JP5577659B2 - Photosensitive black resin composition, resin black matrix substrate, color filter substrate, and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive black resin composition and a colored pattern formed using the same, and more specifically, a photosensitive black resin composition for a color filter, and a resin black matrix substrate, a color filter substrate and a liquid crystal display device using the same. It is about.

  A color filter is usually manufactured by a method in which different hues of red, green, and blue are sequentially formed in a striped or mosaic color pattern on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. Yes. The black matrix used as the light-shielding film plays a role of preventing a decrease in contrast and color purity due to light leakage between pixels.

  Conventionally, vapor deposition films of metals or metal compounds such as chromium, nickel, and aluminum have been used as the black matrix, but the process is complicated and expensive, and the surface of the metal thin film is highly reflective. There is a problem. Therefore, as a solution to this problem, a pigment dispersion method using a resin composition in which a pigment is dispersed is currently mainstream.

  There are negative and positive pigment dispersion methods, but negative photosensitive compositions mainly composed of acrylic polymers, acrylic polyfunctional monomers or oligomers, photoinitiators, solvents and pigments are widely used. Yes. As the light shielding material, carbon black, titanium black such as low-order titanium oxide and titanium oxynitride, metal oxides such as iron oxide, and other organic pigment mixed colors are used, but carbon black and titanium oxynitride are the mainstream. It has become. As an example of such a general-purpose pigment dispersion system, Patent Document 1 describes a resin black matrix in which carbon black is dispersed in a photosensitive acrylic resin.

  However, with recent demands for color filter thinning, higher performance, and higher brightness of backlights used in liquid crystal display devices, there is an increasing demand for higher OD values for resin black matrices. The conventional resin black matrix using such carbon black has an insufficient OD value. In addition, when the resin black matrix is thick, the surface step generated by the color pixels mounted on the resin black matrix becomes large, so that the flatness of the color filter is deteriorated and the liquid crystal orientation is disturbed. There is also a growing demand for computerization.

  On the other hand, if the volume ratio of the light shielding material is increased in order to achieve such a high OD value and thin film, the resin ratio in the resin black matrix is decreased, and the adhesion between the resin black matrix and the glass is reduced. There arises a problem that the resin black matrix is peeled off and a sufficient resistance value cannot be obtained. Further, there has been a problem that due to the high concentration of the light-shielding agent, sufficient sensitivity cannot be obtained and it becomes difficult to form a high-definition pattern, and a taper shape is urged. In order to increase the sensitivity of the photosensitive resin composition, various studies have been made on the types of initiators and photosensitive resins (Patent Documents 2 and 3). In addition, studies have been made to increase the sensitivity by using a light shielding material having a high light transmittance in the ultraviolet region (365 nm), for example, titanium oxynitride (Patent Document 4). However, it is very difficult and insufficient to pattern the coating film with a very high light-shielding property exceeding OD value = 5 (light transmittance = 0.001%). Therefore, a light shielding material that achieves a higher OD value and has a high light transmittance in the ultraviolet region is required even with a small content.

  Other black pigments include titanium nitride, and techniques used in photosensitive resin compositions have been disclosed (Patent Documents 5 and 6), but minimum transmittance in the visible light region required as a black matrix. That is, in terms of blackness, it is not sufficient, and it is difficult to form on a substrate simply because it is not applied and patterned as a black composition.

Japanese Patent Laid-Open No. 10-300923 JP 2005-338328 A JP-A-2005-77451 WO2005-037926 JP 2003-252955 A JP 2004-339499 A

  The present invention was devised in view of the drawbacks of the prior art. The object of the present invention is to easily produce a black matrix having a high OD value, a high adhesion, a high resolution, and a good taper shape. It is providing the black resin composition which can be formed in. By using such a black resin composition, a resin black matrix having a thin OD and a good shape can be obtained. By using a color filter in which such a resin black matrix is formed, display characteristics are excellent. A liquid crystal display device is obtained.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have selected the following specific titanium nitride particles as a light-shielding material and combined them with a resin having a photosensitive group. I found that I could solve the problem.

That is, the object of the present invention is achieved by the following configuration.
(1) A photosensitive black resin composition containing at least a light shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer and an organic solvent, wherein the light shielding material contains at least titanium nitride particles, and the black Regarding the light transmittance when the optical density (OD value) of the coating film formed using the resin composition is 3, the ratio of the light transmittance at 365 nm to the light transmittance at 550 nm is 0.3 or more. A photosensitive black resin composition characterized by the above.
(2) The diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays of the titanium nitride particles are used as an X-ray source is 42.5 ° or more and 42.8 ° or less, and the (200) plane The photosensitive black resin composition as described in (1) whose crystallite size calculated | required from the half width of the peak originating in is 20 nm or more and 50 nm or less.
(3) The photosensitive black resin composition according to either (1) or (2), wherein the ratio of titanium nitride particles in the total weight of the light shielding material is 10 wt% or more.
(4) The photosensitive black resin composition according to any one of (1) to (3), wherein the titanium nitride particles are produced by a thermal plasma method.
(5) The photosensitive black resin composition according to any one of (1) to (4), wherein the photopolymerization initiator contains (a) an alkylphenone compound at least.
(6) The photopolymerization initiator includes at least two components (a) an alkylphenone compound and (b) an oxime ester compound, and the content of (b) in the total weight of the photopolymerization initiator is 30 wt. % Of the photosensitive black resin composition as described in (5).
(7) A resin black matrix substrate obtained by applying the black resin composition according to any one of (1) to (6) on a transparent substrate and forming a pattern, wherein the optical property of the resin black matrix A resin black matrix substrate having a concentration (OD value) of 4.0 or more per 1 μm thickness.
(8) A color filter substrate, wherein red, green, and blue pixels are formed in openings of the resin black matrix substrate according to (7).
(9) A liquid crystal display device comprising the color filter substrate according to (8).

  By using the black resin composition of the present invention, there is obtained an effect that a thin resin black matrix can be easily obtained with high light-shielding properties, high adhesion, high sensitivity, good pattern shape and taper shape.

Hereinafter, the present invention will be described in more detail.
The black resin composition of the present invention needs to contain at least a light shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, and at least titanium nitride particles having specific characteristics as the light shielding material. The desirable characteristics are shown below.

  The black resin composition of the present invention includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, electrode (conductor circuit) ) It can be used for the production of light-shielded images such as patterns, wiring patterns of electronic components, conductive pastes, conductive films, and black matrices. Preferably, in order to improve display characteristics of a color filter used in a color liquid crystal display device or the like and a touch panel, a light-shielded image (including a black matrix) is provided on the spacing portion of the coloring pattern, the peripheral portion, and the outside light side of the TFT. In order to provide, it can use suitably.

  Particularly preferably, a liquid crystal display device, a plasma display device, an EL display device having an inorganic EL, a black edge provided at the periphery of a display device such as a CRT display device, or between red, blue and green colored pixels. It is suitably used as a black matrix such as a grid-like or stripe-like black portion, and more preferably a dot-like or linear black pattern for shielding the TFT.

In the black resin composition of the present invention, it is important to use at least titanium nitride particles as a light shielding material. The titanium nitride contains titanium nitride as a main component, and usually titanium oxide TiO ₂ as a subcomponent. Contains low-order titanium oxide expressed by Ti _n O _2n-1 (1 ≦ n ≦ 20) and titanium oxynitride expressed by TiN _x O _y (0 <x <2.0, 0.1 <y <2.0) To do. Regarding the ultraviolet transmittance when the optical density (OD value) of the coating film formed using the black resin composition of the present invention is 3, the ratio of the light transmittance at 365 nm to the light transmittance at 550 nm is 0.00. It is preferably 3 or more, more preferably 1.0 or more. When the ratio of the light transmittance at 365 nm to the light transmittance at 550 nm is smaller than 0.3, the adhesion after development is poor when a coating film having a very high light shielding property with an OD value of 5 or more is formed. In addition, there is a problem that a high-definition resin black matrix cannot be formed and a problem that the shape of the resin black matrix is deteriorated. When carbon black is used as the light shielding material, the ratio of the light transmittance of 365 nm to the light transmittance of 550 nm of the coating film formed using the black resin composition is 0.01 or less. It can be said that it is important to use at least titanium nitride particles as a light shielding material. By using such a black resin composition, it is possible to form a high-definition and taper-shaped black matrix having a high OD value. Further, since the resin black matrix of the present invention has a high OD value per film thickness, the film thickness is 1.0 μm or less at a practical OD value (4.0). As a result, even when a resin black matrix is used, a color filter having no practical problem in flatness without a protective film can be obtained.

  In order to make the effect of the present invention remarkable, the diffraction angle 2θ of the peak derived from the (200) plane when the CuKα ray of the titanium nitride used in the present invention is an X-ray source is 42.5 °. It is preferably 42.8 ° or less and more preferably 42.5 ° or more and 42.7 ° or less. By using titanium nitride particles having a diffraction angle θ in this range as a light shielding material, it becomes possible to achieve a high OD value while keeping the concentration of the light shielding material in the black resin composition low. Since it has a transmittance, it is possible to easily form a resin black matrix having a high definition and a good taper shape.

The X-ray diffraction spectrum of the titanium compound shows that when CuKα ray is used as the X-ray source, TiN has a peak derived from the (200) plane as the strongest peak, and 2θ = 42.5 ° in the vicinity of TiO and (200) plane of TiO The peak derived from is seen in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO ₂ is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO ₂ is 2θ = 39. Observed around 2 °. Therefore, a titanium compound having a crystal structure having nitrogen atoms and oxygen atoms has the strongest peak in the diffraction angle 2θ range of 42.5 ° to 43.4 °, and is in a crystalline state containing a large amount of oxygen atoms. The more the peak position is shifted to the higher angle side with respect to 42.5 °. In titanium oxynitride obtained by nitriding titanium oxide and insufficiently reduced by nitriding, the strongest peak is confirmed at a diffraction angle 2θ of 42.9 ° to 43.2 ° (Japanese Patent Laid-Open No. 2006-209102). Thus, it can be seen that the crystal structure is different from the titanium nitride of the present invention. When titanium oxide TiO ₂ is contained as an accessory component, the peak derived from anatase TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3 ° and derived from rutile TiO ₂ (110). A peak is observed in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.

  The crystallite size constituting the titanium nitride particles can be determined from the half width of the X-ray diffraction peak, and is calculated using the Scherrer equation shown in the following equations (1) and (2).

Here, K = 0.9, λ (0.15418 nm), β _e : half width of diffraction peak, β _o : correction value of half width (0.12 °). Where β, β _e and β _o are calculated in radians.

  The crystallite size is preferably 20 nm or more, and more preferably 20 nm or more and 50 nm or less. By forming a black matrix using titanium nitride particles having a crystallite size of 20 nm or more, the transmitted light of the coating film exhibits a blue to violet color having a peak wavelength of 475 nm or less, and has high light shielding properties and ultraviolet rays. A black matrix having both sensitivity can be obtained.

  A gas phase reaction method is generally used to synthesize titanium nitride, and examples include an electric furnace method and a thermal plasma method. The thermal plasma method has few impurities, has a uniform particle size, and has high productivity. The synthesis by is preferred. Examples of the method for generating thermal plasma include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma in which impurities from the electrode are less mixed is more preferable. Specific methods for producing titanium nitride fine particles by the thermal plasma method include a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 22221/1990), or evaporating titanium powder by high-frequency thermal plasma. A method of introducing nitrogen as a carrier gas and nitriding and synthesizing it in the cooling process (Japanese Patent Laid-Open No. 61-11140), a method of blowing ammonia gas into the peripheral edge of plasma (Japanese Patent Laid-Open No. 63-85007), and the like. However, the present invention is not limited to these, and the production method is not limited as long as titanium nitride particles having desired physical properties can be obtained. Various titanium nitride particles are commercially available, and a plurality of particles satisfying the diffraction angle and the oxygen atom amount defined in the present invention, and further satisfying the preferred crystallite size and specific surface area described above are also commercially available. ing. In the present invention, those commercially available products can be preferably used.

  In the present invention, in order to adjust the chromaticity of the black film, it is possible to change a part of the titanium nitride to another pigment within a range where the OD value does not decrease, but in order to obtain good pattern processability The titanium nitride particles are preferably contained in an amount of 10% by weight or more, more preferably 30% by weight or more based on the total amount of the light shielding material. As pigments other than titanium nitride, black organic pigments, mixed color organic pigments, inorganic pigments, and the like can be used. As the black organic pigment, carbon black, resin-coated carbon black, perylene black, aniline black, etc., and as the mixed color organic pigment, at least two kinds selected from red, blue, green, purple, yellow, magenta, cyan, etc. Inorganic pigments that have been pseudo-blackened by mixing pigments include graphite and fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, metal oxides, and composites. Examples thereof include oxides, metal sulfides, and metal nitrides. These may be used alone or in combination of two or more. In particular, if carbon black is used, the decrease in the OD value of the black coating can be minimized, and the resistance value, chromaticity, etc. of the black coating can be adjusted. That is, titanium nitride particles are high resistance, whereas carbon black has low resistance, so the resistance value of the black coating can be controlled by the mixing ratio of both. Moreover, if the surface-treated carbon black is used, the width of resistance value control of the black coating is further expanded. On the other hand, with regard to chromaticity, although depending on the crystallite size of the titanium nitride particles used, the transmitted color is generally blue, whereas the transmitted color of carbon black is red. Black without neutrality (neutral black) is obtained. When carbon black is used, its content can be appropriately selected and is not particularly limited, but is usually about 5 to 75% by weight with respect to the weight of the titanium nitride particles.

  In the present invention, an alkali-soluble resin is an essential component, but it is particularly limited as long as it acts as a binder with respect to the pigment and is soluble in an alkali developer in the development process when producing a color filter. Is not to be done. Among these, an alkali-soluble resin having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, or acid anhydrides thereof, phthalic acid mono (2 -(Meth) acryloyloxyethyl) and other polycarboxylic acid monoesters. In particular, an acrylic polymer containing a structural unit derived from (meth) acrylic acid is preferable, and a carboxylic acid contained in the structural unit is reacted with a compound containing an ethylenically unsaturated group and an epoxy group. When the obtained acrylic polymer is used, the sensitivity during exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable.

  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, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene, α-methylstyrene, (crosslinked) cyclic hydrocarbon groups such as tricyclodecanyl (meth) acrylate, and unsaturated carboxylic acids such as aminoethyl acrylate Acid aminoalkyl esters, unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, 1 Aliphatic conjugated dienes such as 1,3-butadiene and isoprene, polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate having acryloyl group or methacryloyl group at each end. Rate, and poly butyl methacrylate, but is not limited thereto. In particular, an acrylic polymer comprising (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable from the viewpoints of dispersion stability and pattern processability.

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

  In addition to the acrylic polymer obtained by reacting (meth) acrylic acid contained in the structural unit described above with a compound containing an ethylenically unsaturated group and an epoxy group, the side chain is ethylenic. An acrylic polymer having an unsaturated group can be preferably used. Specific examples include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a photocurable resin “Cyclomer (registered trademark) P” (Daicel), which is a commercially available acrylic polymer. Chemical Industry Co., Ltd.), alkali-soluble cardo resin and the like.

  The average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 40,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve). Further, a polymer having an average molecular weight of 8,000 to 30,000 and an acid value of 70 to 150 (mg KOH / g) is from the viewpoints of photosensitive properties, solubility in an ester solvent, solubility in an alkali developer, and residue control. Most preferred.

  As the monomer, a polyfunctional or 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 (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, Japanese Patent No. 3621533 and Japanese Patent Application Laid-Open No. 8-278630 Or full propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol Nord A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (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, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- ( 3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl Ether, 4,4′-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9 -Bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bis Examples thereof include phenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate, and biscresol full orange methacrylate. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having a functional group of 3 or more, more preferably 5 or more. preferable. In addition, an unsaturated group-containing alkali-soluble monomer obtained by reacting a polybasic carboxylic acid or its acid anhydride with a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid is also developable and processed. It is preferably used from the viewpoint of sex. Further, the combined use of (meth) acrylate having a fluorene ring having a large amount of aromatic rings and high water repellency in the molecule is preferable because the pattern can be controlled to a desired shape during development.

  In order to make the effect of the present invention remarkable, the photopolymerization initiator preferably contains at least (a) an alkylphenone series. In addition, in accordance with the wavelength at which the black resin composition of the present invention is exposed and exposed, particularly when there is no light emission of 340 nm or less, at least two components of (a) alkylphenone-based and (b) oxime ester-based are included. The content of (b) the oxime ester photopolymerization initiator at that time is preferably 30% by weight or less based on the total amount of the photopolymerization initiator.

  Examples of the alkylphenone-based photopolymerization initiator include α-aminoalkylphenone and α-hydroxyalkylphenone, and α-aminoalkylphenone is particularly preferable from the viewpoint of high sensitivity. For example, 2,2-diethoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, Ciba Specialty Chemicals Inc. “Irgacure (registered trademark)” 369 A 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemicals Co., Ltd. “Irgacure®” 379 2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Can be given.

  As specific examples of the oxime ester-based photopolymerization initiator, 1,2-octanedione, 1- [4- (phenylthio) -2- (O, which is Ciba Specialty Chemical Co., Ltd. “Irgacure (registered trademark)” OXE01 -Benzoyloxime)], an etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], Ciba Specialty Chemicals Co., Ltd. "Irgacure (registered trademark)" OXE02 -, 1- (0-acetyloxime), “Adeka (registered trademark) optomer” N-1818, N-1919 and the like manufactured by Asahi Denka Kogyo Co., Ltd.

  By selecting these photopolymerization initiators, a black matrix having a good pattern shape and tapered shape can be obtained even in a high OD region. In particular, even when an exposure machine with the j-line cut is used, an alkylphenone photopolymerization initiator is an essential component, and the oxime ester photopolymerization initiator is 30% by weight or less of the total photopolymerization initiator amount. By using in combination, a pattern with high sensitivity and excellent taper shape can be obtained. If the content of the oxime ester system exceeds 30% by weight, the pattern shape deteriorates, and the taper shape becomes a problem because it approaches the vertical.

  In addition to these photopolymerization initiators, inorganic compounds such as benzophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, triazine compounds, phosphorus compounds or titanates A known photopolymerization initiator such as a photopolymerization initiator can also be used in combination. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone Thioxanthone, 2-chlorothioxanthone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-Fe Nantraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-me Mercaptobenzothiazole, 2-mercaptobenzoxazole, 4-(p-methoxyphenyl) -2,6-- such as (trichloromethyl) -s-triazine and the like.

  In the black composition of the present invention, the weight composition ratio of the light shielding material / resin component is preferably in the range of 80/20 to 40/60 in order to obtain a black film having a high OD value. Moreover, it is more preferable that the weight composition ratio of the light shielding material / resin component is in the range of 75/25 to 60/40 in terms of the balance of adhesion, pattern workability, and OD value. Here, the resin component is the total of the polymer, monomer or oligomer and the polymer dispersant. If the amount of the resin component is too small, the adhesion of the black coating to the substrate becomes poor. Conversely, if the amount of the light shielding material is too small, the optical density per unit thickness (OD value / μm) is lowered, causing a problem.

  The solvent used in the black resin composition of the present invention is not particularly limited, and water and an organic solvent can be used in accordance with the dispersion stability of the pigment to be dispersed and the solubility of the resin to be added. The organic solvent is not particularly limited, and esters, aliphatic alcohols, ketones and the like can be used.

  Specific esters include benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), γ-butyrolactone (boiling point 204 ° C.), methyl benzoate (boiling point 200 ° C.), diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate ( Boiling point 181 ° C.), cyclohexyl acetate (bp 174 ° C.), 3-methoxy-butyl acetate (bp 173 ° C.), methyl acetoacetate (bp 172 ° C.), ethyl-3-ethoxypropionate (boiling point 170 ° C.), 2- Ethyl butyl acetate (boiling point 162 ° C), isopentyl propio (Boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C) ) And the like, but is not limited thereto.

  Among these solvents, acetate-type or propionate-type solvents include 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl. Particularly preferred are acetate and propylene glycol monomethyl ether acetate.

  In addition to the above solvents, propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.) Aliphatic ethers such as propylene glycol derivatives such as, aliphatic esters other than those described above, for example, ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.), or butanol ( Boiling point 118 ° C.), aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone and cyclohexanone, xylene ( Boiling point 14 ° C.), ethylbenzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: it is also possible to use a solvent such as boiling point 165 to 178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with the increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, and the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable.

  A silane coupling agent can be included as an adhesion improver used in the black resin composition of the present invention. Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane and the like are preferable because of easy availability of raw materials. Since the above-mentioned compound used in the present invention has an effect of improving adhesion in a small amount, it is not necessary to add a large amount, preferably 0.2 to 20% by mass, more preferably 0, based on the total solid content of the color resist. 0.5 to 5% by mass.

  In the black resin composition of the present invention, it is preferable to add a pigment dispersant in order to disperse the light shielding material uniformly and stably in the resin solution. Examples of pigment dispersants include polyester polymer pigment dispersants, acrylic polymer pigment dispersants, polyurethane polymer pigment dispersants, polyallylamine polymer dispersants, pigment derivatives, cationic surfactants, and nonionic interfaces. Examples thereof include an activator, an anionic surfactant, and a carbodiimide pigment dispersant. These pigment dispersants are appropriately selected and used according to the type of pigment. These pigment dispersants may be used alone or in combination of two or more. Since these polymer dispersants do not have photosensitivity, there is a concern that the photosensitivity of the target color resist may be deteriorated if added in a large amount. Therefore, an appropriate addition amount considering dispersion stability and photosensitivity is required. Is desirable. Addition of 1 to 50 (mass%), more preferably 3 to 30 (mass%) with respect to the pigment is more preferable because it has the effect of highly stabilizing dispersion without deteriorating the photosensitive performance.

  In addition, a surfactant can be added to the black resin composition of the present invention for the purpose of preventing coating properties, smoothness of the colored coating, and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  In the black resin composition of the present invention, the solid content concentration of the resin component (including additives such as monomers, oligomers and photopolymerization initiators) and the light shielding material is 2% or more from the viewpoint of coating properties and drying properties. It is preferably 30% or less, and more preferably 5% or more and 20% or less. Therefore, the black composition of the present invention preferably consists essentially of a solvent, a resin component and a light shielding material, and the total amount of the resin component and the light shielding material is preferably 2% or more and 30% or less, more preferably 5% or more and 20% or less, and the balance is the solvent. As described above, a surfactant may be further contained at the concentration described above.

  In the black resin composition in the present invention, a method of dispersing a pigment directly in a resin solution using a disperser, or a pigment dispersion is prepared by dispersing a pigment in water or an organic solvent using a disperser, Thereafter, it is manufactured by a method of mixing with a resin solution. The method for 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 preferred from the viewpoint of dispersion efficiency and fine dispersion. As the bead mill, a coball mill, a basket mill, a pin mill, a dyno mill, or the like can be used. As the beads of the bead mill, titania beads, zirconia beads, zircon beads and the like are preferably used. The bead diameter used for dispersion is preferably 0.01 mm to 5.0 mm, more preferably 0.03 mm to 1.0 mm. When the primary particle diameter of the pigment and the secondary particles formed by agglomeration of the primary particles are small, it is preferable to use fine dispersed beads of 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to disperse using a bead mill having a centrifugal separator capable of separating fine dispersion beads and dispersion. On the other hand, when dispersing a pigment containing coarse particles of about submicron, it is preferable to use dispersed beads of 0.10 mm or more because sufficient pulverization force can be obtained and the pigment can be finely dispersed.

  The example of the manufacturing method of the color filter by the die coating apparatus using the black resin composition of this invention is demonstrated. As the substrate, a transparent substrate such as soda glass, non-alkali glass, or quartz glass is usually used, but is not particularly limited thereto. Examples of the die coating apparatus include a single wafer coating apparatus disclosed in Japanese Patent No. 3139358 and Japanese Patent No. 3139359. By this apparatus, the black resin composition (coating liquid) of the present invention is discharged from the die and the substrate is moved, whereby the black resin composition can be applied on the substrate. In this case, since a large number of substrates are applied in a single sheet, when the apparatus is operated for a long time, agglomerates of pigments are formed in the base part for discharging the coating liquid from the slits, which may cause a coating defect and reduce the yield. In this case, by providing a step of wiping the base, which is a discharge port of the apparatus, with a solvent containing 40% by mass or more of the ester solvent having a boiling point of 150 ° C. or higher with respect to the total solvent, the coating defects are eliminated and the base is removed. The rate is improved. After applying a black resin composition on a board | substrate by the above, a solvent is removed by air drying, reduced pressure drying, heat drying, etc., and the coating film of a black resin composition is formed. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of room temperature to 100 ° C., 5 seconds to 10 minutes, and a degree of vacuum of 500 to 10 (Pa), more preferably a degree of vacuum of 150 to 50 (Pa). Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes.

  Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. It is preferable to use an alkaline developer added with 0.1 to 5% of a surfactant such as a nonionic surfactant because a better pattern can be obtained. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine.

  The concentration of the alkaline substance is 0.01% by mass to 50% by mass. Preferably it is 0.02 mass% to 10 mass%, More preferably, it is 0.02 to 1 mass%. In the case where the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the developer.

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

  The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After development, a washing process with pure water or the like is added.

  The coating film pattern of the obtained black resin composition is then patterned by heat treatment (post-baking). The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

  Thus, the optical density (optical density, OD value) of the resin black matrix obtained from the black resin composition of the present invention is 4.0 or more per 1.0 μm film thickness in the visible light range of 380 to 700 nm. Preferably, it is 4.5 or more, more preferably 5.0 or more. The OD value can be obtained from the following relational expression (3) by measuring using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics).

OD value = log ₁₀ (I ₀ / I) (3)
Here, I _{0 is} incident light intensity, and I is transmitted light intensity.

  In the present invention, a color filter for liquid crystal display can be manufactured using the above-described resin black matrix. That is, the present invention also provides a color filter comprising the resin black matrix of the present invention. The color filter includes at least a transparent substrate, a resin black matrix formed on a partial region of the transparent substrate, and a pixel formed on a region of the transparent substrate where the resin black matrix is not formed. The resin black matrix is the resin black matrix of the present invention.

  When the resin black matrix of the present invention is used for a color filter for liquid crystal display, as a normal manufacturing process, for example, as shown in Japanese Patent Publication No. 2-1311, a black matrix is first formed on a transparent substrate and then red ( Pixels having color selectivity of R), green (G), and blue (B) are formed, and an overcoat film is formed thereon as necessary. Specific materials of the pixel include an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, and a colored resin film in which dyeing, dye dispersion, or pigment dispersion is performed. Further, the pixel formation order can be arbitrarily changed as necessary. Further, if necessary, a transparent conductive film can be formed after forming the three primary color layers or after forming the overcoat film on the three primary color layers. An oxide thin film such as ITO is employed as the transparent conductive film, and an ITO film of about 0.1 μm is usually formed by sputtering or vacuum deposition.

  The pigment used for the pixel of the color filter of the present invention is not particularly limited, but a pigment excellent in light resistance, heat resistance and chemical resistance is desirable. When specific examples of typical pigments are indicated by color index (CI) numbers, the following are preferably used, but they are not limited to these.

  Examples of the red pigment include pigment red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR190, PR192, PR209, PR215, PR216, PR217. PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, etc. are used.

  Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, and PO71.

Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY14, PY17, PY20, PY24, PY83, PY86, PY93, PY94, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138. , PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY173, PY180, PY185, and the like are used.
Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV36, PV37, PV38, PV40, and PV50.

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

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

These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment, etc., if necessary, and a pigment derivative may be added as a dispersant.
Although there is no restriction | limiting in particular in the matrix resin used for the pixel of the color filter of this invention, Acrylic resin, polyvinyl alcohol, polyamide, a polyimide, etc. can be used. It is preferable to use a pigment-dispersed resin film as a pixel from the viewpoint of simplicity of the manufacturing process, heat resistance, and light resistance. From the viewpoint of ease of pattern formation, it is preferable to use a photosensitive acrylic resin in which a pigment is dispersed. However, it is preferable to use a pigment-dispersed polyimide film from the viewpoint of heat resistance and chemical resistance.

  In the substrate color filter for a liquid crystal display device of the present invention, a black matrix is arranged between pixels. A black matrix is also arranged in the frame portion of the pixel. The arrangement of the black matrix can improve the contrast of the liquid crystal display device and can prevent malfunction of the drive element of the liquid crystal display device due to light.

  A spacer fixed on the color filter for a liquid crystal display device of the present invention may be formed. The fixed spacer is fixed to a specific location of a substrate for a liquid crystal display device as disclosed in JP-A-4-318816, and is in contact with a counter substrate when the liquid crystal display device is manufactured. As a result, a constant gap is maintained between the counter substrate and liquid crystal is injected between the gaps. By arranging the fixed spacer, it is possible to omit the step of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the step of kneading the rod-shaped spacer in the sealing agent.

  The fixed spacer is formed by a method such as photolithography, printing, or electrodeposition. Since the spacer can be easily formed at the designed position, it is preferable to form the spacer by photolithography. The spacer may be formed in a laminated structure at the same time as the R, G, and B pixels are manufactured, or may be formed after the R, G, and B pixels are manufactured.

  In the present invention, since the resin black matrix can be formed into a thin film as described above, the color pixel height mounted on the black matrix is reduced, and a color with high flatness can be obtained without forming an overcoat film. A filter can be produced. However, when higher flatness is required, or when flattening holes and steps processed in color pixels, and for the purpose of preventing elution of components contained in color pixels into the liquid crystal layer, an overcoat film is used. It is preferable to form. Examples of the material for the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film. The overcoat film may be formed after the resin black matrix is formed, after the pixel is formed, or after the fixed spacer is arranged. The thickness of the overcoat after heat-curing, when applied on an uneven substrate, is thicker at the concave portion (lower portion than the surroundings) and thinner at the convex portion (higher than the surrounding portion) due to the leveling property of the overcoat agent. Tend to be. Although there is no restriction | limiting in particular in the thickness of the overcoat in this invention, 0.01-5 micrometers, Preferably it is 0.03-4 micrometers, More preferably, it is 0.04-3 micrometers.

  The present invention further provides a liquid crystal display device comprising the color filter of the present invention. The liquid crystal display device of the present invention includes the color filter of the present invention, an electrode substrate disposed to face the color filter, a liquid crystal alignment film provided on the color filter and the electrode substrate, and A spacer for ensuring a space between the liquid crystal alignment films and a liquid crystal filled in the space are provided.

  An example of the liquid crystal display device prepared using a color filter will be described. The color filter and the electrode substrate are bonded to each other through a liquid crystal alignment film that has been subjected to a rubbing treatment for liquid crystal alignment provided on the substrate and a spacer for maintaining a cell gap. Note that a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, or the like can be provided over the electrode substrate, whereby a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Next, a liquid crystal display device is completed by mounting an IC driver or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example.

<Evaluation method>
"X-ray diffraction"
X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.

  The diffraction angle of the peak derived from the (200) plane observed near the diffraction angle 2θ = 46 ° was measured. Further, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using the Scherrer equation of the above-described equations (1) and (2).

"Composition analysis"
The content of titanium atoms was measured by ICP emission spectroscopic analysis (ICP emission spectroscopic analyzer SPS3000 manufactured by Seiko Instruments Inc.).

  The content of oxygen atoms and nitrogen atoms was measured using (Horiba oxygen / nitrogen analyzer EMGA-620W / C), and the oxygen atoms were converted into inert gas by infrared gas absorption-infrared absorption method. The nitrogen atom was determined by the method.

[OD value]
A resin black matrix having a film thickness of 1.0 μm was formed on an alkali-free glass and obtained from the above formula (3) using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

[Light transmittance]
A resin black matrix was formed on an alkali-free glass, and measurement was performed using an ultraviolet / visible / near infrared spectrophotometer (Shimadzu spectrophotometer UV-2500PC). (Measurement conditions are measurement wavelength region; 300 to 780 nm, sampling pitch: 1.0 nm, scan speed; low speed, slit width; 2.0 nm.)
[Adhesion]
Using a resolution test mask, development is performed 1.7 times as long as the unexposed portion dissolves, and the 8 micron resist pattern on the substrate does not peel off, while the 8 micron resist pattern peels off. The micron resist pattern was not peeled and Δ was the 10 micron resist pattern peeled.

[sensitivity]
The minimum required exposure amount necessary to form a pattern having no surface roughness even when developed is shown. Through a photomask (manufactured by HOYA Co., Ltd., negative mask, stripe design line width 50 μm, 100 μm gap), ultraviolet rays containing wavelengths of i-line: 365 nm, h-line: 405 nm and g-line 436 nm were applied to the coating film at 200 mJ / Exposure was carried out by reducing the exposure amount as needed, with the maximum exposure amount being cm ^2, and the minimum required exposure amount in a range where the pattern surface was not roughened after development was defined as sensitivity.

[Pattern shape]
The pattern shape was observed using Olympus BH3-C1410. Those with linearity were marked with ◯, and those with meandering or chipping at the end of the shape were marked with Δ or x depending on the degree.

[Taper shape]
The taper shape was observed with a field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). A taper angle of 60 ° or less was evaluated as “◯”, and a taper angle of 60-80 ° was evaluated as “Δ”.

Synthesis of acrylic polymer (P-1) After synthesizing a methacrylic acid / benzyl methacrylate / cyclodecanyl methacrylate copolymer (weight composition ratio 40/30/30), 25 parts by weight of glycidyl methacrylate was added and reprecipitated with purified water. By filtration and drying, an acrylic polymer (P-1) powder having properties of an average molecular weight (Mw) of 49000 and an acid value of 110 (mgKOH / g) was obtained.

Synthesis of acrylic polymer (P-2) An acrylic polymer (P-2) powder having the characteristics of an average molecular weight (Mw) of 36500 and an acid value of 104 (mgKOH / g) in the same manner as the acrylic polymer (P-1) Obtained.

Synthesis of acrylic polymer (P-3) An acrylic polymer (P-3) powder having the characteristics of an average molecular weight (Mw) of 12000 and an acid value of 100 (mgKOH / g) in the same manner as the acrylic polymer (P-1). Obtained.

Synthesis of acrylic polymer (P-4) An acrylic polymer (P-4) powder having the characteristics of an average molecular weight (Mw) of 7700 and an acid value of 110 (mgKOH / g) was obtained in the same manner as the acrylic polymer (P-1). Obtained.

Synthesis of Acrylic Polymer (P-5) An acrylic polymer (P-5) powder having the characteristics of an average molecular weight (Mw) of 3000 and an acid value of 102 (mgKOH / g) is obtained in the same manner as the acrylic polymer (P-1). Obtained.

Example 1
The diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride particles (sample 1, manufactured by Nissin Engineering Co., Ltd., TiN UFP Lot 13406810) manufactured by the thermal plasma method is 42.61 °, the half-value width of this peak The crystallite size obtained was 25.6 nm. Further, X-ray diffraction peaks attributed to TiO ₂ were slightly observed at 25.23 ° and 27.50 °.

  Sample 1 (200 g), propylene glycol monomethyl ether acetate 45 wt% solution (115 g) of acrylic polymer (P-3), Big Chemie Japan BYK 2001 as polymer dispersant, 20 wt% solution (43.3 g) and propylene glycol monomethyl Ether acetate (659 g) was charged into a tank, and stirred for 1 hour with a homomixer (made by Tokushu Kika) to obtain a preliminary dispersion 1. Thereafter, the preliminary dispersion 1 was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 70% 0.05 mmφ zirconia beads (manufactured by Nikkato, YTZ ball), and rotated for 2 hours at a rotational speed of 8 m / s. Dispersion was performed to obtain Pigment Dispersion Liquid 1 having a solid content concentration of 25% by weight and a pigment / resin (weight ratio) = 80/20.

  This pigment dispersion 1 (654.6 g) was mixed with 50% by weight of a propylene glycol monomethyl ether acetate solution (33.9 g) of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, a photopolymerization initiator. Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG (13.0 g), Shin-Etsu Chemical Co., Ltd. KBM503 (6.0 g), silicone surfactant, propylene glycol monomethyl A solution obtained by dissolving a 10 wt% ether acetate solution (3.2 g) in propylene glycol monomethyl ether acetate (196.2 g) was added, and the total solid concentration was 20 wt%. Pigment / resin (weight ratio) = 70/30 The black resin composition 1 was obtained.

This black resin composition 1 was coated on a non-alkali glass AN100 substrate with a spinner 1H-DS manufactured by Mikasa Co., Ltd. and prebaked at 100 ° C. for 10 minutes to prepare a coating film. By using a mask aligner PEM-6M manufactured by Union Optical Co., Ltd., exposure (200 mJ / cm ² ) through a photomask, development using a 0.045 mass% KOH aqueous solution, and subsequent pure water cleaning, A patterned substrate was obtained. Furthermore, it was cured at 230 ° C. for 30 minutes. Thus, a black matrix 1 having a thickness of 1.00 μm was prepared so that the OD value was 5.0.

Example 2
The diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride particles (sample 2, manufactured by Nissin Engineering Co., Ltd., TiN UFP Lot 13307215) produced by the thermal plasma method is 42.62 °, the half-value width of this peak The crystallite size obtained was 29.4 nm. Further, no X-ray diffraction peak attributed to TiO ₂ was observed.

  A pigment dispersion 2 and a black resin composition 2 were obtained in the same manner as in Example 1 except that the sample 2 was used instead of the sample 1 as the pigment to be used.

  Further, a black matrix 2 having a thickness of 0.85 μm was prepared using the black resin composition 2 so as to have an OD value of 5.0 in the same manner as in Example 1.

Example 3
The diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride particles (sample 3, Nisshin Engineering Co., Ltd., TiN UFP Lot 13307218) produced by the thermal plasma method is 42.60 °, the half-value width of this peak The crystallite size obtained was 38.3 nm. Further, no X-ray diffraction peak attributed to TiO ₂ was observed.

  A pigment dispersion 3 and a black resin composition 3 were obtained in the same manner as in Example 1 except that the sample 3 was used instead of the sample 1 as a pigment to be used.

  Further, a black matrix 3 having a thickness of 0.90 μm was prepared using the black resin composition 3 so that the OD value was 5.0 in the same manner as in Example 1.

Example 4
The peak diffraction angle 2θ derived from the (200) plane of a commercially available titanium nitride reagent (Sample 4, manufactured by Wako Pure Chemical Industries, Ltd., titanium nitride 50 nm) is 42.57 °, and the crystal obtained from the half width of this peak The child size was 44.6 nm. Further, no X-ray diffraction peak attributed to TiO ₂ was observed.

  A pigment dispersion 4 and a black resin composition 4 were obtained in the same manner as in Example 1 except that the sample 4 was used instead of the sample 1 as the pigment to be used.

  Further, a black matrix 4 having a thickness of 0.95 μm was prepared using the black resin composition 4 so that the OD value was 5.0 in the same manner as in Example 1.

Example 5
In pigment dispersion 2 (560.1 g), a propylene glycol monomethyl ether acetate solution (27.6 g) of (P-3) as an acrylic polymer (27.6 g) as an acrylic polymer, and propylene glycol monomethyl ether acetate 50 of dipentaerythritol hexaacrylate as a polyfunctional monomer Weight% solution (38.3 g), Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG (10.45 g) as a photopolymerization initiator, Shinetsu Chemical Co., Ltd. KBM503 (4 7 g), a 10% by weight solution of propylene glycol monomethyl ether acetate (2.5 g) of a silicone surfactant dissolved in propylene glycol monomethyl ether acetate (105.0 g) was added, and the total solid content concentration was 20 wt. %, Charge / resin to obtain a black resin composition 5 (weight ratio) = 60/40.

  Further, a black matrix 5 having a thickness of 1.10 μm was prepared using the black resin composition 5 so that the OD value was 5.0 in the same manner as in Example 1.

Example 6
As a photopolymerization initiator, 11.3 g of 379EG and 1.7 g of “Adeka (registered trademark) Optomer” N-1919 were mixed instead of Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG. A black resin composition 6 was obtained in the same manner as in Example 2 except that was used.

  Further, a black matrix 6 having a thickness of 0.85 μm was prepared using the black resin composition 6 so that the OD value was 5.0 as in Example 2.

Example 7
As a photopolymerization initiator, instead of Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG, 379 EG mixed with 9.5 g and “Adeka (registered trademark) Optomer” N-1919 mixed with 3.5 g A black resin composition 7 was obtained in the same manner as in Example 2 except that was used.

  Further, a black matrix 7 having a thickness of 0.85 μm was prepared using the black resin composition 7 so that the OD value was 5.0 in the same manner as in Example 2.

Example 8
As a photopolymerization initiator, instead of Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG, 379 EG was mixed with 7.8 g and “Adeka (registered trademark) Optomer” N-1919 mixed with 5.2 g. A black resin composition 8 was obtained in the same manner as in Example 2 except that was used.

  Further, a black matrix 8 having a thickness of 0.85 μm was prepared using the black resin composition 8 so that the OD value was 5.0 in the same manner as in Example 2.

Example 9
As a photopolymerization initiator, instead of using Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 379EG, a mixture of 5.2 g of “Adeka (registered trademark) Optmer” N-1919 was used. A black resin composition 9 was obtained in the same manner as in Example 2.

  In addition, a black matrix 9 having a thickness of 0.85 μm was prepared using the black resin composition 9 so that the OD value was 5.0 as in Example 2.

Example 10
A black resin composition 10 was obtained in the same manner as in Example 2 except that (P-2) was used instead of (P-3) as the acrylic polymer.

  Moreover, the black matrix 10 of thickness 0.85 micrometer was created so that OD value might be set to 5.0 similarly to Example 2 using the black resin composition 10. FIG.

Example 11
A black resin composition 11 was obtained in the same manner as in Example 2 except that (P-4) was used instead of (P-3) as the acrylic polymer.

  Further, a black matrix 11 having a thickness of 0.85 μm was prepared using the black resin composition 11 so that the OD value was 5.0 as in Example 1.

Comparative Example 1
The diffraction angle 2θ of the peak derived from the (200) plane of titanium compound particles (sample 5, manufactured by Nissin Engineering Co., Ltd., TiN UFP Lot 13306B10) produced by the thermal plasma method is 42.68 °, from the half-value width of this peak The obtained crystallite size was 14.3 nm. X-ray diffraction peaks attributed to TiO ₂ were slightly seen at 25.31 ° and 27.52 °.

  A pigment dispersion 5 and a black resin composition 12 were obtained in the same manner as in Example 1 except that the sample 5 was used instead of the sample 1 as the pigment to be used.

  Further, a black matrix 12 having a thickness of 1.20 μm was prepared using the black resin composition 12 so that the OD value was 5.0 in the same manner as in Example 1.

Comparative Example 2
The diffraction angle 2θ of the peak derived from the (200) plane of the commercially available titanium black pigment “13-MC” (sample 6, manufactured by Mitsubishi Materials Corporation) is 42.91 °, and the crystallite obtained from the half width of this peak The size was 29.6 nm. In addition, X-ray diffraction peaks attributed to TiO ₂ were observed at 25.28 ° and 27.44 °.

  A pigment dispersion 6 and a black resin composition 13 were obtained in the same manner as in Example 1 except that the sample 6 was used instead of the sample 1 as the pigment to be used.

  Further, a black matrix 13 having a thickness of 1.20 μm was prepared using the black resin composition 13 so that the OD value was 5.0 in the same manner as in Example 1.

  The evaluation results are shown in Table 1. With titanium oxynitride, the OD value and sensitivity were lower than when titanium nitride particles had the same pigment / resin weight composition ratio.

Comparative Example 3
Carbon black (“9930CF” manufactured by Daido Kasei, 160 g), 80.0 g of 20% by weight solution of propylene glycol monomethyl ether acetate of “Ajisper (registered trademark)” PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, acrylic polymer Using a mill-type disperser in which 120.0 g of a 40 mass% propylene glycol monomethyl ether acetate solution of (P-3) and 640.0 g of propylene glycol monomethyl ether acetate were weighed and filled with 80% 0.40 mmφ zirconia beads. Then, dispersion was performed at a rotational speed of 8 m / s for 2 hours to obtain a pigment dispersion 7 having a solid content concentration of 22.4% by weight and a pigment / resin (weight ratio) = 71/29.

  This pigment dispersion 7 (639.1 g) was mixed with a 50 wt% solution of propylene glycol monomethyl ether acetate in bisphenoxyethanol fluorenediacrylate (40.9 g) and a 50 wt% solution of propylene glycol monomethyl ether acetate in dipentaerythritol hexaacrylate (13. 6 g), Adekaoptomer “N-1919 (23.2 g) as a photopolymerization initiator, KBM503 (12.0 g) as an adhesion improver, 10% by weight solution of propylene glycol monomethyl ether acetate in a silicone surfactant (4 0.0000 g) in propylene glycol monomethyl ether acetate (267.2 g) was added to obtain a black resin composition 14 having a total solid content concentration of 20 wt% and pigment / resin (weight ratio) = 60/40. The

  Further, a black matrix 14 having a thickness of 1.20 μm was prepared using the black resin composition 14 so that the OD value was 5.0 in the same manner as in Example 1.

Comparative Example 4
Except that (P-1) was used instead of (P-3) as the acrylic polymer, pigment dispersion was carried out in the same manner as in Example 2, but an increase in viscosity was observed and a stable dispersion was obtained. There wasn't.

Comparative Example 5
Except that (P-5) was used instead of (P-3) as the acrylic polymer, pigment dispersion was carried out in the same manner as in Example 2. It was not obtained.

Example 12
A black resin composition 15 was obtained in the same manner as in Example 1 except that instead of the pigment dispersion 1, a mixture of the pigment dispersion 2 and the pigment dispersion 6 was used at a weight ratio of 50/50.

  Further, using the black resin composition 15, a black matrix 15 having a thickness of 0.90 μm was prepared so that the OD value was 5.0 as in Example 1.

Example 13
A black resin composition 16 was obtained in the same manner as in Example 1 except that the pigment dispersion 2 and the pigment dispersion 6 were mixed in a weight ratio of 25/75 instead of the pigment dispersion 1.

  Further, using the black resin composition 16, a black matrix 16 having a thickness of 1.00 μm was prepared so that the OD value was 5.0 similarly to Example 1.

Reference example 1
A black matrix 17 having a thickness of 0.85 μm was prepared in the same manner as in Example 2 except that a J-ray cut filter (Asahi Techno Glass UV35) was inserted during exposure so that the OD value was 5.0.

Example 14
Except that a J-ray cut filter (Asahi Techno Glass UV35) was inserted at the time of exposure, a black matrix 18 having a thickness of 0.85 μm was prepared so that the OD value was 5.0.

Example 15
Except that a J-ray cut filter (Asahi Techno Glass UV35) was inserted at the time of exposure, a black matrix 19 having a thickness of 0.85 μm was prepared so that the OD value was 5.0.

Example 16
A black matrix 20 having a thickness of 0.85 μm was prepared so as to have an OD value of 5.0 in the same manner as in Example 8 except that a J-ray cut filter (UV35 manufactured by Asahi Techno Glass Co., Ltd.) was inserted during exposure.

Example 17
A black matrix 21 having a thickness of 0.85 μm was prepared in the same manner as in Example 9 except that a J-ray cut filter (UV35 manufactured by Asahi Techno Glass Co., Ltd.) was inserted during the exposure.

  The evaluation results are shown in Table 1. Since the resin composition shown in the Examples has high ultraviolet transmittance, it can be seen that the sensitivity and adhesion after development are good. On the other hand, even when titanium nitride particles are used as the light shielding material, the ratio of the light transmittance at 365 nm to the light transmittance at 550 nm is 0.5 when the optical density (OD value) is 3. In the black matrix having the following properties, the light transmittance in the ultraviolet region is low, so the sensitivity is low and the adhesion after development is poor.

  In addition, since the titanium nitride particles of the examples have a high ultraviolet light transmittance, the sensitivity becomes too high when the oxime ester photopolymerization initiator such as N1919 is used in a certain amount or more, the pattern shape is meandering, or the taper is tapered. It can be seen that workability has deteriorated, such as vertical cutting.

  Compared to the titanium nitride particle system having the same pigment / resin weight composition ratio, both the OD value and sensitivity of carbon were very low. In addition, despite the use of a highly sensitive oxime ester than in the case of titanium nitride particles, the sensitivity was insufficient and the adhesion and shape were poor.

  In addition to the light transmittance factor, the specific gravity is higher than that of carbon, so even with the same weight ratio, the resin coverage is higher than that of carbon. It is done.

  The photosensitive black resin composition of this invention can be utilized for the black matrix of the color filter substrate for liquid crystal display devices.

Claims (8)

A photosensitive black resin composition containing at least a light shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, wherein the black resin composition contains at least titanium nitride particles as the light shielding material. the light transmittance in the case the optical density (OD value) of 3 of the formed coating film by using a state, and are ratios of 365nm light transmittance of 0.3 or more with respect to the light transmittance of 550 nm, the titanium The diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays of the nitride particles are used as an X-ray source is 42.5 ° or more and 42.8 ° or less, and the peak derived from the (200) plane photosensitive black resin composition crystallite size determined from the half bandwidth is characterized der Rukoto than 50nm or less 20 nm. 2. The photosensitive black resin composition according to claim 1, wherein a ratio of titanium nitride particles in the total weight of the light shielding material is 10 wt% or more. Photosensitive black resin composition according to claim 1 or 2, wherein the titanium nitride particles are those prepared by thermal plasma method. The photosensitive black resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator contains at least (a) an alkylphenone compound. The photopolymerization initiator includes at least two components (a) an alkylphenone compound and (b) an oxime ester compound, and the content of (b) in the total weight of the photopolymerization initiator is 30 wt% or less. The photosensitive black resin composition according to claim 4 , wherein the photosensitive black resin composition is present. A resin black matrix substrate obtained by applying the black resin composition according to any one of claims 1 to 5 on a transparent substrate and forming a pattern, wherein the optical density (OD value) of the resin black matrix is a film thickness. Resin black matrix substrate having a value of 4.0 or more per 1 μm. 7. A color filter substrate, wherein red, green and blue pixels are formed in openings of the resin black matrix substrate according to claim 6 . A liquid crystal display device comprising the color filter substrate according to claim 7 .