KR20140061346A - Colored resin composition and resin black matrix substrate - Google Patents

Abstract

Provided is a colored resin composition capable of easily forming a resin black matrix having high adhesion and high chemical resistance. Further, by using the colored resin composition of the present invention, a black matrix substrate having excellent reliability can be obtained. The present invention relates to a colored resin composition containing at least (A) a coloring pigment, (B) an alkali-soluble resin, (C) a contact improving agent, and (D) an organic solvent, wherein a specific silane coupling agent And a coloring resin composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin composition and a resin black matrix substrate,

The present invention relates to a colored resin composition and a resin black matrix substrate using the same.

At present, the use of a light-shielding material has many aspects. In a flat panel display (FPD) such as a liquid crystal display (abbreviated as LCD) and a plasma display panel (abbreviated as PDP hereinafter) The edge of the peripheral portion of the display region, and the external light side of the TFT.

In the color filter for LCD, generally, other colors of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed . The black matrix used as the light-blocking film serves to prevent the contrast and the color purity from deteriorating due to light leakage between the pixels.

Further, also in the case of a substrate for a touch panel, a black matrix is formed as a light-shielding film and is generally formed by a printing ink on a cover glass or a cover film facing the sensor substrate. On the other hand, a demand for lightening the weight of the touch panel is increasing, and development of technology for simultaneously forming a light-shielding film and a touch sensor on the cover glass is under development. In such a case, since it is necessary to form an electrode or the like after the black matrix is formed on the cover glass, high adhesion and chemical resistance are required in addition to high insulation. Particularly, in the use of color filters, non-alkali glass is used as a glass substrate. In touch panel applications, it is common to use a soda glass substrate containing a large amount of ionic impurities as a glass substrate, It is becoming necessary.

Conventionally, a vapor-deposited film of a metal or a metal compound such as chromium, nickel, or aluminum has been used as a black matrix, but the process is complicated and expensive, and the surface of the thin metal film is highly reflective. To solve this problem, a pigment dispersion method using a resin composition in which a pigment is dispersed is currently the mainstream.

Although the pigment dispersion method has a negative type and a positive type, a negative type photosensitive composition containing an acrylic polymer, an acrylic polyfunctional monomer or oligomer, a photoinitiator, a solvent and a pigment as a main component is widely used. As the light shielding material, titanium black such as carbon black, low-order titanium oxide and titanium oxynitride, metal oxides such as iron oxide, and other organic pigment coloring systems are used, but carbon black and titanium oxynitride are mainstream. In order to obtain a black matrix having high insulating properties, carbon black or an organic pigment surface-treated with titanium black or a resin or the like is mixed as a light shielding material (Patent Document 1).

A technique of adding at least one selected from an amine-based silane compound, a ketimine-based silane compound and an isocyanate-based silane compound to improve the adhesion of the black matrix to the substrate (Patent Document 2), and a technique of adding a silane coupling agent (Patent Document 3) is known. However, when the soda glass is used as the substrate, there is a problem that sufficient adhesion can not be obtained, and peeling occurs due to high-temperature and high-humidity treatment of the black matrix substrate and chemical treatment such as wastewater or amine release agent. On the other hand, a silane coupling agent having an imide group (Patent Document 4, Patent Document 5) has been proposed in order to improve adhesion in a hard coating agent containing no coloring pigment. However, It was insufficient.

Japanese Patent Application Laid-Open No. 2008-260927 Japanese Patent Application Laid-Open No. 2006-330209 Japanese Patent Application Laid-Open No. 2010-102086 International Publication No. 2008/065944 International Publication No. 2009/096050

SUMMARY OF THE INVENTION The present invention was conceived in view of the drawbacks of the prior art, and it is an object of the present invention to provide a method for easily forming a black matrix having excellent adhesion to a substrate surface composed of a metal or an inorganic material and having high chemical resistance And to provide a colored resin composition which can be obtained. By using such a colored resin composition, a resin black matrix excellent in reliability and a substrate for a touch panel can be obtained.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the problems of the prior art and found that the problems of the present invention can be solved by using a silane coupling agent having a specific structure as the adhesion improver.

That is, the object of the present invention is achieved by the following constitution.

(1) A colored resin composition containing at least (A) a coloring pigment, (B) an alkali-soluble resin, (C) a contact improving agent and (D) an organic solvent, And a silane coupling agent represented by the following formula (1).

(Each R ¹ may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) The alkyl group may further have a substituent, n represents 0 or 1. R ² represents a trivalent organic group having 3 to 30 carbon atoms . R ³ is or different may gatahdo respectively, having 1 to 6 carbon alkyl group, represents a C 1 -C 6 alkoxy group, a phenyl group, a hydroxyl group or a phenoxy group. Further, among these groups of R ^3, other than a hydroxyl group substituent May be further included.)

(2) The colored resin composition according to (1), wherein the adhesion modifier (C) is a silane coupling agent represented by n = 0 in the general formula (1).

(3) The colored resin composition according to (1) or (2), wherein at least two kinds of silane coupling agents are contained as the (C) adhesion improver.

(4) The colored resin composition according to any one of (1) to (3), wherein the colored pigment (A) is a black light shielding material.

(5) The colored resin composition according to any one of (1) to (4), wherein at least titanium nitride particles and / or carbon black is contained as the black light-blocking material.

(6) The colored resin composition according to (5), wherein the weight ratio of the titanium nitride particles to the total weight of the black shading material is 20 to 80 wt%.

(7) A resin black matrix substrate characterized by being obtained by applying the colored resin composition according to any one of (4) to (6) on a transparent substrate to form a pattern.

By using the colored resin composition of the present invention, a resin black matrix having high adhesiveness and high chemical resistance can be easily obtained, and a black matrix substrate having excellent reliability can be obtained.

Hereinafter, the present invention will be described in more detail.

The colored resin composition of the present invention is a colored resin composition comprising at least (A) a coloring pigment, (B) an alkali-soluble resin, (C) a contact improving agent and (D) an organic solvent, and (C) And a ring agent.

The silane coupling agent has a structure represented by the following general formula (1).

(Each R ¹ may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) The alkyl group may further have a substituent, n represents 0 or 1. R ² represents a trivalent organic group having 3 to 30 carbon atoms . R ³ is or different may gatahdo respectively, having 1 to 6 carbon alkyl group, represents a C 1 -C 6 alkoxy group, a phenyl group, a hydroxyl group or a phenoxy group. Further, among these groups of R ^3, other than a hydroxyl group substituent May be further included.)

Here, as R ¹ , a methyl group, an ethyl group and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable from the viewpoint of raw material availability. R ¹ may have a substituent such as an alkoxy group, an aryl group, a phenoxy group or a halogen group. As R ^{2, a} trivalent organic group having 3 to 10 carbon atoms is more preferable in terms of solubility in an organic solvent.

Examples of the silane coupling agent represented by the general formula (1) include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert- butylamino) (Trimethylsilyl) pentanoic acid, 3- (isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (isopropylamino) (Trimethylsilyl) hexanoic acid, 2- (2- (isobutylamino) -2 (2-oxoethyl) (Trimethoxysilyl) pentanoic acid, 3- (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (Trimethylsilyl) pentanoic acid, 3- (tert-butylcarbamoyl) -6- (triethoxysilyl) hexanoic acid, 2- (2- (tert- butylamino) (Dimethoxy (methyl) silyl) -3- (tert-butylcarbamoyl) hexanoic acid, 5- (dimethoxy Silyl-2- (2- (tert-butylamino) -2-oxoethyl) pentanoic acid, 3- (tert- 2- (tert-butylamino) -2-oxoethyl) -5- (trimethoxysilyl) butanoic acid, 2- (tert- (2- (trimethoxysilyl) ethyl) cyclohexanecarboxylic acid, 2- (tert-butylcarbamoyl) -5- Cyclohexanecarboxylic acid, and the like.

Of these, compounds in which n = 0 in the general formula (1) are preferable from the standpoint of soda glass and the effect of improving the ITO adhesion.

Specific examples thereof include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert- butylamino) -2-oxoethyl) (Trimethoxysilyl) hexanoic acid, 3- (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (Trimethoxysilyl) pentanoic acid, 3- (tert-butylcarbamoyl) -6- (triethoxysilyl) hexanoic acid, 2 - (2- (tert-butylamino) -2-oxoethyl) -5- (triethoxysilyl) pentanoic acid, 6- (dimethoxy Acid, 5- (dimethoxy (methyl) silyl-2- (2- (tert- butylamino) -2-oxoethyl) pentanoic acid, 3- (tert- butylcarbamoyl) -6- (trimethoxysilyl ) 2- (tert-butylcarbamoyl) -4- (2- ((tert-butylamino) -2-oxoethyl) Trimethoxysilyl) ethyl) cyclohexanehexanecarboxylic acid, 2- (tert-butylcarbamoyl) -5- (2- (trimethoxysilyl) Butyl) cyclohexane, hexane carboxylic acid is appropriate.

When a silane coupling agent having these specific structures is added to the colored resin composition as the (C) adhesion improver, it may be used singly, but it is more preferable to use a known silane coupling agent in combination. Although it can be achieved by increasing the amount of the silane coupling agent added in order to improve the adhesion of the coating film to the base substrate and the chemical resistance, there arises a problem that when the coating film is subjected to alkali development, the fine pattern is lost and the resolution is lowered easy to do. Therefore, it is preferable to use at least two kinds of silane coupling agents in combination from the viewpoint of improving the adhesion to the base during development.

The silane coupling agent to be used in combination is not particularly limited and examples thereof include silane coupling agents having functional groups such as vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group and amino group. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2- (3-chloropropyltrimethoxysilane) Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butyryl) Diene) propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanate propyltri Sisilran the like, p- tree tilt rime silane are preferred.

As a method for producing these silane coupling agents, a method for producing the silane coupling agent by reaction of an alkylamine with a silane coupling agent containing an acid anhydride is preferable for ease of production. In this case, depending on the structure of the silane coupling agent containing an acid anhydride, two kinds of silane coupling agents are simultaneously produced. However, it is possible to use them as a mixture particularly without separating and purifying them. In this synthesis method, a small amount of oligomer or the like can also be considered, but it does not greatly affect the adhesion improving effect and need not be considered.

The addition amount is preferably 1 to 15% by weight, more preferably 2 to 10% by weight based on the total amount of the solid components of the colored resin composition, that is, the total amount of the coloring pigment (A) and the alkali-soluble resin (B). If the amount is less than 1% by weight, the effect of improving the adhesiveness is not sufficient, and if it is more than 15% by weight, the fine pattern is lost in the alkali development and the resolution is lowered.

Among the colored resin compositions of the present invention, a black resin composition using a black light-shielding material as a coloring pigment in particular can be applied to a printing ink, an inkjet ink, a photomask producing material, a printing proof fabrication material, an etching resist, a solder resist, , An electrode (conductor circuit) pattern, a wiring pattern of an electronic component, a conductive paste, a conductive film, a black matrix, or the like. Preferably, in order to improve the display characteristics of the color filter used for a color liquid crystal display device or the like, in order to form a shielded image (including a black matrix) on the interval portion of the color pattern, the peripheral portion and the external light side of the TFT, And can be suitably used.

Particularly preferably, a black edge formed on a peripheral portion of a display device including a liquid crystal display device, a plasma display device, an EL display device including an inorganic EL, a CRT display device, and a touch panel, or a coloring pixel of red, And is preferably used as a black matrix formed on a black matrix formed on a color filter for a liquid crystal display device or a cover glass for a touch panel.

The black matrix formed on the cover glass for the touch panel serves as a frame for shielding the leakage light from the LCD panel. However, in order to enhance the designability, the frame may be formed by the coloring matrix formed by the composition of the colored resin other than black , The colored resin composition of the present invention can be suitably used.

As the colored pigment (A) of the colored resin composition of the present invention, any of an organic pigment and an inorganic pigment can be suitably used. Among pigments, those having strong tinting power, excellent in light resistance, heat resistance and chemical resistance are particularly preferable. A specific example of a representative pigment is represented by a color index (CI) number, the following is preferably used, but not all of them are limited thereto.

Examples of the red pigment include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like are used.

Examples of the orange pigment include pigment orange (hereinafter abbreviated as PO) 13, PO36, PO38, PO43, PO51, PO55, PO59, PO61, PO64, PO65 and PO71.

Examples of the yellow pigment include Pigment Yellow (hereinafter abbreviated as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY185 and the like are used.

Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40 and PV50.

Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, PB64 and the like.

Examples of the green pigment include pigment green (hereinafter abbreviated as PG) 7, PG10, PG36, PG58, and the like.

Examples of the black pigment include black organic pigments, mixed color organic pigments and inorganic pigments. Examples of the black organic pigments include carbon black, perylene black and aniline black. Examples of the mixed organic pigments include pigments obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, magenta, Examples of the inorganic pigments include graphite and fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, metal oxides, complex oxides, metal sulfides, metal nitrides and metal oxynitrides. These may be used alone or in combination of two or more.

Particularly, carbon black and titanium nitride are preferably used since they have a high light shielding property.

Examples of white pigments include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, silicon dioxide and the like.

Next, preferable characteristics when titanium nitride particles are used as the coloring pigment will be described in detail. Wherein titanium nitride is included in the titanium nitride as a main component, usual additives as titanium oxide _{TiO 2, Ti n O 2n -} 1 (1≤n≤20) indicated that low-order titanium oxide and _{TiN x O y (0 <x} < a 2.0, 0.1 < y < 2.0).

The diffraction angle 2? Of the peak derived from the (200) plane in the case where the CuK? Ray of the titanium nitride used in the present invention is an X-ray source is preferably 42.5 ° to 43.2 °, more preferably 42.5 ° to 42.8 ° , More preferably from 42.5 DEG to 42.7 DEG. By using the titanium nitride particles having the diffraction angle? Within this range as the light shielding material, it becomes possible to achieve a high OD value while maintaining the light shielding material concentration in the black resin composition at a low level, and also has a high ultraviolet transmittance, A resin black matrix having a good shape can be easily formed.

The X-ray diffraction spectrum of the titanium compound shows that the peak having the strongest intensity when the CuK? Ray is an X-ray source has a peak derived from the (200) plane in the vicinity of 2? = 42.5 占 and TiO originates from the The peak is seen in the vicinity of 2? = 43.4 °. On the other hand, the peaks derived from the (200) plane of the anatase type TiO ₂ are in the vicinity of 2? = 48.1 ° and the peaks derived from the (200) plane of the rutile TiO ₂ are in the vicinity of 2? = 39.2 ° Lt; / RTI &gt; Therefore, a titanium compound having a crystal structure having nitrogen atoms and oxygen atoms has a peak with the strongest intensity when the diffraction angle 2? Is in the range of 42.5 ° to 43.4 °, and the peak position in the crystal state containing a large amount of oxygen atoms is And is shifted toward the high angle side with respect to 42.5 deg. In titanium oxynitride obtained by nitriding titanium oxide with insufficient nitriding and reduction, a peak having the strongest intensity at 42.9 ° to 43.2 ° as a diffraction angle 2θ is confirmed (JP-A-2006-209102).

In the case of containing titanium oxide TiO ₂ as a subcomponent, a peak derived from anatase TiO ₂ (101) has a peak derived from rutile TiO ₂ (110) at a peak near 2θ = 25.3 ° 2 &amp;thetas; = 27.4 DEG. However, since TiO ₂ is white, it is a factor that deteriorates the light shielding property of the black matrix. Therefore, it is preferable that TiO ₂ is reduced to such an extent that it can not be observed as a peak.

The crystallite size constituting the titanium nitride particles can be obtained from the half width of the X-ray diffraction peak and is calculated using the Scherr's equation shown in the following formulas (2) and (3).

Here, K = 0.9, λ is the wavelength of the X-ray (0.15418 nm), β _e is the half width of the diffraction peak, and β _o is the correction value (0.12 °) of the half width. However, β, β _e and β _o are calculated in radians.

The crystallite size is preferably 10 nm or more, more preferably 10 to 50 nm, and further preferably 10 to 30 nm. When titanium nitride particles having a crystallite size of less than 10 nm are used, there arises a problem that the light shielding property of the black matrix is deteriorated and the dispersibility is deteriorated. On the other hand, when it exceeds 50 nm, there arises a problem that the light shielding property is deteriorated and the storage stability tends to be deteriorated. However, the smaller the crystallite size, the lower the light shielding property. However, since the color tone of the reflection is close to achromatic color, it is preferable that the crystallite size is suitably small in the present invention.

The specific surface area of the titanium nitride particles used in the present invention can be determined by the BET method. The value is preferably 5 to 100 m 2 / g, more preferably 10 to 100 m 2 / g, Lt; 2 &gt; / g. Further, from the specific surface area obtained by the BET method, the particle diameter in the case where the particles are perfectly spherical and the particle diameter is assumed to be uniform can be obtained by the following equation (4).

BET-converted average particle diameter (nm) = 6 / (S x d x 1000) (4)

Here, S; Specific surface area (m &lt; 2 &gt; / g), d; Density (g / cm 3), d = 5.24 (g / cm 3) for titanium nitride and d = 4.3 (g / cm 3) for titanium oxynitride.

When the specific surface area is small, that is, when the primary particle diameter is large, it is difficult to finely disperse the particles, the particles are precipitated during storage, the flatness when the resin is black matrix is lowered, . On the other hand, if the specific surface area is large, that is, if the primary particle diameter is small, the particles tends to re-agglomerate at the time of dispersion, so that dispersion stability tends to deteriorate or sufficient hiding power as a light shielding material is not obtained when the resin black matrix is used There is a problem that the OD value is lowered, which is not preferable.

The primary particles of the particles can be said to have several crystallites, but it is preferable that they consist of a single crystallite. That is, the relationship between the crystallite size determined from the half width of the X-ray diffraction peak and the particle diameter determined from the specific surface area is preferably in the range of the following formula (5).

BET-converted average particle diameter (nm) < Crystallite size (nm) x 2 (5)

The titanium nitride particles to be used in the present invention contain TiN as a main component and are usually remarkable in the case of incorporation of oxygen during synthesis thereof and particularly in the case of small particle diameter, . A smaller amount of oxygen contained is preferable because a higher OD value can be obtained, and it is particularly preferable that TiO ₂ is not contained as a subcomponent. However, the smaller the oxygen content, the more red color is expressed as the color taste of reflection, so that it is preferable that the oxygen content is appropriately contained. The content of the oxygen atom is preferably 5 to 20% by weight, more preferably 8 to 20% by weight.

The content of titanium atoms can be analyzed by ICP emission spectroscopy, the content of nitrogen atoms can be analyzed by inert gas fusion-thermal conductivity method, and the content of oxygen atoms can be analyzed by inert gas fusion-infrared absorption method.

Generally, the vapor phase reaction method is used for the synthesis of titanium nitride, and the electric furnace method and the thermal plasma method are exemplified. However, the incorporation of impurities is small and the particle diameter is likely to be uniform and the synthesis by the thermal plasma method desirable. Specifically, the primary particles of the titanium nitride synthesized by the thermal plasma method are formed of a single crystallite, and the titanium nitride synthesized by the thermal plasma method is used to form a black matrix having a lower dielectric constant Is preferable.

Examples of a method of generating thermal plasma include DC arc discharge, polyphase arc discharge, high frequency (RF) plasma, hybrid plasma, and the like, and a high frequency plasma with less impurities from the electrode is more preferable. As a specific method for producing titanium nitride microparticles by the thermal plasma method, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Application Laid-Open No. 2-22110) or a method in which titanium powder is evaporated by a high-frequency thermal plasma, (Japanese Patent Application Laid-Open No. 61-11140), and a method of blowing ammonia gas into the peripheral portion of the plasma (Japanese Patent Application Laid-Open No. 63-85007) However, the present invention is not limited to these, and any manufacturing method may be used if titanium nitride particles having desired physical properties can be obtained. A variety of titanium nitride particles are commercially available, and a plurality of titanium nitride particles satisfying the above-described diffraction angle and oxygen atom amount specified in the present invention, and the above-mentioned preferable crystallite size and specific surface area are also commercially available. In the present invention, those commercially available products can be preferably used.

Preferable properties when carbon black is used as a coloring pigment will be described in detail below.

As the carbon black used in the present invention, it is preferable to use surface-treated carbon black in order to increase the insulating property. As the treatment for improving the insulating property, generally, a surface coating with a resin (Japanese Patent Laid-Open Publication No. 2002-249678) Oxidation treatment (Japanese Patent No. 4464081), and surface modification by an organic group comprising a non-polymer group (Japanese Patent Publication No. 2008-517330). Among them, it is preferable to use a carbon black surface-modified with an organic group comprising a non-polymer group, because it is possible to obtain a resin black matrix having high insulation even after a high-temperature heat treatment. In particular, use of the carbon black surface-modified with an organic group having a sulfonic acid group is preferable because it can suppress the deterioration of the insulation property in high-temperature treatment and high insulation.

The surface composition of the carbon black used in the present invention is required to have a carbon atom content of 95% or less and a sulfur atom content of 0.5% or more, a carbon atom content of 95% or less and a sulfur atom content of 1.0% or more , More preferably not more than 90% of carbon atoms, and not less than 1.0% of sulfur atoms. The higher the proportion of the sulfur atom occupying the surface of the carbon black, the more effectively the binder resin is adsorbed to the carbon black, whereby the contact between the carbon blacks can be suppressed by the steric hindrance, and the insulating property of the resin black matrix is improved.

The sulfur atom component present on the surface of the carbon black used in the present invention exists in the form of disulfide, carbon disulfide and oxide. However, in order to obtain higher insulation, it is preferable that the sulfur atom component exists in the form of oxide. SO and SOx (2 &amp;le; x &amp;le; 4). The state of the S atom on the surface of the carbon black can be confirmed by X-ray photoelectron spectroscopy (XPS), and the S2p peak component is classified into a component belonging to CS and SS and a component belonging to SO and SOx (2? X? 4) It is possible to confirm the existence ratio thereof. As the carbon black used in the present invention, it is preferable that the proportion of the sulfur atom component present on the surface of the carbon black is a component derived from SO and SOx of 70% or more, more preferably 80% or more.

The higher the ratio of the sulfur atom component present on the surface to the component derived from SO and SOx, the higher the insulating property and the lower the insulating property in the high temperature treatment is. The mechanism for obtaining higher insulation and thermal stability by the large amount of components derived from SO and SOx is not clear, but it is presumed that the adsorption of the binder resin to carbon black becomes stronger. On the other hand, if the surface state of the conventional surface oxidation-treated carbon black is similarly analyzed, it can be said that the ratio of the sulfur atom component present on the surface of the carbon black to that originating from SO and SOx is 70% or less and the surface state is completely different .

The specific surface area of the carbon black used in the present invention is not particularly limited, but is preferably 10 to 600 m 2 / g, more preferably 20 to 200 m 2 / g, as measured by the BET method of nitrogen adsorption, And preferably 20 to 100 m &lt; 2 &gt; / g. When the specific surface area is large, that is, when the primary particle diameter is small, the particles easily aggregate, making dispersion stabilization difficult and deteriorating storage stability. On the other hand, when the specific surface area is small, that is, when the primary particle diameter is large, the light shielding property is lowered or the insulating property of the black resin coating film is lowered due to the contact of the carbon black in the resin coating film.

In order to make the effect of the present invention remarkable, it is preferable to use titanium nitride and / or carbon black as the color pigment (A), and the proportion of the titanium nitride occupying in the total weight of the light shielding material (A) is preferably 20 to 80% , And more preferably 30 to 70 wt%. When the proportion of the titanium nitride is small, the color tone of reflection is achromatic, but in order to obtain the desired light shielding property, the proportion of the coloring pigment in the resin composition needs to be increased so that the adhesiveness is lowered and the insulating property is lowered I do not. Particularly, deterioration of insulation due to high temperature thermal history becomes remarkable, and dielectric constant also becomes high, which is not preferable. On the other hand, as the ratio of the titanium nitride increases, the insulating property and the light shielding property increase, but it is preferable that the range is in the above range because the color tone of reflection indicates red color.

In the present invention, the alkali-soluble resin (B) is not particularly limited as long as it acts as a binder for the pigment and is soluble in an alkaline developer in the development process when forming a pattern such as a black matrix. Any of photosensitive and non-photosensitive can be used. Specifically, an epoxy resin, an acrylic resin, a siloxane polymer resin, a polyimide resin and the like are preferably used. Particularly, an acrylic resin or a polyimide resin is preferably used since it is excellent in heat resistance of a coating film, storage stability of a colored resin composition, and the like. Further, in forming a pattern such as a black matrix, a photosensitive alkali-soluble resin is suitably used because the step of forming a pattern becomes simpler by using a photosensitive resin.

Examples of the photosensitive alkali-soluble resin are shown below, but the present invention is not limited thereto.

The photosensitive alkali-soluble resin is composed of at least an alkali-soluble polymer, a reactive monomer, and a photopolymerization initiator. The amount ratio of these is generally from 10/90 to 90/10 in terms of the weight composition ratio of the alkali-soluble polymer and the reactive monomer, and the amount of the photopolymerization initiator is about 1 to 20% by weight based on the total weight of the polymer and the monomer.

An alkali-soluble polymer having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferably used. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, acid anhydrides thereof, phthalic acid mono (2 - (meth) acryloyloxyethyl), and the like. Particularly, an acrylic polymer comprising a constituent unit derived from (meth) acrylic acid is preferable, and an acrylic polymer obtained by reacting a compound containing an ethylenic unsaturated group and an epoxy group in a carboxylic acid contained in the constituent unit is used , Sensitivity at the time of exposure and development is improved, and therefore, it can be preferably used. The ethylenic unsaturated group is preferably an acryl group or a methacryl group.

These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, propyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, sec-butyl acrylate, sec- Unsaturated carboxylic acid alkyl esters such as pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and? -methylstyrene, (crosslinked) cyclic hydrocarbon groups such as tricyclodecanyl (meth) acrylate, Unsaturated carboxylic acid glycidyl esters such as saturated carboxylic acid aminoalkyl esters, glycidyl acrylate and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, acrylonitrile, methacrylic Acrylonitrile and? -Chloroacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; polystyrenes each having an acryloyl group or methacryloyl group at the ends; polymethyl acrylate; polymethyl acrylate; Methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like, but are not limited thereto.

Particularly, an acrylic polymer comprising (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable in view of dispersion stability and pattern processability.

When the acrylic polymer is added to the pigment in an amount of 5 to 50%, preferably 7 to 40% at the time of pigment dispersion, a highly dispersed pigment dispersion can be obtained.

In addition to the acrylic polymer obtained by reacting the (meth) acrylic acid contained in the constituent unit of the substrate with a compound containing an ethylenic unsaturated group and an epoxy group, an acrylic polymer having an ethylenic unsaturated group in its side chain can be preferably used. Specific examples thereof include copolymers described in Japanese Patent No. 3120476 and Japanese Patent Application Laid-open No. 8-262221, or a commercially available acrylic polymer "CYROMER (registered trademark) P" ), An alkali-soluble cardo resin, and the like.

The weight average molecular weight (Mw) of the alkali-soluble polymer is preferably 5,000 to 40,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted by using a calibration curve with standard polystyrene), and A polymer having a weight average molecular weight of 8,000 to 40,000 and an acid value of 60 to 150 (mgKOH / g) is most preferable from the viewpoints of photosensitivity, solubility in an ester solvent, solubility in an alkaline developer, and residue suppression.

As the reactive monomer, a polyfunctional, monofunctional acrylic monomer or oligomer can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (Meta) acrylate, an alkyd-modified (meth) acrylate, an anhydride-modified (meth) acrylic acid ester, a phthalic anhydride (meth) acrylate, a trimellitic acid diethylene glycol Fluorene diacrylate oligomer or tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate as described in JP-A-3621533 and JP- (Meth) acrylates such as bisphenol A diglycidyl ether di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate and its acid modified product, dipentaerythritol hexa (meth) acrylate and its acid modified product, dipentaerythritol penta (meth) acrylate and its acid modified product, 2, Bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4'-bis [4- Phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- Sphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, The acrylate, biscresol fluorene diacrylate, bis-cresol fluorene di-methacrylate and the like. These may be used alone or in combination.

By selecting and combining these multifunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. Particularly, in order to increase the sensitivity, it is preferable to use a compound having three or more functional groups, and more preferably five or more functional groups. Particularly, it is preferable to use compounds having dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta Body is preferable. Also, an unsaturated group-containing alkali-soluble monomer obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid with a polybasic carboxylic acid or an acid anhydride thereof is also preferably used from the viewpoints of developability and processability. Further, the combined use of (meth) acrylates having a fluorine ring having a high water repellency and containing a large number of aromatic rings in the molecule is preferable because the pattern can be controlled in a desirable shape at the time of development.

The photopolymerization initiator is not particularly limited, but it preferably contains an alkylphenol-based photopolymerization initiator and / or an oxime ester-based photopolymerization initiator.

Examples of the alkylphenon-based photopolymerization initiator include? -Aminoalkylphenone-based,? -Hydroxyalkylphenone-based, and the like. Of these,? -Aminoalkylphenone-based ones are particularly preferred from the viewpoint of high sensitivity. For example, 2,2-diethoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, Ciba Specialty Chemicals Co., Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 369 manufactured by Chiba Specialty Chemical Co., 1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 Phenylpropan-1-one, and the like.

Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime ), 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- N-1819, N-1919, and Adeca Cruz NCI-831 manufactured by Asahi Denka Kogyo Co., Ltd., and the like.

In addition to these photopolymerization initiators, it is also possible to use a photopolymerization initiator such as a benzophenone based compound, an oxytron based compound, an imidazole based compound, a benzothiazole based compound, a benzoxazole based compound, a carbazole based compound, a triazine based compound, A known photopolymerization initiator such as a photopolymerization initiator may be used in combination. Examples thereof include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoin, benzoin methyl ether, benzoin isobutyl Ether, benzyldimethyl ketal,? -Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, t-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, -Methanthraquinone, 2-ethyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethyl anthraquinone, 2- - (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2- mercaptobenzoxazole, 4- (p- methoxyphenyl) Di- (trichloromethyl) -s-triazine, and the like.

The organic solvent (D) used in the colored resin composition of the present invention is not particularly limited, and esters, aliphatic alcohols, ketones and the like can be used.

Specific examples of the esters include benzyl acetate (boiling point 214 占 폚), ethyl benzoate (boiling point 213 占 폚),? -Butyrolactone (boiling point 204 占 폚), methyl benzoate (boiling point 200 占 폚), diethyl malonate Butyl acetate (boiling point: 188 占 폚), diethyl oxalate (boiling point: 185 占 폚), 2-ethylhexyl acetate (boiling point: 199 占 폚), 2-butoxy ethyl acetate (Boiling point 171 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), acetoacetic acid methyl ester (boiling point 172 ° C), ethyl 3-ethoxypropionate Propylene glycol monomethyl ether propionate (boiling point: 160 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), 2-ethylbutyl acetate (boiling point: 162 占 폚), isopentylpropionate ° C.), pentyl acetate (boiling point: 150 ° C.), propylene glycol monomethyl ether acetate Boiling point 146 DEG C), and the like, but are not limited thereto.

Of these solvents, esters of 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy-butyl acetate, propylene glycol Monomethyl ether acetate is particularly preferred.

Propylene glycol monomethyl ether (boiling point: 120 占 폚), propylene glycol monoethyl ether (boiling point: 133 占 폚), propylene glycol tert-butyl ether (boiling point: 153 占 폚), dipropylene glycol monomethyl ether (Bp 77 ° C), butyl acetate (boiling point 126 ° C), isopentyl acetate (boiling point 142 ° C), or butanol (butyl alcohol) Alcohols such as 3-methyl-2-butanol (boiling point 112 ° C) and 3-methyl-3-methoxybutanol (boiling point 174 ° C), ketones such as cyclopentanone and cyclohexanone, It is also possible to use a solvent such as xylene (boiling point: 144 占 폚), ethylbenzene (boiling point: 136 占 폚), and solvent naphtha (petroleum oil fraction: boiling point: 165 to 178 占 폚).

In addition, as the substrate becomes larger, coating by the die coating apparatus has become mainstream, and therefore, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and dryness. When the boiling point of all the solvents constituting the mixed solvent is 150 ° C or lower, film thickness uniformity can not be obtained, and the film thickness of the coating completion portion becomes thick. As a result, aggregation of pigment is generated in the claw portion for discharging the coating liquid from the slit Causing many problems such as occurrence of stripes on the film. On the other hand, when the mixed solvent contains a large amount of a solvent having a boiling point of 200 ° C or higher, the surface of the coating film becomes sticky to cause sticking. Therefore, a mixed solvent containing 30 to 75 wt% of a solvent having a boiling point of 150 to 200 DEG C is preferable.

In the colored resin composition of the present invention, it is preferable to add a pigment dispersant to uniformly and stably disperse the colored pigment in the resin solution. Examples of the pigment dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a polyallyl amine polymer dispersant, a pigment derivative, a cationic surfactant, a nonionic surfactant, an anionic surfactant, a carbodiimide Based pigment dispersing agent and the like. These pigment dispersants are appropriately selected and used depending on the type of pigment.

These pigment dispersing agents may be used alone or in combination of two or more. These polymer dispersants do not have photosensitivity. Therefore, when added in a large amount, there is a fear that the photosensitive performance of a desired color resist may deteriorate, and it is preferable that the added amount is appropriately added in consideration of dispersion stability and photosensitive performance. The addition of 1 to 50 (by weight), more preferably 3 to 30 (% by weight), based on the pigment, is more preferable because it has the effect of stabilizing highly dispersed matters without deteriorating photosensitive performance.

In addition, a surfactant may be added to the colored resin composition of the present invention for the purpose of improving the coatability, the smoothness of the colored film, and the vanadell cell. The amount of the surfactant to be added is usually 0.001 to 10% by weight, preferably 0.01 to 1% by weight, of the pigment. If the addition amount is too small, the coating property, the smoothness of the colored coating and the effect of preventing the vanadic cell are not exhibited, and if it is excessively large, the physical properties of the coating film may be adversely affected.

Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkylether sulfate, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, A nonionic surfactant such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, polydimethylsiloxane, and the like as the main skeleton Based surfactant, a fluorinated surfactant, and the like. The present invention is not limited to these, and one or more surfactants may be used.

In the colored resin composition of the present invention, the weight ratio of the pigment component / the resin component is preferably in the range of 80/20 to 40/60 in order to obtain a film having an OD value high. Here, the pigment component means the sum of (A) the light-shielding material and the coloring pigment for chromaticity adjustment, and the sum of the additives such as oligomers, photopolymerization initiators, and polymer dispersants in addition to the alkali-soluble resin (B) . If the amount of the resin component is too small, the adhesion of the black coat to the substrate becomes poor. On the other hand, if the amount of the pigment component is too small, the optical density (OD value / 탆)

The solid content concentration of the resin component and the pigment component in the colored resin composition of the present invention is preferably 2 to 30%, more preferably 5 to 20%, from the viewpoint of coatability and drying property. Therefore, the colored resin composition of the present invention is preferably essentially composed of a solvent, a resin component and a pigment component, and the total amount of the resin component and the colored pigment is preferably 2 to 30%, more preferably 5 to 20% , And the remainder is the solvent. As described above, the surfactant may be further contained at the above-mentioned concentration.

In the colored resin composition of the present invention, a method of dispersing a pigment directly in a resin solution using a dispersing machine, a method of dispersing a pigment in water or an organic solvent using a dispersing machine to prepare a pigment dispersion, . The method of dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill can be used, but a bead mill is preferable from the viewpoint of dispersion efficiency and differential oxidation. As the bead mill, a cob ball mill, a basket mill, a pin mill, a dynomill, and the like can be used. As the beads of the bead mill, it is preferable to use titania beads, zirconia beads, zircon beads and the like.

The bead diameter used for dispersion is preferably 0.01 to 5.0 mm, more preferably 0.03 to 1.0 mm. When the primary particle size of the pigment and the secondary particle size formed by agglomeration of the primary particles are small, it is preferable to use fine dispersion beads having a particle size of 0.03 to 0.10 mm. In this case, it is preferable to use a bead mill having a separator by a centrifugal separation method capable of separating the fine dispersion beads and the dispersion liquid. On the other hand, when dispersing pigments containing coarse and large particles on the order of submicron, it is preferable to use dispersion beads of 0.10 mm or more to obtain a sufficient crushing power to finely disperse the pigments.

An example of a method for producing a resin black matrix substrate by a die coating apparatus using the colored resin composition of the present invention will be described. As the substrate, a transparent substrate such as soda glass, non-alkali glass, quartz glass, or the like is usually used, but the present invention is not limited thereto. As the die coating apparatus, for example, Japanese Patent No. 3139358, Japanese Patent No. 3139359, and the like can be exemplified. By this apparatus, the colored resin composition (coating liquid) of the present invention can be discharged from the spinneret and the substrate can be moved to apply the colored resin composition on the substrate. In this case, since a large number of substrates are coated on each sheet, agglomerates of the pigment are formed on the claws for discharging the coating liquid from the slits for a long time, which may lead to coating defects, which may lead to a reduction in yield.

In this case, by forming a step of wiping the nozzle, which is a discharge port of the apparatus, with a solvent containing 40 wt% or more of the ester solvent having a boiling point of 150 캜 or more, the coating defects are eliminated and the yield is improved. The colored resin composition is coated on the substrate as described above, and then the solvent is removed by air drying, reduced pressure drying, heat drying, or the like to form a coating film of the colored resin composition. In particular, after the reduced-pressure drying step is performed, further heating and drying in an oven or a hot plate can solve the coating defects caused by convection, thereby improving the yield. The reduced-pressure drying is preferably carried out at a temperature of room temperature to 100 ° C for 5 seconds to 10 minutes, a reduced pressure of 500 to 10 (Pa), and more preferably a reduced pressure of 150 to 50 (Pa). The heating and drying is preferably performed in an oven, a hot plate or the like at a temperature in the range of 50 to 120 ° C for 10 seconds to 30 minutes.

Subsequently, a mask is placed on the film, and ultraviolet rays are irradiated using an exposure apparatus. Subsequently, development is carried out with an alkaline developer. When an alkaline developer containing 0.1 to 5% of a surfactant such as a nonionic surfactant is used, a better pattern can be obtained, which is preferable. The alkaline substance used in the alkaline developer is not particularly limited, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate and ammonia water, , Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) Diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol, and other alcohols such as pyrrole, piperidine, 1,8-diazabicyclo [5, 4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, morpholine, and other cyclic amines.

The concentration of the alkaline substance is 0.01 to 50% by weight. Preferably 0.02 to 10% by weight, more preferably 0.02 to 1% by weight. When the developer is an aqueous alkali solution, a water-soluble organic solvent such as ethanol,? -Butyrolactone, dimethylformamide or N-methyl-2-pyrrolidone may be appropriately added to the developer.

Among these developers, an aqueous developer of an aqueous alkaline solution is preferable from the viewpoint of working environment and waste developer treatment.

The developing method uses a dipping method, a spray method, a paddle method, or the like, but is not particularly limited. After the development, a cleaning process using pure water or the like is added.

The coating film pattern of the obtained colored resin composition is then patterned by heat treatment (post baking). The heat treatment is usually carried out continuously or stepwise for 0.25 to 5 hours at a temperature of 150 to 300 占 폚, preferably 180 to 250 占 폚, in air, in a nitrogen atmosphere or in vacuum.

As described above, the optical density (OD value) of the resin black matrix obtained from the colored resin composition of the present invention is preferably 2.5 or more per 1.0 탆 of the film thickness in the visible light range of wavelengths of 380 to 700 nm, More preferably 3.0 or more and 4.0 or more. The OD value can be obtained from the following relational expression (6) by carrying out measurement with a brown-type spectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

OD value = log ₁₀ (I ₀ / I) (6)

Where I ₀ ; Incident light intensity, I; The transmitted light intensity is obtained.

The reflection chromaticity of the resin black matrix is measured from the surface of the transparent substrate, and the chromaticity value a (a) calculated by the CIE L * a * b * colorimetric system using the reflection spectrum for the standard C light source according to the method of JIS Z8729 *, b *) are preferably from -2.0 to 2.0, more preferably from -1.0 to 1.0. When the chromaticity value (a *, b *) is smaller than -2.0, there is a problem that when the resin black matrix is viewed through the transparent substrate, the image reflected on the film surface is colored and visually colored in blue and green. There is a problem that the image is colored with red and yellow to be recognized.

The surface resistance value? S (? /?) Of the resin black matrix is preferably 10 ¹⁰ (? /?) Or more, more preferably 10 ¹² (? /) Or more. The surface resistance value can be determined by measuring by the method of JIS K6911.

The relative dielectric constant epsilon r of the resin black matrix is preferably 10 or less at 1 MHz, more preferably 8 or less, and further preferably 6 or less. If the relative dielectric constant of the resin black matrix is larger than 10, there is a fear that the sensitivity of the sensor electrode is lowered due to the unevenness of the electric field in the touch panel. The relative dielectric constant of the resin black matrix is preferably as small as possible, and the lower limit thereof is not particularly limited, but is usually 2 or more at 1 MHz.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Evaluation method>

[Surface Element Composition]

The surface elements of carbon black were measured by X-ray photoelectron spectroscopy (XPS). As the measuring conditions, ESCALAB220iXL (trade name) was used, and monochromatic AIK alpha 1 and 2 lines (1486.6 eV) were used as the excitation X-rays, and the X-ray diameter was 1 mm and the photoelectron escape angle was 90 °.

[Specific surface area]

The specific surface area of the particles was determined by measuring the adsorption isotherm at the liquid nitrogen temperature (77 K) of N ₂ gas after vacuum degassing at 100 ° C. using a high precision automatic gas absorption apparatus ("BELSORP" 36) manufactured by Nippon Bell Co. And the isotherm was analyzed by the BET method to determine the specific surface area. Further, from the value of the specific surface area, the BET-converted particle diameter was obtained by using the above-mentioned formula (4). At this time, d = 5.24 (g / cm 3) was used as the specific gravity for the titanium nitride particles and d = 1.80 (g / cm 3) was used as the specific gravity for the carbon black.

&Quot; X-ray diffraction &quot;

X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Denki Co., Ltd.) filled with a powder sample in a standard sample holder made of aluminum. As the measurement conditions, the X-ray source was a CuKα line, and the output was 50 kV / 200 mA, the slit system was 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) was 0.02 ° and the scan speed was 2 ° / . And the diffraction angle of a peak derived from the (200) plane observed near the diffraction angle 2? = 46 was measured. The crystallite size constituting the particles was determined from the half-width of the peak derived from the (200) plane using the Scherr's equation of the above-mentioned formulas (2) and (3).

"Composition analysis"

The content of the titanium atom was measured by ICP emission spectroscopy (ICP emission spectroscopic analyzer SPS3000 manufactured by Seiko Instruments Inc.). The content of oxygen atoms and nitrogen atoms was measured using an oxygen / nitrogen analyzer (EMGA-620W / C, manufactured by Horiba Seisakusho Co., Ltd.) and the oxygen atoms were analyzed by an inert gas melting-infrared absorption method by inert gas fusion- Nitrogen atoms were obtained.

[Adhesion test]

A resin black matrix having a film thickness of 1.0 占 퐉 was formed on soda glass and the adhesion between the soda glass and the cured film was evaluated according to JIS K5400 8.5.2 (1990) lattice tape method. Parallel straight lines of 11 vertically and horizontally orthogonal to each other so as to reach the glass substrate by the cutter knife were formed on the surface of the cured film on the glass substrate at intervals of 1 mm to prepare 100 cells of 1 mm x 1 mm. A cellophane adhesive tape (width = 18 mm, adhesive force = 3.7 N / 10 mm) was attached to the surface of the cut cured film and rubbed with an eraser (JIS S6050 acceptable product) to closely contact. One end of the tape was held at a right angle to the plate, and the remaining number of cells at the moment of peeling was evaluated by naked eyes. The peeling area of the cell was determined as follows.

5: Peel area 0%

4: Peel area 1 to < 5%

3: peeling area 5 to < 15%

2: peeling area 15 to < 35%

1: peeling area 35 to < 65%

0: Peel area 65 to 100%

Further, in order to evaluate the adhesiveness after the wet heat treatment, the adhesion of the black matrix substrate subjected to the PCT (Pressure Cooker Test) treatment was also evaluated as described above. The conditions of the PCT treatment were a temperature of 121 占 폚, a humidity of 100%, and a pressure of 2 atm for 12 hours.

[Chemical resistance test]

A resin black matrix having a film thickness of 1.0 占 퐉 was formed on soda glass, immersed in a water solution and an organic alkali solution, and then the adhesion was evaluated in the same manner as described above. Here, the condition of the water treatment was set at 50 DEG C for 5 minutes in a mixed solution of hydrochloric acid / nitric acid / distilled water = 25/3/72 wt%. The conditions of the organic alkali treatment were set at 80 DEG C for 5 minutes in a mixed solution of MEA (monoethanolamine) / BDG (butyl glycol) = 30/70 wt%.

[resolution]

When forming a resin black matrix having a film thickness of 1.0 占 퐉 on a soda glass, the width of a mask pattern capable of forming a minimum pattern was measured using a 1: 1 width line and space pattern mask.

[OD value]

A resin black matrix having a film thickness of 1.0 占 퐉 was formed on soda glass and was determined from the formula (6) described above using a brown rice spectrometer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

[Surface resistance]

A resin black matrix having a film thickness of 1.0 占 퐉 was formed on soda glass, and the surface resistivity (? /?) Was measured by a high resistivity meter (Mitsubishi Kagaku Hiresta UP).

Also, after the black matrix was heat treated in an oven at 250 캜 for 30 minutes, the surface resistivity was similarly measured.

[Reflection chromaticity]

A resin black matrix having a thickness of 1.0 占 퐉 was formed on a soda glass having a thickness of 1.1 mm and the reflection chromaticity from the glass surface was measured using an ultraviolet / visible / near infrared spectrophotometer (Shimazu Spectrophotometer UV-2500PC) 300 nm to 780 nm, sampling pitch: 1.0 nm, scan speed: low speed, slit width: 2.0 nm).

Synthesis Example 1 Synthesis of silane coupling agent mixed solution (a-1)

41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 11.70 g (160 mmol) of t-butylamine were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while. Stirring time. Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to give 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- Amino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid (a-1).

Synthesis Example 2 Synthesis of silane coupling agent mixed solution (a-2)

41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of t-pentylamino were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while. Stirring time. Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to obtain 2- (2- (t-pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (a-2) of (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.

Synthesis Example 3 Synthesis of silane coupling agent mixed solution (a-3)

41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 9.45 g (160 mmol) of isopropylamine were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while, Lt; / RTI &gt; Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to give 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) tert-isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid (a-3).

Synthesis Example 4 Synthesis of silane coupling agent mixed solution (a-4)

41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of n-propylamine were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while. Stirring time. Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to give 2- (2-oxo-2- (propylamino) ethyl) -5- (trimethoxysilyl) Carbamoyl) -6- (trimethoxysilyl) hexanoic acid (a-4).

Synthesis Example 5 Synthesis of silane coupling agent mixed solution (a-5)

41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 14.90 g (160 mmol) of aniline were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while and then stirred at 40 ° C for 2 hours . Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to give 2- (2-oxo-2- (phenylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- Carbamoyl) -6- (trimethoxysilyl) hexanoic acid (a-5).

Synthesis Example 6 Synthesis of silane coupling agent mixed solution (a-6)

41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 7.37 g (160 mmol) of ethanol were added to 200 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while and then stirred at 40 DEG C for 2 hours . Thereafter, the temperature was raised to 80 DEG C and the reaction was carried out for 6 hours. The resulting solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to give 4-ethoxy-4-oxo-2- (trimethoxysilyl) (Trimethoxysilyl) butanoic acid (a-6).

Synthesis Example 7 Synthesis of silane coupling agent solution (a-7)

41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine were added to 400 g of propylene glycol monomethyl ether acetate, and the mixture was stirred at room temperature for a while. Stirring time. Thereafter, the temperature was raised to 140 占 폚, and propylene glycol monomethyl ether acetate and water were boiled together and reacted for 6 hours. The obtained solution was diluted with propylene glycol monomethyl ether acetate to a solid concentration of 20% to obtain a 1- (tert-butyl) -3-trimethoxysilylpyrrolidine-2,5-dione solution (a-7) .

Synthesis Example 8 Synthesis of acrylic polymer (P-1)

After synthesis of methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30/40/30) by the method described in Example 1 of Japanese Patent No. 3120476, 40 parts by weight of glycidyl methacrylate was added (P-1) powder having an average molecular weight (Mw) of 15,000 and an acid value of 110 (mgKOH / g) was obtained by reprecipitation, filtration and drying with purified water.

Production Example 1 Production of carbon black dispersion (CB-1)

(C: 88%, O: 7%, Na: 3%, S: 2) was used as the surface element composition of the carbon black (CB-Bk1) modified with the sulfonic acid group surface by the method described in Japanese Patent Application Publication No. 2008-517330 %). As the state of the S element, 90% of the components attributed to CS and SS among S2p peak components, 10% of components attributed to SO and SOx, and a BET value of 54 m2 / g.

40 g of a 40 wt% solution (94 g) of propylene glycol monomethyl ether acetate of acrylic polymer (P-1), 40 g of a 40 wt% solution of Bigkemi Japan LPN21116 as a polymer dispersant, Glycol monomethyl ether acetate (675 g) was charged into a tank and stirred for 1 hour in a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a preliminary dispersion. Thereafter, the preliminary dispersion liquid was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 70% of zirconia beads (YTZ ball, manufactured by Nikkato) of 0.05 mm phi, Followed by time dispersion to obtain a carbon black dispersion (CB-1) having a solid content concentration of 25% by weight and a pigment / resin (weight ratio) = 80/20.

Production Example 2 Production of titanium black dispersion (TB-1)

The diffraction angle 2? Of the peak derived from the (200) plane of the titanium nitride particles (Ti-BK1, manufactured by Nisshin Engineering Co., Ltd., TiN UFP Lot 1320910202) produced by the thermal plasma method was 42.62 °, The crystallite size was 21.9 nm and the BET specific surface area was 85.0 m 2 / g. As a result of composition analysis, the titanium content was 70.4 wt%, the nitrogen content was 19.9 wt%, and the oxygen content was 8.86 wt%. In addition, no X-ray diffraction peak due to TiO ₂ was observed at all.

40 wt% solution (94 g) of propyleneglycol monomethyl ether acetate of acrylic polymer (P-1), 40 g of a 40 wt% solution of VICKEMI Japan LPN21116 as a polymeric dispersing agent and 31 g of propylene glycol mono Methyl ether acetate (675 g) was charged into a tank and stirred for 1 hour in a homomixer (manufactured by Toguishikika) to obtain a preliminary dispersion 1. Thereafter, the preliminary dispersion 1 was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 70% of zirconia beads (YTZ ball, manufactured by Nikkato Co., Ltd.) Followed by dispersion for 2 hours to obtain a titanium black dispersion (TB-1) having a solid content concentration of 25% by weight and a pigment / resin (weight ratio) = 80/20.

Production Example 3 Preparation of Red Pigment Dispersion (R-1)

120 g of the organic pigment PY254 (R-1, manufactured by BASF), 100 g of a 40 wt% solution of the acrylic polymer (P-1) in propylene glycol monoethyl ether acetate, 100 g of 40 wt% solution of Big Chemie Japan LPN21116 as a polymer dispersant, 680 g of propylene glycol monoethyl ether acetate was added to the tank and stirred for 20 minutes in a homomixer (made by Primimix) to obtain a preliminary dispersion. Thereafter, a preliminary dispersion liquid was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 75% of zirconia beads (nitrene, YTZ ball) of 0.05 mm phi, and the mixture was stirred at a rotation speed of 8 m / s for 3 hours To obtain a yellow pigment dispersion (Y-1) having a solid concentration of 20% by weight and a colorant / resin (weight ratio) = 60/40.

Production Example 4 Production of blue pigment dispersion (B-1)

A blue pigment dispersion (B-1) was obtained in the same manner as in the case of the red pigment dispersion (R-1) except that the organic pigment PB15: 6 (B-1, manufactured by Toyo Inu K.K.) was used as the pigment.

Production Example 5 Preparation of yellow pigment dispersion (Y-1)

A yellow pigment dispersion (Y-1) was obtained in the same manner as in the red pigment dispersion (R-1) except that the organic pigment PY139 (Y-1, manufactured by Clariant) was used as the pigment.

Example 1

A solution (122.1 g) of a 40 wt% solution of acrylic polymer (P-1) in propylene glycol monomethyl ether acetate was prepared by mixing 267.9 g of the carbon black dispersion (CB-1) and 267.9 g of the titanium black dispersion (TB- , A 50% by weight solution (94.6 g) of propylene glycol monomethyl ether acetate of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, ADEKA "Adeka Cruz" NCI -831 (11.8 g) as a polymerization initiator, a silane coupling agent mixture solution (a-1) (37.5 g) as a adhesion improver and a 10 wt% solution of a silicon surfactant in propylene glycol monomethyl ether acetate (4.0 g) were dissolved in propylene glycol monomethyl ether acetate 194.0 g) was added to obtain a black resin composition 1 having a total solid content concentration of 25% by weight and a pigment / resin (weight ratio) of 45/55.

This black resin composition 1 was coated on a soda glass substrate with a spinner 1H-DS manufactured by Mikasa Co., Ltd., and prebaked at 100 ° C for 10 minutes to prepare a coating film. (200 mJ / cm 2) through a photomask using a mask aligner PEM-6M manufactured by Union Kogaku Co., Ltd., developed using 0.045 wt% KOH aqueous solution, and then cleaned pure to obtain a patterned substrate. Further, it was cured at 230 DEG C for 30 minutes. Thus, a black matrix 1 having a thickness of 1.00 m was formed.

Example 2

A black resin composition 2 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-2) was used in place of the silane coupling agent mixture solution (a-1).

Using black resin composition 2, black matrix 2 having a thickness of 1.00 탆 was formed similarly to Example 1.

Example 3

A black resin composition 3 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-3) was used in place of the silane coupling agent mixture solution (a-1).

Using the black resin composition 3, a black matrix 3 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 4

Black resin composition 4 was obtained in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixture solution (a-1) was changed to 6.3 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 225.2 g.

Using the black resin composition 4, a black matrix 4 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 5

Black resin composition 5 was obtained in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixture solution (a-1) was changed to 12.5 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 219.0 g.

Using the black resin composition 5, a black matrix 5 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 6

Black resin composition 6 was obtained in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixture solution (a-1) was changed to 62.5 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 169.0 g.

Using the black resin composition 6, a black matrix 6 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 7

Black resin composition 7 was obtained in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixture solution (a-1) was changed to 187.5 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 44.0 g.

Using the black resin composition 7, a black matrix 7 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 8

Except that 7.5 g of 3-methacryloxypropyltrimethoxysilane (a-8) was added in addition to the silane coupling agent mixture solution (a-1), and the addition amount of propylene glycol monomethyl ether acetate was changed to 186.5 g A black resin composition 8 was obtained in the same manner as in Example 1.

Using the black resin composition 8, a black matrix 8 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 9

Black resin composition 9 was obtained in the same manner as in Example 8 except that the addition amount of silane coupling agent mixture solution (a-1) was changed to 12.5 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 211.5 g.

Using the black resin composition 9, a black matrix 9 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Example 10

Black resin composition 10 was obtained in the same manner as in Example 8 except that the addition amount of the silane coupling agent mixture solution (a-1) was changed to 62.5 g and the addition amount of propylene glycol monomethyl ether acetate was changed to 161.5 g.

Using the black resin composition 10, a black matrix 10 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 11

A black resin composition 11 was obtained in the same manner as in Example 8 except that the addition amount of the carbon black dispersion (CB-1) was changed to 0 g and the addition amount of the titanium black dispersion (TB-1) was changed to 534.8 g.

Using the black resin composition 11, a black matrix 11 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1. [

Example 12

A black resin composition 12 was obtained in the same manner as in Example 8 except that the addition amount of the carbon black dispersion (CB-1) was changed to 134.0 g and the addition amount of the titanium black dispersion (TB-1) was changed to 401.9 g.

Using the black resin composition 12, a black matrix 12 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 13

A black resin composition 13 was obtained in the same manner as in Example 8 except that the addition amount of the carbon black dispersion (CB-1) was changed to 401.9 g and the addition amount of the titanium black dispersion (TB-1) was changed to 134.0 g.

Using the black resin composition 13, a black matrix 13 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Example 14

A black resin composition 14 was obtained in the same manner as in Example 8 except that the addition amount of the carbon black dispersion (CB-1) was 534.8 g and the addition amount of the titanium black dispersion (TB-1) was 0 g.

Using the black resin composition 14, a black matrix 14 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Example 15

The red pigment dispersion (R-1) (160.2 g), the blue pigment dispersion (B-1) (320.4 g) and the yellow pigment dispersion (Y- 40.8 wt% of a 40 wt% solution of propylene glycol monomethyl ether acetate, 38.7 g of a 50 wt% solution of propylene glycol monomethyl ether acetate in dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 1) (30.0 g) as an adhesion improver, and 3-methacryloxypropyltrimethoxysilane (a-1) as a adhesion improver were used as a photopolymerization initiator, Adeka Cruz NCI-831 (9.7 g) -8) (7.5 g) and a solution prepared by dissolving 4.0 g of a 10% by weight solution of propylene glycol monomethyl ether acetate in a silicone surfactant in propylene glycol monomethyl ether acetate (44.3 g) were added to obtain a solution having a total solids concentration of 25 wt% %, Pigment / resin (weight ratio) = 40/60.

Further, using the pseudo black resin composition 15, a black matrix 15 having a thickness of 1.00 탆 was prepared similarly to Example 1.

Comparative Example 1

Except that 7.5 g of 3-methacryloxypropyltrimethoxysilane (a-8) was added without adding the silane coupling agent mixture solution (a-1), and the addition amount of propylene glycol monomethyl ether acetate was 224.0 g A black resin composition 16 was obtained in the same manner as in Example 1.

Using the black resin composition 16, a black matrix 16 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Comparative Example 2

A black resin composition 17 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-4) was used in place of the silane coupling agent mixture solution (a-1).

Using the black resin composition 17, a black matrix 17 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Comparative Example 3

A black resin composition 18 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-5) was used in place of the silane coupling agent mixture solution (a-1).

Using the black resin composition 18, a black matrix 18 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Comparative Example 4

A black resin composition 19 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-6) was used in place of the silane coupling agent mixture solution (a-1).

Using the black resin composition 19, a black matrix 19 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Comparative Example 5

A black resin composition 20 was obtained in the same manner as in Example 1 except that the silane coupling agent mixture solution (a-7) was used in place of the silane coupling agent mixture solution (a-1).

Using the black resin composition 20, a black matrix 20 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Comparative Example 6

Except that 7.5 g of 3-methacryloxypropyltrimethoxysilane (a-9) was added instead of the silane coupling agent mixture solution (a-1), and the amount of propylene glycol monomethyl ether acetate added was changed to 224.0 g. 1, a black resin composition 21 was obtained.

Using the black resin composition 21, a black matrix 21 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

Comparative Example 7

Except that 7.5 g of 3-aminopropyltriethoxysilane (a-10) was added instead of the silane coupling agent mixture solution (a-1), and the amount of propylene glycol monomethyl ether acetate added was changed to 224.0 g. In the same manner, a black resin composition 22 was obtained.

Using the black resin composition 22, a black matrix 22 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Comparative Example 8

Except that 7.5 g of 3-ureidopropyltriethoxysilane (a-11) was added instead of the silane coupling agent mixture solution (a-1), and the addition amount of propylene glycol monomethyl ether acetate was changed to 224.0 g. The black resin composition 23 was obtained.

Using the black resin composition 23, a black matrix 23 having a thickness of 1.00 탆 was prepared similarly to Example 1. [

Comparative Example 9

7.5 g of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (a-12) was added instead of the silane coupling agent mixture solution (a-1), and propylene glycol monomethyl ether A black resin composition 24 was obtained in the same manner as in Example 1 except that the amount of acetate added was changed to 224.0 g.

Using the black resin composition 24, a black matrix 24 having a thickness of 1.00 占 퐉 was prepared similarly to Example 1.

The evaluation results are shown in Table 1. It can be seen that the black matrix formed using the resin composition shown in the examples has high adhesion and excellent chemical resistance and is not easily peeled off even after the wet heat treatment or the chemical immersion.

(Industrial availability)

The colored resin composition of the present invention can be used for a black matrix of a color filter substrate for a liquid crystal display device.

Claims (7)

A colored resin composition containing at least (A) a coloring pigment, (B) an alkali-soluble resin, (C) a contact improving agent, and (D) an organic solvent, And a silane coupling agent.

(Each R ¹ may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) The alkyl group may further have a substituent, n represents 0 or 1. R ² represents a trivalent organic group having 3 to 30 carbon atoms . R ³ is or different may gatahdo respectively, having 1 to 6 carbon alkyl group, represents a C 1 -C 6 alkoxy group, a phenyl group, a hydroxyl group or a phenoxy group. Further, among these groups of R ^3, other than a hydroxyl group substituent May be further included.) The method according to claim 1,
Wherein the adhesion modifier (C) is a silane coupling agent represented by n = 0 in the general formula (1). 3. The method according to claim 1 or 2,
Wherein at least two kinds of silane coupling agents are contained as the (C) adhesion improver. 4. The method according to any one of claims 1 to 3,
Wherein the colored pigment (A) is a black light shielding material. 5. The method of claim 4,
Wherein the black light-shielding material contains at least titanium nitride particles and / or carbon black. 6. The method of claim 5,
Wherein the weight ratio of the titanium nitride particles to the total weight of the black shading material is 20 to 80 wt%. A resin black matrix substrate characterized by being obtained by applying the colored resin composition according to any one of claims 4 to 6 on a transparent substrate to form a pattern.