CN1329749C - Photosensitive black composition, black matrix substrate and color filter using same - Google Patents

Abstract

The invention provides a photosensitive black composition, which contains 50-200 m of specific surface area²Carbon black, a pigment derivative represented by the following general formula , and an ethylenically unsaturated compound. The invention also provides a black matrix substrate with a black matrix formed by the photosensitive black composition and a color filter with a color filter area of at least two colors except black formed on the black matrix substrate. General formula : wherein Q represents an organic dye residue.

Description

Photosensitive black composition, black matrix substrate and color filter using same

technical field

The present invention relates to a photosensitive black composition used in the manufacture of a black matrix (black matrix) of a color filter used in combination with a liquid crystal display device or a solid-state imaging element, a black matrix substrate using the composition, and a color filter ( Also known as color filter, color filter).

Background technique

In the gap between the red, green, and blue filter segments of the color filter, in order to improve the contrast, usually, a grid-like black pattern called a black matrix with light-shielding properties is formed.

In the past, the black matrix was formed of metal thin films such as chromium and nickel, but from the viewpoint of display quality and cost, attempts are being made to use a black colorant (a colorant in which black pigments such as carbon black or several pigments are mixed to become black) ) of the photosensitive black composition forms a black matrix. The black matrix formed by using the photosensitive black composition has low light reflectance on the surface, can shorten the manufacturing process, and it is possible to produce large-scale color filters, so it has more advantages than the black matrix formed by using metal materials such as chromium.

However, when using a photosensitive black composition to form a black matrix by photolithography, in order to obtain high light-shielding properties, it is necessary to mix a large amount of black colorant such as carbon black in the composition, but the higher the content of the black colorant , the more difficult it is to disperse the black colorant uniformly, the problem arises that the dispersion stability of the photosensitive black composition decreases with time, such as an increase in viscosity. Furthermore, as the photosensitivity increases, the sensitivity decreases remarkably, and even when irradiated with active energy rays, it becomes difficult to obtain a cured coating film. In order to obtain a sufficiently cured coating film, a larger amount of exposure is required, which causes problems such as a decrease in productivity and deterioration of the shape of the black matrix.

In order to solve such a problem, it has been proposed to blend a pigment derivative represented by the following general formula (B) into a color filter-forming composition containing a black matrix (for example, see JP-A-3-153780).

General formula (B):

Wherein, Q represents organic pigment residue,

X ₁ represents a hydrogen atom, a carboxyl group or a sulfonic acid group,

X ₂ represents the formula

or

Represented substituents,

i and j each independently represent an integer of 1 to 4,

R ₁ and R ₂ each independently represent a hydrogen atom, or an alkyl, aryl or heterocyclic residue which may have a substituent,

Y represents a hydrogen atom, a halogen atom, -NO ₂ , -NH ₂ or -SO ₃ H,

k represents an integer of 1 to 4,

n represents an integer of 1 to 4,

A is a divalent bond represented by the following general formula:

Z ₁ represents a direct bond, -CONH-R ₃ -, -SO ₂ NH-R ₃ -, or -CH ₂ NHCOCH ₃ -R ₃ -,

Z ₂ represents -NH- or -O-,

_Z represents hydroxyl, alkoxy or in the following general formula:

or

The substituent represented by wherein, when i is 1, Z ₃ may be -NH-Z1-Q.

The photosensitive black composition containing the pigment derivative represented by the general formula (B) exhibits excellent characteristics in heat resistance, chemical resistance, etc., but cannot satisfy the requirements for dispersion stability, sensitivity, black matrix shape, and Performance required for substrate adhesion (adhesion) and light-shielding properties.

Contents of the invention

Therefore, the object of the present invention is to provide a photosensitive black composition, a black matrix substrate and a color filter using the composition, and the photosensitive black composition is excellent in heat resistance, chemical resistance, etc. characteristics, and excellent dispersion stability, sensitivity, black matrix shape, adhesion to the substrate, and light-shielding properties.

According to the first aspect of the present invention, there is provided a photosensitive black composition comprising carbon black with a specific surface area of 50 to 200 m ² /g, a pigment derivative represented by the following general formula (A), and an ethylenic bond Formula unsaturated compounds (also known as ethylenically unsaturated compounds).

General formula (A):

Wherein, Q represents organic pigment residue,

X represents a direct bond, -CONH-Y ₂ -, -SO ₂ NH-Y ₂ -, or -CH ₂ NHCOCH ₂ NH-Y ₂ -,

_Y represents an alkylene or aryl group which may have a substituent,

Y ₁ means -NH- or -O-,

Z represents a hydroxyl group, an alkoxy group or a substituent represented by the following general formula (i),

Wherein, when n is 1, Z can be -NH-X-Q,

Y ₃ represents -NH- or -O-,

R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, or R ₁ and R ₂ can be bonded to each other to form a heterocyclic ring containing at least a nitrogen atom,

m represents an integer of 1 to 6,

n represents an integer of 1 to 4,

In the photosensitive black composition of the present invention, the absorption of dibutyl phthalate of carbon black is preferably 120 cm ³ /100 g or less, and the average primary particle diameter of carbon black is preferably 20 to 50 nm.

Next, according to the second aspect of the present invention, there is provided a black matrix substrate having a black matrix formed from the photosensitive black composition of the present invention. The optical density per 1 µm of the dry film thickness of the black matrix was 3.0 or more.

Furthermore, according to a third aspect of the present invention, there is provided a color filter in which color filter regions of at least two colors other than black are formed on the black matrix substrate (substrate) of the present invention.

Detailed ways

First, the photosensitive black composition of the present invention will be described.

The photosensitive black composition of the present invention contains carbon black having a specific surface area of 50 to 200 m ² /g, a dye derivative represented by the following general formula (A), and an ethylenically unsaturated compound.

The carbon black contained in the photosensitive black composition of the present invention is a black pigment having light-shielding properties, and examples of commercially available carbon black include #260, #25, #30, and #32 manufactured by Mitsubishi Chemical Corporation. , #33, #40, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, DEGUSSA Printex L, Printex P, Printex 30 , Printex 35, Printex 40, Printex 45, Printex 55, Printex 60, Printex 300, Printex 350, Special Black 4, Special Black 350, Special Black 550, etc. Carbon black can be used alone or in combination of two or more.

As carbon black, one having a specific surface area of 50 to 200 m ² /g is used. The reason is that when using carbon black with a specific surface area of less than 50m ^{2 /} g, the shape of the black matrix will deteriorate; The dye derivative represented by the general formula (A) needs to be blended with a large amount of the dye derivative represented by the general formula (A) in order to express various physical properties.

In addition, carbon black preferably has a dibutyl phthalate (hereinafter referred to as DBP) absorption of 120 cm ³ /100 g or less from the viewpoint of sensitivity, and the smaller the absorption of DBP, the better. The DBP absorption can be measured using an oil absorption meter (refer to Japanese Industrial Standard JIS K6217-4).

In addition, the average primary particle diameter of carbon black is preferably 20 to 50 nm. The reason is that carbon black with an average primary particle size of less than 20 nanometers is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition with good stability over time; and if carbon black larger than 50 nanometers is used, it will cause black matrix deterioration of the shape.

The content of carbon black in the photosensitive black composition is preferably 20 to 70% by weight, more preferably 30 to 60% by weight, based on the solid content of the composition. When the content of carbon black is less than 20% by weight, sufficient photosensitivity cannot be obtained, and when the content of carbon black exceeds 70% by weight, it is difficult to obtain dispersion stability, resulting in a decrease in sensitivity, and it may be difficult to form a black matrix.

The pigment derivative contained in the photosensitive black composition is represented by the above-mentioned general formula (A), and functions to disperse carbon black in the ethylenically unsaturated composition.

In the general formula (A), Q represents an organic dye residue. Examples of organic dyes that provide the organic dye residue Q include phthalocyanine-based dyes having a phthalocyanine skeleton, quinacridone-based dyes having a quinacridone skeleton, and quinacridone-based dyes having a quinacridone-quinone skeleton. Pyridonequinone-based dyes, isoindolinone-based dyes having an isoindolinone skeleton, quinophthalone-based dyes having a quinophthalone skeleton, diketopyrrolopyrrole-based dyes having a diketopyrrolopyrrole skeleton Pigments, perylene dyes having a perylene skeleton, perinon dyes having a perinone skeleton, indigo dyes having an indigo skeleton, thioindigo dyes having a thioindigo skeleton, and dioxazine dyes having a dioxazine skeleton , anthraquinone dyes having an anthraquinone skeleton, pyranthrone dyes having a pyranthrone skeleton, anthrone dyes having an anthrone skeleton, yellow anthrone skeletons Yellow anthrone pigments, standard vat blue pigments with standard vat blue skeleton, metal complexes and other fused polycyclic organic pigments, benzimidazolone pigments with benzimidazolone skeleton, insoluble azo pigments , condensed azo pigments, soluble azo pigments, etc. Among these dyes, phthalocyanine dyes, anthraquinone dyes, and benzimidazolone dyes are preferable.

In the general formula (A), X represents a direct bond, -CONH-Y ₂ -, -SO ₂ NH-Y ₂ -, or -CH ₂ NHCOCH ₂ NH-Y ₂ -, where Y ₂ represents that it may have substitution The alkylene or aryl group of the group. Preferable examples of _Y2 include alkyl groups having 1 to 6 carbon atoms, phenyl groups, and the like.

In the general formula (A), Y ₁ represents -NH- or -O-,

In the general formula (A), Z represents a hydroxyl group, an alkoxy group or a substituent represented by the general formula (i),

However, when n is 1, Z may be -NH-XQ. Wherein, Y ₃ represents -NH- or -O-. As the alkoxy group represented by Z, an alkoxy group having 1 to 6 carbon atoms is preferable.

In the general formula (A) (also in the general formula (i)), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, and R ₁ and R ₂ may be bonded to each other so that A heterocyclic ring containing at least a nitrogen atom is formed. The alkyl group represented by R ₁ or R ₂ is preferably an alkyl group having 1 to 6 carbon atoms. As the substituent of the alkyl group, a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms are preferable. The heterocyclic ring formed by combining _R1 and _R2 is preferably imidazolyl, imino, piperidinyl, or pyrrolidinyl.

In general formula (A) (it is the same in general formula (i)), m represents the integer of 1-6.

In general formula (A) (it is the same in general formula (i)), n represents the integer of 1-4.

Examples of the dye derivative represented by the general formula (A) include dye derivatives represented by the following general formulas (1) to (10).

The pigment derivatives in the general formula (A) may be used alone or in combination of two or more.

The content of the pigment derivative represented by the general formula (A) is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of carbon black. When the content of the pigment derivative is less than 0.1 parts by weight, the effect of dispersing carbon black cannot be fully exerted, and when the content of the pigment derivative exceeds 30 parts by weight, the dispersion of carbon black becomes unstable, so it is not preferable. .

The ethylenically unsaturated compound contained in the photosensitive black composition is a compound having one, two or more ethylenically unsaturated double bonds, and monomers, oligomers, and photosensitive resins can be used. Examples of monomers include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Moreover, an epoxy (meth)acrylate, a urethane (meth)acrylate, an ester (meth)acrylate etc. are mentioned as an oligomer. Examples of the photosensitive resin include polyesters, polyurethanes, epoxy resins, acrylic resins, and the like introduced with ethylenically unsaturated double bonds by known methods. The ethylenically unsaturated compounds may be used alone or in combination of two or more. As the ethylenically unsaturated compound, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferable. The ethylenically unsaturated compound is preferably used in a ratio of 5% to 30% by weight of the solid content of the composition.

In addition, when the photosensitive black composition is cured by ultraviolet irradiation to form a black matrix, a photopolymerization initiator is contained in the photosensitive black composition. As a photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one Acetophenone-based photopolymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethylaldehyde acetophenone and other benzoin-based photopolymerization initiators, Benzophenone, Benzoylbenzoic Acid, Methyl Benzoylbenzoate, 4-Phenylbenzophenone, Hydroxybenzophenone, Acrylylated Benzophenone, 4-Benzoyl-4'-Methyl Benzophenone-based photopolymerization initiators such as diphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diiso Thioxanthone-based photopolymerization initiators such as propylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s -triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2 -(naphthalene-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphthalene-1-yl)-4,6-bis(trichloro Methyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6- Triazine-based photopolymerization initiators such as triazine, carbazole-based photopolymerization initiators, and imidazole-based photopolymerization initiators. The photopolymerization initiators may be used alone, or in combination of two or more. These photopolymerization initiators are preferably used in a ratio of 5 to 25% by weight of the solid content of the composition.

In addition, a sensitizer may be contained in the photosensitive black composition. Examples of sensitizers include α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylic acid, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthaloylphenone, 3,3',4,4'-tetrakis(butylcarbonylperoxy)benzophenone, 4,4'-diethylamino Benzophenone etc. The above-mentioned sensitizers may be used alone or in combination of two or more. The sensitizer is preferably used in a ratio of 3% to 60% by weight of the photopolymerization initiator.

Moreover, in order to make a photosensitive black composition alkali-developable type, you may contain an alkali-soluble resin in this composition. In addition, the photosensitive black composition may contain a resin not having alkali solubility together with the alkali-soluble resin, depending on the purpose of imparting heat resistance and adhesiveness.

Examples of alkali-soluble resins include (meth)acrylic acid copolymers, styrene-maleic anhydride copolymers, and polyester resins having carboxyl groups.

Alkali-soluble resins may be used in combination of two or more for various purposes such as imparting heat resistance, solvent resistance, and chemical resistance to the coating film.

The content of the alkali-soluble resin is preferably 3 to 70% by weight, more preferably 5 to 60% by weight, based on the solid content of the photosensitive black composition. When the content of the alkali-soluble resin is less than 3% by weight, alkali developability decreases, and when the content of the alkali-soluble resin exceeds 70% by weight, the curability of the photosensitive black composition and light-shielding properties when used to form a black matrix decrease.

In order to sufficiently disperse carbon black and form a black matrix having a desired film thickness, a solvent may be contained in the photosensitive black composition. Examples of solvents include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether , ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, iso Propanol, butanol, isobutyl ketone, petroleum solvents, etc. These solvents are used alone or in combination. The solvent is preferably used in a ratio of 60 to 95% by weight of the total amount of the photosensitive black composition.

In the photosensitive black composition, chain transfer agents, surfactants, silane coupling agents, and other additives may be added for the purpose of improving paintability (coatability), sensitivity, and adhesion.

By mixing carbon black, a pigment derivative represented by the general formula (A), an ethylenically unsaturated compound, and a photopolymerization initiator, an alkali-soluble resin, a solvent, and other additives as needed, using a three-roll kneader, The photosensitive black composition can be produced by dispersing with various dispersing devices such as a two-roll mixer, a sand mill, a kneader, and a fine grinder.

For the photosensitive black composition, it is preferred to remove coarse particles of 5 microns or more, preferably 1 micron or more, Coarse particles of 0.5 micron or more and mixed dust are more preferable.

The black matrix substrate will be described below.

The black matrix substrate is prepared by the following steps: after coating the photosensitive black composition on a transparent substrate such as a glass plate by spin coating, slit coating, roll coating, etc. The mask is irradiated with active energy rays from the composition-coated side, immersed in a solvent or alkaline developer, or sprayed with the developer by spraying, etc., and the unirradiated portion, that is, the unhardened portion, is removed and developed to form a black matrix of a desired shape.

The film thickness of the photosensitive black composition is preferably in the range of 0.2 to 5 micrometers (when dry), and more preferably in the range of 0.5 to 2 micrometers in which a balance between paintability and light-shielding properties is easily achieved.

From the viewpoint of having high light-shielding properties, the optical density per 1 micron of dry film thickness of the black matrix is preferably 3.0 or more. The higher the optical density, the better, but when the active energy rays are ultraviolet light or visible light, it is difficult to obtain a cured coating film, so the optical density is preferably about 4.5 or less.

As an alkaline developing solution, aqueous solutions of sodium carbonate, sodium hydroxide, etc. are used, and organic bases, such as dimethylbenzylamine and triethanolamine, can also be used. Furthermore, an antifoaming agent or surfactant may be added to the developer.

In addition, in order to increase the exposure sensitivity of active energy rays, after coating and drying the photosensitive black composition, coating a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin, etc., and drying to form a After forming a film that prevents polymerization, active energy rays are irradiated from the side where the composition is applied.

As the active energy rays, electron rays, ultraviolet rays, and visible light of 400 to 500 nanometers can be used. As a source of electron rays irradiated from the composition-coated side, a thermionic emission gun, a field emission gun, or the like can be used. In addition, as a line source (light source) of ultraviolet light and visible light of 400 to 500 nanometers, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, etc. can be used. Specifically, as a point light source, from the viewpoint of stabilizing luminance, an ultra-high pressure mercury lamp or a xenon mercury lamp is used in many cases. The amount of active energy rays irradiated from the composition-coated side can be appropriately set in the range of 5 to 1000 mJ, preferably in the range of 50 to 300 mJ which is easy to manage in engineering.

Finally, the color filter will be described.

The color filter is formed on the above-mentioned black matrix substrate with color filter regions of at least two colors other than black. The color of the filter area is about 2 to 6 colors selectable from blue, green, red, cyan, yellow, magenta (magneta), orange, purple, and the like. Colors of the same color system can form filter areas with different densities.

Examples of methods for forming a color filter region on a black matrix substrate include gravure offset printing, anhydrous offset printing, screen printing, and photolithography using a solvent-developed or alkali-developed colored resist. , the electrodeposition method of forming a coloring material on a transparent conductive film by electrophoresis of colloidal particles, the transfer method of transferring a pre-formed color filter region layer on the surface of a transfer film to a black matrix substrate, etc.

Since the printing method enables patterning only by repeating printing and drying, the printing method is low-cost and excellent in mass productivity as a manufacturing method of color filters. In addition, with the development of printing technology, it is possible to print fine patterns with high dimensional accuracy and smoothness. When manufacturing a color filter by a printing method, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted with a dispersant or an extender pigment.

The photolithography method using a solvent-developed or alkali-developed colored resist is to apply a colored resist on a black matrix substrate by spin coating, slit coating, roll coating, etc. The mask is exposed to ultraviolet rays, and after the unexposed part is rinsed with a solvent or alkali developer to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. This manufacturing method can manufacture a color filter with higher precision than the above-mentioned printing method.

Coloring resist (coloring resist) is, replaces the black pigment that contains in the photosensitive black composition of the present invention, can use the resist that the coloring agent of required color is prepared, can not necessarily contain general formula (A) The indicated pigment derivatives. As the colorant, various colorants with excellent durability can be used, but pigments are preferably used from the viewpoint of light resistance, heat resistance and solvent resistance, and organic pigments are particularly preferably used from the viewpoint of light absorption energy. Specific examples of typical pigments are shown below by color index (CI).

Examples of yellow colorants include: Pigment Yellow 12, 13, 14, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 173, etc.

Examples of orange colorants include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and the like.

Examples of red and magenta colorants include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255 and the like.

Examples of purple colorants include Pigment Violet 19, 23, 29, 32, 33, 36, 37, 38 and the like.

Examples of blue and cyan colorants include Pigment Blue 15 (15, 15:1, 15:2, 15:3, 15:4, 15:6, etc.), 21, 22, 60, 64, and the like.

Pigment Green 7, 10, 36, 47 etc. are mentioned as a green coloring agent.

Of these colorants, two or more of them may be used in combination to obtain a desired color.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, in the following examples and comparative examples, "part" means a weight part, and "%" means weight%.

(Preparation of Acrylic Resin Solution)

Add 800 parts of cyclohexanone into the reaction vessel, and while injecting nitrogen gas into the reaction vessel, heat it to 100°C. At this temperature, 60.0 parts of methacrylic acid, 65.0 parts of butyl methacrylate are added dropwise within 1 hour. ester, 65.0 parts of methyl methacrylate, 60.0 parts of styrene and 10.0 parts of azobisisobutyronitrile, after further reacting at 100°C for 3 hours, add 2.0 parts of azobisisobutyronitrile to dissolve in 50 parts The resulting mixture in cyclohexanone was further reacted at 100° C. for 1 hour to synthesize a resin solution. After cooling to room temperature, extract about 2 grams of resin solution, heat and dry at 180°C for 20 minutes, and measure the non-volatile components. The amount of cyclohexanone added in the previously synthesized resin solution is such that the non-volatile components are 20%, thereby preparing The desired acrylate resin solution. In addition, the weight average molecular weight of the acrylate resin was 40,000.

(Preparation of Carbon Black Dispersion)

The carbon black and pigment derivatives recorded in the following examples and comparative examples are uniformly mixed with 24 parts of the above-mentioned acrylate resin solution and 40 parts of cyclohexanone, and the glass beads with a diameter of 1 mm are used to disperse them with a sand mill. After 5 hours, a carbon black dispersion was prepared.

Table 1 shows the physical property values of carbon black used in Examples and Comparative Examples.

Table 1

carbon black Average primary particle size DBP absorption (cm ³ /100g) Specific surface area (m ² /g) #40 24nm 110 115 #260 40nm 74 79 MA77 23nm 68 130 ブラツクパルズ800 17nm 68 210 MONARCH 120 75nm 71 25

Furthermore, the pigment derivatives used in the following Examples and Comparative Examples are shown below.

Pigment Derivatives①

Pigment derivative②

(CuPc: copper phthalocyanine residue)

Pigment derivatives③

Example 1

Carbon black ("#40" manufactured by Mitsubishi Chemical Corporation) 10.0 parts

Pigment derivatives ① 0.5 parts

Example 2

Carbon black ("#260" manufactured by Mitsubishi Chemical Corporation) 8.0 parts

Pigment derivatives ② 0.3 parts

Example 3

Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts

Pigment derivatives ③ 1.0 parts

Comparative example 1

Carbon black ("BratsukuPailzu 800" manufactured by CABOT Co., Ltd.) 8.0 parts

Pigment derivatives ① 0.2 parts

Comparative example 2

Carbon black ("MONARCH 120" manufactured by CABOT Corporation) 10.0 parts

Pigment derivatives ② 0.8 parts

<Time-dependent stability evaluation of carbon black dispersion>

The viscosity of the black dispersion immediately after the dispersion was completed was compared with the viscosity after storage at 40° C. for 7 days to evaluate stability over time. The results are shown in Table 2.

<Preparation of Photosensitive Black Composition>

60 parts of carbon black dispersion, 4.3 parts of (trimethylolpropyl) triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Chemical Co., Ltd.), 1.4 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy Corporation), A mixture of 0.2 parts of a sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.) and 21.6 parts of cyclohexanone was uniformly stirred and mixed, and filtered through a 1-micron filter to prepare a photosensitive black composition. About the obtained photosensitive black composition, the sensitivity, black matrix shape, glass adhesion, and optical density were evaluated by the following method. The results are listed in Table 2 together.

[Sensitivity]

The photosensitive black composition was coated on a 10 cm×10 cm glass substrate by spin coating, and then dried at 70° C. for 15 minutes to form a coating film with a dry film thickness of 1 μm. Then, it was exposed to ultraviolet rays of 100 mJ/cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, the unexposed portion was sprayed with a sodium carbonate aqueous solution for development, and then washed with ion-exchanged water to remove the unexposed portion, and the film thickness after development of the exposed portion was measured. The results are also listed in Table 2.

[black bottom shape]

A black matrix substrate was fabricated by the above-mentioned method. The linearity of the shape of the black matrix formed in the exposed part was evaluated by observation with an optical microscope. The results are also listed in Table 2.

[glass adhesion]

The photosensitive black composition was coated on a glass substrate by the above-mentioned method, and exposed to ultraviolet rays of 300 mJ/cm ² through a photomask using an ultra-high pressure mercury lamp. Next, the unexposed portion was sprayed with an aqueous sodium carbonate solution for development, washed with ion-exchanged water to remove the unexposed portion, and heated at 230° C. for 1 hour. Next, glass adhesion was evaluated based on the substrate mesh adhesion test method of JIS K5400, and the number of peeled objects in 100 substrate meshes was calculated. The results are also listed in Table 2.

[Optical density]

After coating the photosensitive black composition on the glass substrate by the above-mentioned method, it heated at 230 degreeC for 1 hour. The optical density (OD) of the photosensitive black composition-coated substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was obtained. The results are also listed in Table 2.

Table 2

carbon black dispersion Temporal stability of carbon black dispersions Sensitivity black bottom shape glass adhesion Optical density Example 1 ○ △ ○ ○ 3.6/micron Example 2 ○ ○ △ ○ 3.6/micron Example 3 ○ ○ ○ ○ 3.8/micron Comparative example 1 x x x x 2.9/micron Comparative example 2 △ x x x 3.5/micron

In Table 2,

Stability over time: ○: Viscosity after storage at 40°C for 7 days/Viscosity immediately after production<1.3

△: 1.3≤viscosity after storage at 40°C for 7 days/viscosity immediately after production＜1.8

×: Viscosity after storage at 40°C for 7 days/viscosity immediately after production ≥ 1.8

Sensitivity: ○: film thickness ≥ 0.95 microns

△: 0.90 microns ≤ film thickness < 0.95 microns

×: film thickness <0.90 microns

Black bottom shape: ○: Good linearity

△: Local linearity is good

×: Poor linearity

Glass adhesion: ○: The number of pieces peeled off from the base plate is less than 3 pieces

△: 3 pieces ≤ the number of stripped pieces of the base plate < 10 pieces

×: The number of stripped objects of the base plate is ≥10

As shown in Table 2, when carbon black with a specific surface area of 50 to 200 m ² /g is not used, the time-dependent stability and sensitivity of the carbon black dispersion cannot be obtained, resulting in poor shape of the black matrix, and cannot obtain Glass adhesion. On the other hand, when carbon black having a specific surface area of 50 to 200 m ² /g is used, the carbon black dispersion has good stability over time, excellent sensitivity, good black matrix formability, and good glass adhesion.

As shown above, according to the present invention, carbon black can be stably dispersed at a high concentration. Moreover, the photosensitive black composition of the present invention is excellent in stability over time and has high sensitivity; the photosensitive black composition of the present invention also has good black matrix shape, glass adhesion, and optical density, and obtains a composition having a black matrix. A black matrix substrate with the performance required for the bottom.

Claims (8)

1, a kind of photosensitive black composition, it contains:

(a) specific surface area is 50～200m ²/ g and average primary particle diameter are the carbon black of 20～50nm, and wherein the content ratio of this carbon black is, are that benchmark is 20～70 weight % with total shape branch weight admittedly of described composition,

(b) pigment derivative of representing with following general formula (A),

Wherein, Q represent the organic pigment residue,

X represent Direct Bonding ,-CONH-Y ₂-,-SO ₂NH-Y ₂-or-CH ₂NHCOCH ₂NH-Y ₂-,

Y ₂Expression can have substituent alkylidene or aryl,

Y ₁Expression-NH-or-O-,

Z represents hydroxyl, alkoxy or the substituting group of representing with following general formula (i),

Wherein, Y ₃Expression-NH-or-O-,

R ₁And R ₂Expression independently of one another has the alkyl or the R of substituting group or unsubstituted ₁And R ₂Mutually bonding with form the heterocycle contain nitrogen-atoms at least,

M represent 1～6 integer,

N represents 1～4 integer, and

(c) ethylenically unsaturated compounds.

2, photosensitive black composition according to claim 1, the uptake of the dibutyl phthalate of wherein said carbon black is 120cm ³/ 100g or following.

3, photosensitive black composition according to claim 1, wherein the n in general formula (A) is 1 occasion, Z is-NH-X-Q.

4, photosensitive black composition according to claim 1, the content ratio of the pigment derivative that wherein said general formula (A) is represented are to be 0.1～30 weight portion with respect to 100 weight portion carbon blacks.

5, photosensitive black composition according to claim 4, wherein said ethylenically unsaturated compounds think that 5%～30% ratio of weight that the solid shape of composition is divided contains.

6, a kind of black matrix substrate, it has the black matrix that is formed by each described photosensitive black composition of claim 1 to 5.

7, black matrix substrate according to claim 6, wherein the per 1 micron optical density of the dry film thickness of black matrix be 3.0 or more than.

8, on the described black matrix substrate of claim 6, form the color filter in the colour filter zone of black at least two kinds of colors in addition.