parts of Compound G, and the colorant 3 was changed to 3.75 parts of Cromophtal Orange K 2960, and a black matrix ( F-13) was obtained.

(Example 19)

The same operation as in Example 6 was performed except that the colorant 1 of Example 6 was changed to 7.5 parts of Pigment A-5, the colorant 2 was changed to 3.75 parts of Compound G, and the colorant 3 was changed to 3.75 parts of Cromophtal Orange K 2960, and a black matrix ( F-14) was obtained.

(Comparative Example 3)

The same operation as in Example 6 was performed except that the coloring agents 1 to 3 of Example 6 were changed to 12.0 parts of Fastogen Blue EP-CF, 1.5 parts of Cromophtal Orange K 2960, and 1.5 parts of Paliogen Red Violet K 5411, and a black matrix ( F-15) was obtained.

(Comparative Example 4)

The same operation as in Example 6 was performed except that the colorants 1 to 3 of Example 6 were changed to Fastogen Blue EP-CF 7.5 parts, Cromophtal Orange K 2960 3.75 parts, and Paliogen Red Violet K 5411 3.75 parts, and a black matrix ( F-16) was obtained.

(Comparative Example 5)

The black matrix (black matrix ( F-17) was obtained.

(Comparative Example 6)

The same procedure as in Example 6, except that the coloring agents 1 to 3 of Example 6 were changed to 12.0 parts of Fastogen Blue EP-CF and 3.0 parts of FASTOGEN Super Red ATY-TR (C.I. Pigment Red 177 manufactured by DIC Corporation). was performed to obtain a black matrix (F-18).

(Comparative Example 7)

A black matrix (F-19) was obtained in the same manner as in Example 6 except that the coloring agents 1 to 3 of Example 6 were changed to 7.5 parts of Fastogen Blue EP-CF and 7.5 parts of FASTOGEN Super Red ATY-TR. .

(Comparative Example 8)

A black matrix (F-20) was obtained by performing the same operation as in Example 6 except that the coloring agents 1 to 3 of Example 6 were changed to 3.0 parts of Fastogen Blue EP-CF and 12.0 parts of FASTOGEN Super Red ATY-TR. .

(Comparative Example 9)

The same operation as in Example 6 was performed, except that the coloring agents 1 to 3 of Example 6 were changed to 12.0 parts of Paliogen Blue L 6360, 1.5 parts of Cromophtal Orange K 2960, and 1.5 parts of Paliogen Red Violet K 5411, and the black matrix (F -21) was obtained.

(Comparative Example 10)

The black matrix (F- 22) was obtained.

(Comparative Example 11)

The black matrix (F- 23) was obtained.

<Evaluation>

The OD value, 365 nm absorbance, and 700 nm absorbance of the black matrix produced in Examples 6-19 and Comparative Examples 3-11 converted the value of Comparative Example 4 into 100, and it described in the following table|surface.

Although the black matrix obtained from the composition of this invention had the absorbance of 365 nm lower than the black matrix of the comparative example 4, compared with the black matrix of Comparative Examples 3-11, OD value improved remarkably.

Moreover, when comparing the black matrices of Examples 7, 10, 13, 16, 17, 18, 19 containing 50% of PB-25, Examples 13, 16, 17 which used PB-25 and compound G together. The black matrices of , 18 and 19 are preferable because the absorbance at 700 nm is large. In addition, the absorbance at 700 nm of the black matrix of Examples 13, 16, 17, 18, and 19 can be considered to be about the same if it is a value around 200 compared to Comparative Example 4, and in this case, the absorbance at 700 nm is large and small. Rather, the magnitude of the OD value becomes an important characteristic. From this point of view, the black matrices of Examples 13, 17 and 18 each containing pigments A-2, A-3, and A-4 having an average primary particle diameter in the range of 50 nm to 160 nm have a large absorbance at 700 nm, , and also has a high OD value, so it can be seen that particularly excellent performance is exhibited.

[Table 2]

Claims (5)

A light-shielding pigment composition comprising two or more organic pigments,
As an organic pigment, at least the following general formula (1):

(in formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a sulfonyl group which may have a substituent, a substituent The light-shielding pigment composition containing the organic pigment (A) represented by the carboxy group which may have, or the monovalent hydrocarbon group which may have a substituent. The method of claim 1,
The said organic pigment (A) is CI Pigment Blue 25 or CI Pigment Blue 26, The light-shielding pigment composition characterized by the above-mentioned. 3. The method of claim 1 or 2,
The said organic pigment (A) is an organic pigment which satisfies the following conditions, The light-shielding pigment composition characterized by the above-mentioned.
(Conditions: absorbance in the visible region (380 nm to 780 nm) becomes the maximum at a wavelength of 580 nm to 780 nm, and the absorbance at 365 nm is 50% or less of the maximum absorbance, at 555 nm and 700 nm absorbance is 50% or more of the maximum absorbance) 3. The method of claim 1 or 2,
Among the benzimidazolone pigments containing the chemical structures represented by the following general formulas (2) and (3), and the benzimidazolonedioxazine pigments containing the chemical structures represented by the following general formulas (4), The light-shielding pigment composition further contains one or both.

(In formula (2), R ¹ to R ³ each represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent)

(in formula (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom; X ³ , X ⁴ , X ⁵ , X ⁶ 1 more than one is a halogen atom; R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent) The light-shielding member for displays containing the light-shielding pigment composition of Claim 1 or 2.