Specification
DESCRIPTION
BLACK RESIN COMPOSITION, RESIN BLACK MATRIX, COLOR FILTER
AND LIQUID CRYSTAL DISPLAY
Technical Field
[0001]
The present invention relates to a black resin composition optimum for producing a black matrix constituting a display apparatus with a light source such as a cold-cathode tube and an LED, a resin black matrix using the black resin composition, a color filter for liquid crystal displays using the resin black matrix, as well as a liquid crystal display.
Background Art [0002]
Liquid crystal displays are apparatuses for displaying images and characters and for carrying out information processing by utilizing the electro-optical response of liquid crystal, and are widely employed for large display size uses such as personal computers, monitors, liquid display television sets and, in recent years, also for middle and small display size uses such as cellular phones, personal digital assistances, and car navigation systems. Such liquid crystal displays usually have a structure in which a liquid crystal layer is sandwiched between a pair of substrates, and can express light and dark utilizing the electro-optical response of liquid crystal layers caused by extemally-applied electric field. They are also able to display colors by using color filters comprising pixels having color selectivity. [0003]
Conventionally, metal thin films utilizing chromium-based materials have been used as a black matrix material. Recently, from the viewpoint of cost and environmental pollution, resin black matrices comprising resins and light shielding materials are used. The resin black matrix is obtained by coating the black resin
composition containing a light shielding agent such as the resin and carbon black on a substrate and drying to form a black coated film, followed by micro-patterning into lattices by photolithography. For instance, Patent Literature 1 describes the resin black matrix in which a carbon black is dispersed in a non-photosensitive polyimide resin. [0004]
Yet, along with recent demand for a thimier color filter and a higher performance, as well as along with higher luminance of a back light used in the liquid crystal displays, demand for a higher OD value is increasing and the OD value in the conventional resin black matrices was not sufficient. In cases where the resin black matrix is thick, problems arise in that flatness of the color filter is deteriorated lower and thus the alignment of the liquid crystal is disturbed due to increased surface steps generated by color pixels running over onto the resin black matrix, so that demand for a thinner resin black matrix is increasing. [0005]
Increasing the volume ratio of the light shielding agent allows the higher OD value and thinner film to be attained but, on the other hand, causes a decrease in the ratio of the resin in the black matrix. Problems arise in that the adhesion of the resin black matrix to glass decreases and the resin black matrix is peeled off and that sufficient resistance cannot be attained. Therefore, a light shielding material by which a higher OD can be attained even if the content is small is needed, [0006]
As the light shielding agent, carbon black, titanium black such as low oxidized titanium and titanium nitride oxide, metal oxides such as iron oxide, and mixtures of other organic pigments are used. The carbon black and titanium nitride oxide have become the mainstream, [0007]
In regard to the carbon black, various efforts have been made in order to obtain a coated fihn with a high OD vaLUe and Patent Literature 2 has been, for instance, disclosed. Patent Literature 2 describes that the resin black matrix with the OD value of 3.5 per a film thickness of 1.0 (4,m can be obtained by defining a primary particle diameter, DBP absorption, and pH of the carbon black, as well as the amine value and molecular weight of organic compounds which are concomitantly used. However, the OD value is not sufficient and the resistant value is as low as not more than 1x10^, so that that they cannot be used for applications in which an insulation performance is required. [0008]
Meanwhile, titanium nitride oxide obtained by partially nitriding oxygen in titanium dioxide or titanium hydroxide is used in a resin black matrix having high resistance. In order to obtain the high OD value, it is crucial not to include white titanium dioxide during nitriding, and various studies therefore have been made (Patent Literatures 3 and 4). In particular. Patent Literature 4 describes that a titanium nitride oxide with a higher nitriding degree and a smaller crystallite diameter could be obtained by optimizing a heating calcination temperature when titanium oxide undergoes nitriding-reduction. A resin black matrix with the OD value of 4.0 per a film thickness of 0.8 μm could be reportedly obtained by ufilizing the titanium nitride oxide. However, titanium nitride oxide contains a large amount of alkali metals such as Na, K, Mg, and Ca originated from a production method including nitriding reduction, which causes a decrease in adhesion between the resin black matrix and glass, and a decrease in the resistance (Patent Literature 5). Thus, there was a problem in that a procedure for removing the alkali metals such as K and Na, including ion exchange with an ion exchange resin and wash with pure water, was required and hence productivity decreased. [0009]
Meanwhile, another example of the black pigment is titanium nitride (Patent Literature 6). The technique utilizing titanium nitride compound particles with a diameter of not more than 200 nm in the use of solar isolation shielding has been disclosed (Patent Literature 7), The physical property was optimized with the aim of minimizing transmittance near the infrared region (800-2500 nm) and attaining high transmittance in the visible wavelength region. However, it was not satisfactory in view of minimum transmittance in the visible wavelength region, in other words, in view of the degree of blackness which is required as the black matrix. [0010]
In addition, to form a titanium nitride film and to use it as a black matrix is disclosed in Patent Literature 8. However, it was difficuh to form the film on a substrate because the film is not formed by coating a black composition. [0011]
Patent Literature 1: Japanese Patent No. 3196638 (pages 1 and 9-11, and Table 1) Patent Literature 2: Japanese Laid-open Patent Application (Kokai) No. 2004-292672 Patent Literature 3: Japanese Laid-open Patent Application (Kokai) No. 2005-514767 Patent Literature 4: Japanese Laid-open Patent Application (Kokai) No. 2006-209102 Patent Literature 5: Japanese Laid-open Patent Application (Kokai) No. 2004-4651 Patent Literature 6: Japanese Laid-open Patent Application (Kokai) No, 64-37408 Patent Literature 7: Japanese Laid-open Patent Application (Kokai) No. 2005-179121 Patent Literature 8: Japanese Laid-open Patent Application (Kokai) No. 10-104663
DISCLOSURE OF THE INVENTION Problems to be solved by the Invention [0012]
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a black resin composition capable of forming a black
matrix that has the high OD value and high adhesiveness as well as high resistance value. By using such a black resin composition, a resin black matrix which is thin and has a high OD value and which is highly adhesive can be obtained. As a result, a color filter having higher flatness without an over-coat can be provided. Additionally, by using such a color filter, a liquid crystal display with superior display performance can be attained.
Means for Solving the Problems [0013]
In order to solve the problems in the prior art, the present inventors intensively studied to discover that the above-described problems to be solved by the present invention may be solved by using a specific titanium nitride compound particles described below as a light shielding agent. [0014]
The object of the present invention is attained by the following constitutions:
(1) A black resin composition comprising at least a light shielding agent, a resin and a solvent, the light shielding agent containing at least titanium nitride compound particles, wherein the angle of diffraction 26 of the peak originated from (200) plane of the titanium nitride compound particles when CuKa line is used as the X-ray source is not less than 42.5° and not more than 42.8°.
(2) The black resin composition according to (1), wherein the angle of diffraction 20 originated from the (200) plane of the titanium nitride compound particles when CuKa line is used as the X-ray source is not less than 42.5° and less than 42.7°.
(3) The black resin composition according to (1) or (2), wherein the crystallite size determined from half bandwidth of the peak originated from the (200) plane when CuKa line is used as the X-ray source is not more than 50 nm.
(4) The black resin composition according to any one of (1) to (3), wherein the specific surface area of the titanium nitride compound particles determined by BET
method is not less than 5 m2/g and not more than 100m2/g.
(5) The black resin composition according to any one of (1) to (4), wherein the amount of oxygen atoms contained in the titanium nitride compound particles is not more than 12 % by weight.
(6) The black resin composition according to any one of (1) to (5), wherein the titanium nitride compound particles are prepared by thermal plasma method.
(7) A resin black matrix formed of a coated film of the black resin composition according to any one of (1) to (6), which resin black matrix has an optical density (OD value) of not less than 4.0 per 1.0 μm of film thickness.
(8) A color filter comprising the resin black matrix according to (7).
(9) A liquid costal display comprising the color filter according to (8)
Effects of the Invention [0015]
By using the black resin composition of the present invention, an effect that a thin resin black matrix is readily obtained, which resin black matrix has a high light shielding and a high resistant value, is obtained.
Brief description of the Drawings [0016]
Figure 1 shows the intensity spectra of the angle of diffraction 20 of titanium nitride compound particles according to the present invention and of a conventional titanium black.
Best Mode for Carrying Out the Invenfion [0017]
The present invention will be further described below in detail. [0018]
The black resin composition according to the present invention contains at least the light shielding agent, a resin and a solvent. The black resin composition
needs to contain titanium nitride compound particles having at least a specific property as the light shielding agent. Desired properties will now be described below. [0019]
The black resin composition according to the present invention can be used to produce printing ink, Inkjet ink, material for photomask production, material for proof printing production, etching resist, solder resist, bulkheads of plasma display panel (PDP), derivative pattern, electrode (conductor circuit) pattern, circuit pattern of electronic component, conductive paste, conductive film, light shielding image such as black matrix and the like. Preferably, the black resin composition can be advantageously employed to set a light shielding image (including black matrix) in a gap of a coloring pattern, vicinity portions, and in the side of the outside light of TFT and the like to improve a display property of a color filter for the color liquid crystal display. [0020]
Especially preferably, the black resin composition is used as a black matrix used for the black edges formed on the periphery portion, lattice- or stripe-like black portions between color picture elements of red, blue and green, more preferably, dotted and linear black patterns for TFT light shielding in display apparatuses such as liquid crystal displays, plasma displays, EL displays equipped with inorganic EL, CRT displays. [0021]
The titanium nitride compound particles used as the light shielding agent in the present invention contain titanium nitride as a main component and usually titanium oxide Ti02, low order titanium oxide represented by TinOin-i (l "X-ray diffraction"
X-ray diffraction was measured by filling a powdered sample in an aluminum standard sample holder by the wide angle X-ray scattering method (RU-200R manufactured by Rigaku Corporation). As for the measurement conditions, CuKa line was employed as the X-ray source; 50kV/200mA for X-ray output; 1°-1°-0.15 mm-0.45 mm for a slit system; 0.02° for a measurement step (20); and 27minute for a scan rate. [0093]
The angle of diffraction at the peak originated from the (200) plane observed around 29=46° was measured. Further, from the half bandwidth originated from this (200) plane, the crystallite size constituting the particles was calculated using Scherrer's formula of the above-described equations (1) and (2). [0094] "Specific surface area"
The specific surface area of the pigment was measured with high performance automatic gas adsorption apparatus ("BELSORP"36) manufactured by BEL Japan, Inc. After vacuum degassing at 100°C, the adsorption isotherm of N2 gas at a temperature of liquid nitrogen (77 K) was measured and analyzed by BET method to determine the specific surface area. From the value of this specific surface area, a BET-converted particle size was determined by using the above-described equation (3). In this case, the value for titanium nitride d~5.24(g/cm ) was used for the titanium nitride compound particles as a specific gravity whereas d=4.30(g/cm^) was used for titanium nitride oxide samples as the specific gravity. [0095] "Composition analysis"
The content of titanium atoms was measured by ICP optical emission spectrometry (ICP optical emission spectrometer SPS3000 manufactured by Seiko Instruments Inc). [0096]
The contents of the oxygen atoms and nitrogen atoms were measured with Oxygen/Nitrogen analyzer EMGA-620W/C manufactured by HORIBA Ltd. The oxygen atoms and nitrogen atoms were determined by inert gas fusion-infrared absorption method and inert gas fusion-thermal conductivity method, respectively. [0097] "OD value"
The resin black matrix with a film thickness of 1.0 ^.m or 0.8 |im was formed on a non-alkali glass and an OD value was determined with a multi channel photo detector (manufactured by Otsuka Electronics Co. Ltd., MCPD2000) by the above-described equation (8). [0098] "Peak wavelength of transmitted light"
The resin black matrix with a film thickness of 0,6 μm was formed on a non-alkali glass and a peak wavelength was measured with a multi channel photo detector (manufactured by Otsuka Electronics Co. Ltd., MCPD2000). [0099] "Adhesion"
The resin black matrix with a film thickness of 1.0 p-m or 0.8 [im was formed on the non-alkali glass. A sealing agent with a film thickness of 7 μm was formed on the resin black matrix. A cover slip was placed on the resultant. After adhesion between the resin black matrix and the sealing agent, as well as between the sealing agent and the cover slip became sufficient, the resultant sample was subjected to a tensile test at a rate of 10 min/min with "Tensilon" (manufactured by ORIENTEC Co. Ltd., RTM-100). The adhesion was determined by the Equation (10) below from the breaking strength and the torn surface area when the resin black matrix and the glass were broken. Since a value of adhesion strength tends to be smaller as the torn surface area is larger, the value when the torn surface area was 5 mm^ was set as the adhesion strength in the present invention. Adhesion strength (MPa) - breaking strength (kgf) x 9.8/tom surface area (mO(lO). [0100] "Resistance value"
Volume resistance p (fl-cm) was measured with an insulating resistance tester (manufactured by Keithley Instruments Inc., 6517A). The resin black matrix with a film thickness of 1.0 μm or 0.8μm formed on an aluminum substrate was set in a test fix chair (manufactured by Keithley Instruments Inc., 8090) and an alternation voltage of about several volts was applied. A leak current through the coated film was measured to determine the volume resistance. [0101] "Synthesis of poly(amic acid)s"
4,4'-diaminophenyl ether (0,30 molar equivalent), p-phenylenediamine (0.65 molar equivalent) and bis(3-aminopropyl)tetramethy]disiloxane (0.05 molar equivalent) were fed together with 850g of y-butyrolactone and 850g of N-methyl-2-pyrrolidone. To the mixture, 3,3',4,4'-oxydiphthaIcarboxylic dianhydride (0.9975 molar equivalent) was added and the mixture was allowed to react at 80°C for three hours. Thereafiter, maleic anhydride (0.02 molar equivalent) was added, and the resuhing mixture was allowed to react at 80°C for another one hour to obtain a poly(amic acid) A-1 (polymer concentration: 20% by weight). [0102]
4,4'-diaminophenyl ether (0.95 molar equivalent) and bis (3-aminopropyI)tetramethyldisiloxane (0.05 molar equivalent) were fed together with 1700g (100%) of y-butyrolactone. To the mixture, pyromellitic dianhydride (0.49molar equivalent) and benzophenone tetracarboxylic dianhydride (O.SOmolar equivalent) were added and the mixture was allowed to react at 80°C for three hours. Thereafter, maleic anhydride (0.02 molar equivalent) was added, and the resulting mixture was allowed to react at 80°C for another one hour to obtain a poly(amic acid) A-2 (polymer concentration: 20%) by weight). [0103] "Synthesis of acrylic polymers"
Methyl methacrylate/methacrylic acid/styrene copolymer (weight composition ratio 30/40/30) was synthesized in accordance with the method described in Example 1 in Japanese Patent No. 3120476. To the copolymer, 40 parts by weight of glycidyl methacrylate was then added, redeposited with aqua purificata followed by filtration and drying to yield an acrylic polymer (P-1) powder having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH/g). [0104] "Synthesis of adhesion promoters"
1,3-bis (3-aminopropyi)tetramethyldisiloxane in an amount of 4.8 g (0.1 mol), 56.9 g (0.4 mol) of glycidyl methacrylate, and 0.08 g of a polymerization terminator, hydroquinone monomethyl ether, were placed in a flask, and the mixture was allowed to react at 55°C for four hours under stirring, followed by adding 81.7g of propylene glycol monomethyl ether acetate. The mixture was diluted to a concentration of 50% by mass and further allowed to react at 55°C for two hours to yield an adhesion promoter solution (AP-1). [0105] "Synthesis of titanium nitride oxide pigments"
Titanium dioxide powder (4.0 kg) with an average of the primary particle diameter of 40 nm was placed in a reactor. By flowing ammonia gas at linear velocity inside furnace of 3 cm/sec, a reaction was carried out for 6 hours at a furnace temperature of 750°C to yield titanium nitride oxide (Bkl, 3.2 kg). [0106] Example 1
The angle of diffraction 20 of the peak originated from the (200) plane of titanium nitride compound particles (sample 1, manufactured by NISSHIN ENGINEERING INC., TiN UFP Lot 13307412) prepared by thermal plasma method was 42.65°. The crystallite size determined from the half bandwidth of this peak was 17.0 nm and the BET specific surface area was 105.8 m^/g. A composition analysis revealed that the content of titanium was 69.9% by weight; the content of nitrogen was 19.1% by weight; and the content of oxygen was 9.94% by weight. No X-ray diffraction peaks originated from Ti02 were observed at all. [0107]
This sample 1 (96 g), poIy(aniic acid) solution A-1 (120 g), y-butyrolactone (114 g), N-methyl-2-pyrrolidone (538 g) and 3-methyl-3methoxybutyl acetate (132 g) were fed to a tank and the mixture was stirred with a homo mixer (manufactured by
Tokusyu Kika Kogyo) for a hour to yield pre-dispeision 1. Subsequently, the pre-dispersion 1 was provided in Ultra Apex Mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) equipped with a centrifugation separator 70%-filled with zirconia beads having a diameter of 0.05 mm (manufactured by Nikkato Corporation, YTZ balls), and dispersion treatment was canued out for two hours at a revolving rate of 8 m/s to yield pigment dispersion 1 having a solid concentration of 12% by weight, and pigment/resin (weight ratio) =80/20. [0108]
To this pigment dispersion 1 (728 g), were added poly(amic acid) A-1 (63 g), y-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3-methyl-3-methoxybutyl acetate (39 g) and a surfactant LC951 (manufactured Kusumoto Chemicals, Ltd., Ig) to yield black resin composition 1 having a total solid concentration of 10% by weight and the pigment/resin (weight ratio) =70/30. [0109]
This black resin composition 1 was coated on a non-alkali glass (manufactured by Corning Incorporated, "1737") substrate with a curtain flow coater, and vacuum-dried at 80°C, IC' Torr for 2 minutes. Subsequently, the resultant was semi-cured at 140°C for 20 minutes, and a positive photoresist (manufactured by Shipley Company L.L.C, "SRC-100") was coated with a reverse roll coater, pre-baked at 120 °C for 5 minutes in a hot plate, and exposed via a photomask using an exposure apparatus "XG-5000" manufactured by DAINIPPON SCREEN MFG. CO., LTD. Development of a posi-type resist and etching of a polyimide precursor were simultaneously carried out with a tetramethylammonium hydroxide aqueous solution, and then the positive resist was peeled off with methyl cellosolve acetate. Further, the resultant was cured at 300°C for 30 minutes, thereby preparing black matrix 1 with a thickness of 1.0 μm [0110]
Example 2
The angle of diffraction 29 of the peak originated from the (200) plane of titanium nitride compound particles (sample 2, manufactured by Hefei Kai'er.) prepared by thermal plasma method was 42,65". The crystallite size determined from the half bandwidth of this peak was 16.5 nm and the BET specific surface area was 55.8 m^/g. Composition analysis revealed that the content of titanium was 69.8% by weight; the content of nitrogen was 18.6% by weight; and the content of oxygen was 9.95% by weight. No X-ray diffraction peaks originated from TiOz were observed at all. [0111]
Except that the sample 2 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pigment dispersion 2 and black resin composition 2. [0112]
Using the black resin composition 2, black matrix 2 was prepared in the same manner as Example 1. [0113] Example 3
The angle of diffraction 20 of the peak originated from the (200) plane of titanium nitride compound particles (sample 3, manufactured by NISSHIN ENGINEERING INC., TiN UFP Lot 13406810) prepared by thermal plasma method was 42.61°. The crystallite size determined from the half bandwidth of this peak was 25.6 nm and the BET specific surface area was 45.6 mVg. The composition analysis revealed that the content of titanium was 69.9%) by weight; the content of nitrogen was 15.4%) by weight; and the content of oxygen was 13.7%o by weight, X-ray diffraction peaks originated from Ti02 were slightly seen at 25.23° and 27.50°. [0114]
Except that the sample 3 instead .jf th.^ sample 1 was ikicd as a pigment to be used, the same procedure as in Example 1 was canied out to obtain pigment dispersion 3 and black resin composition 3. [0115]
Using the black resin composition 3, black matrix 3 was prepared in the same manner as Example 1. [0116] Example 4
The angle of diffraction 20 of the peak originated from the (200) plane of titanium nitride compound particles (sample 4, manufactured by NISSHIN ENGINEERING INC., TiN UFP Lot 13307215) prepared by thermal plasma method was 42.62°. The crystallite size determined from the half bandwidth of this peak was 29.4 nm and the BET specific surface area was 36.0 m /g. The composition analysis revealed that the content of titanium was 72.2% by weight; the content of nitrogen was 19.4% by weight; and the content of oxygen was 6.37% by weight. No X-ray diffraction peaks originated from Ti02 were observed at all. [0117]
Except that the sample 4 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pigment dispersion 4 and black resin composition 4. [0118]
Using the black resin composition 4, black matrix 4 was prepared in the same manner as Example 1. [0119] Example 5
The angle of diffraction 26 of the peak originated from the (200) plane of titanium nitride compound particles (sample 5, manufactured by NISSHIN
ENGIxNEI'RING INC., TiN UFP Lot 133(^218) prepared by thermal plasma method was 42.60°. The crystallite size determined from the half bandwidth of this peak was 38.3 nm and the BET specific surface area was 31.7 m^/g. The composition analysis revealed that the content of titanium was 73.5% by weight; the content of nitrogen was 20.4% by weight; and the content of oxygen was 4.63% by weight. Any X-ray diffraction peaks originated from TiOa were not observed at all. [0120]
Except that the sample 5 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pigment dispersion 5 and black resin composition 5. [0121]
Using the black resin composition 5, black matrix 5 was prepared in the same manner as Example 1. [0122] Example 6
The angle of diffraction 29 of the peak originated from the (200) plane of a commercially available titanium nitride sample (sample 6, manufactured by Wako Pure Chemical Industries, Ltd., Titanium nitride) was 42.57°. The crystallite size determined from the half bandwidth of this peak was 44.6 nm and the BET specific surface area was 12.4 m^/g. The composition analysis revealed that the content of titanium was 74.3% by weight; the content of nitrogen was 20.3% by weight; and the content of oxygen was 2.94%) by weight. Any X-ray diffraction peaks originated from Ti02 were not observed at all. [0123]
Except that the sample 6 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pre-dispersion 6. Thereafter, except that the pre-dispersion 6 was provided in Dyno-Mill KDL
(manufactured by Shimnaru Enterprises Corporation) 85%-filled with zirconia beads having a diameter of 0.40 mm (manufactured by Toray Industries, Inc., Torayceram beads) and dispersion treatment was earned out at a revolving rate of 11 m/s for four hours, Pigment dispersion 6 and blaclc resin composition 6 were obtained in the same manner as Example 1. [0124]
Using the black resin composition 6, black matrix 6 was prepared in the same manner as Example 1. [0125] Example 7
The angle of diffraction 26 of the peak originated from the (200) plane of a commercially available titanium nitride sample (sample 7, manufactured by Wako Pure Chemical Industries, Ltd., Titanium nitride with an average particle diameter of 1.0 to 1.5 ^.m) was 42.51 °. The crystallite size determined from the half bandwidth of this peak was 67.7 nm and the BET specific surface area was 2.0 mVg. The composition analysis revealed that the content of titanium was 76.2% by weight; the content of nitrogen was 20.3% by weight; and the content of oxygen was 1.43%) by weight. No X-ray diffraction peaks originated from TiOa vvere observed at all. [0126]
Except that the sample 7 instead of the sample 6 was used as a pigment to be used, the same procedure as in Example 6 was carried out to obtain pigment dispersion 7 and black resin composition 7. [0127]
Using the black resin composition 7, black matrix 7 was prepared in the same manner as Example 1. [0128] Example 8
A commercially available titanium nitride sample (manufactured by Wako Pure Chemical Industries, Ltd., Titanium nitride with an average particle diameter of 1.0 to 1.5 μm) was dry-milled at a grinding pressure of 1.4 MPa with Nano Jetmizer (manufactured by Aishin Nano Technologies Co., Ltd.) to obtain sample 8. The angle of diffraction 29 of the peak originated from the (200) plane of the sample 8 was 42.48°, The crystallite size determined from the half bandwidth of this peak was 55.5 nm and the BET specific surface area was 3.2 m^/g. The composition analysis revealed that the content of titanium was 76.7% by weight; the content of nitrogen was 19.9% by weight; and the content of oxygen was 1.78% by weight. No X-ray diffraction peaks originated from Ti02 were observed at all. [0129]
Except that the sample 8 instead of the sample 6 was used as a pigment to be used, the same procedure as in Example 6 was carried out to obtain pigment dispersion 8 and black resin composition 8. [0130]
Using the black resin composition 8, black matrix 8 was prepared in the same manner as Example 1. [0131] Example 9
To the pigment dispersion 4 using the sample 4 (781 g), were added poly(amic acid) A-1 (31 g), y-butyrolactone (86 g), N-methyl-2-pyrrolidone (69 g), 3-methyl-3-methoxybutyI acetate (32 g), a surfactant LC951 (manufactured Kusumoto Chemicals, Ltd., Ig) to yield black resin composition 9 having a total solid concentration of 10% by weight and pigment/resin (weight ratio) =75/25. [0132]
Using the black resin composition 9, black matrix 9 was prepared in the same manner as Example 1 except that coating was carried out such that the thickness of
the black matrix is 0.70μm.
[0133]
Example 10
Except that the sample 4 instead of the sample 6 was used as a pigment to be
used, the same procedure as in Example 6 was carried out to obtain pigment
dispersion 10 and black resin composition 10.
[0134]
Using the black resin composition 10, black matrix 10 was prepared in the
same manner as Example 1.
[0135]
Example 11
Carbon black ("MAI00", manufactured by Mitsubishi Kasei Corporation,
96 g), poly(amic acid) solution A-1 (120 g), y-butyrolactone (114 g), N-methyl-2-pyrrolidone (538 g), and 3-methyl'3-methoxybutyl acetate (132 g) were added to a tanJc and stirred with a homo mixer (manufactured by Tokusyu Kika Kogyo) for a hour to obtain pre-dispersion 11. Thereafter, the pre-dispersion 11 was provided in Ultra Apex Mill Tmanufactured by KOTOBUKI INDUSTRIES CO., LTD.) equipped with a centrifugation separator 70%-fiIled with zirconia beads with a diameter of 0.05 mm (manufactured by Nikkato Corporation, YTZ balls), and dispersion treatment was carried out for two hours at a revolving rate of 8 m/s to obtain a pigment dispersion 11 having a solid concentration of 12% by weight, and pigment/resin (weight ratio) =80/20. [0136]
The pigment dispersion 11 (164 g) and the pigment dispersion 4 using the sample 4 (492 g) were mixed and stirred. To this mixture poly(amic acid) A-1 (106 g), y-butyrolactone (76 g), N-methyl-2-pyrrolidone (112 g), 3-methyl-3-methoxybutyl acetate (48 g) and a surfactant LC951 (manufactured Kusumoto Chemicals, Ltd., Ig)
were added to yield black resin composition 11 having a total solid concentration of
10% by weight and pigment /resin (weight ratio) =63/37.
[0137]
Using the black resin composition 11, black matrix 11 was prepared in the same marmer as Example 1. [0138] Example 12
The sample 4 (200 g), 3-methyl-3-methoxybutanol 45% (by weight) solution of the aci7lic polymer (P-1) (lOOg), and propylene glycol tertiary butyl ether (700g) were fed together to a tank and stirred with a homo mixer (manufactured by Tokusyu Kika Kogyo) for a hour to obtain a pre-dispersion 12. Thereafter, the pre-dispersion 12 was provided in Ultra Apex Mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) equipped with a centrifugation separator 70%-filled with zirconia beads with a diameter of 0.05 mm (manufactured by Nikkato Corporation, YTZ balls), and dispersion treatment was carried out for two hours at a revolving rate of 8 m/s to obtain pigment dispersion 12 having a solid concentration of 24.5% by weight, and pigment/resin (weight ratio) =82/18. [0139]
To the pigment dispersion 12 (525.8 g), a solution containing 50%) by weight solution of bis-phenoxyethanol fluorene diacrylate (27.0 g) in propylene glycol monomethyl ether acetate, 50% by weight solution of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DHPA) (27.0 g) as a multi-functional monomer in propylene glycol monomethyl ether acetate, "Irgacure (registered trademark)" 369 (14.7 g), Asahi"Denka Kogyo K.K., Adeka (registered trademark) optomer" N-1919 (4.0 g), and N,N'-tetraethyl- 4,4'-diaminobenzophenone (1.5g) as a photoinitiator, 8.57 g of AP-1 (50%) (by weight) solution as an adhesion promoter, and a 10%) by weight solution of propylene glycol monomethyl ether acetate solution
(3.6 g) which is a sihcone-based surfactant, in 3-methyl-3-metlioxy-butyl acetate (374.8g) and propylene glycol monomethyl ether acetate (14.4g), was added, to obtain black resin composition 12 having a total solid concentration of 18% by weight, and pigment/resin (weight ratio) =67.5/22.5. [0140]
The black resin composition 12 was coated on a non-alkali glass (manufactured by Corning Incorporated," 1737") substrate with a curtain flow coater, and vacuum-dried at 80°C, 10"' Torr for 2 minutes. Thereafter, the resultant was prebaked at 90°C for 2 minutes, exposed (200 mJ/cm^) via a photomask using an exposure apparatus "XG-5000" manufactured by DAINIPPON SCREEN MFG. CO., LTD., and developed with 0.04% (by mass) KOH aqueous solution, followed by washing with aqua purificata, to obtain a patterning substrate. Further, the patterning substrate was cured at 230°C for 30 minutes, thereby preparing black matrix 12 with a thickness of 0.8 \xm. [0141] Comparative example 1
The angle of diffraction 29 of the peak originated from the (200) plane of a commercially available pigment "13-MC" (sample 9, manufactured by Mitsubishi Material Corporation) was 42.91°. The crystallite size determined from the half bandwidth of this peak was 29.6 rmi and the BET specific surface area was 20.3 m^/g. The composition analysis revealed that the content of titanium was 70.3% by weight; the content of nitrogen was 17.8% by weight; and the content of oxygen was 10.3% by weight. X-ray diffraction peaks originated from Ti02 were seen at 25.28° and 27.44°. [0142]
Except that the sample 9 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pigment
dispersion 13 and black resin composition 13. [0143]
Using the black resin composition 13, black matrix 13 was prepared in the same manner as Comparative example 1 except that coating was carried out such that the thickness of the black matrix is 1.2μm. [0144] Compai'ative example 2
The angle of diffraction 26 of the peak originated from the (200) plane of the titanium nitride oxide Bkl (sample 10) was 43.01°. The crystallite size determined from the half bandwidth of this peak was 28.8 nm and the BET specific surface area was 20.7 m /g. The composition analysis revealed that the content of titanium was 70.6% by weight; the content of nitrogen was 18.8% by weight; and the content of oxygen was 8.64% by weight. X-ray diffraction peaks originated from Ti02 were seen at 25.30° and 27.42°. [0145]
Except that the sample 10 instead of the sample 1 was used as a pigment to be used, the same procedure as in Example 1 was carried out to obtain pigment dispersion 14 and black resin composition 14. [0146]
Using the black resin composition 14, black matrix 14 was prepared in the same manner as Example 1. [0147]
Table 1 shows the properties of the titanium nitride compound particles or titanium nitride oxide used in Examples 1 to 12 and Comparative examples 1 and 2. Figure 2 shows the composition of the black resin composition and the results of evaluation of the resin black matrix prepared using the black resin composition. Figure 1 shows the spectrum of X-ray diffraction of the sample 4 and sample 9.
[0148]
It is seen that any of the resin black matrixes prepared using the titanium nitride compound particles shown in Examples has a high OD value, adhesion, and high volume resistance.
[0151]
Example 13 ■
Preparation of the colored resin composition
Green pigment (Pigment Green 36);44 g, yellow pigment (Pigment Yellow 138);19 g, poly(amic acid) A-2;47 g, and y-butyrolactone; 890 g were added to a tank and stirred with a homo mixer (manufactured by Tokusyu Kika Kogyo) for a hour, to obtain G pigment pre-dispersion Gl. Subsequently, the pre-dispersion Gl was provided in Dyno-Mill KDL (manufactured by Shinmaru Enterprises Corporation) 85%-filled with zirconia beads with a diameter of 0.40 mm (Torayceram beads, manufactured by Toray Industries, Inc.) and dispersion treatment was carried out at a revolving rate of 11 m/s for three hours to yield dispersion Gl having a solid concentration of 7% by weight and pigment/polymer (weight ratio) =90/10. The dispersion Gl was diluted with the poly(amic acid) A-2 and solvent to yield a green resin composition. [0152]
In the same manner, instead of green pigment and yellow pigment, red pigment (Pigment Red 254);63g was added to obtain R pigment dispersion Rl having the solid concentration of 7% by weight and pigment/polymer (weight ratio)=90/l 0. Further, the R pigment dispersion Rl was diluted with the poly(amic acid) A-2 and solvent to yield a red resin composition. [0153]
In the same manner, instead of green pigment and yellow pigment, blue pigment (Pigment Red 15:6);63g was added to obtain B pigment dispersion Bl having the solid concentration of 7% by weight and pigment/polymer (weight ratio)=90/10. Further, the B pigment dispersion Bl was diluted with the poiy(amic acid) A-2 and solvent to yield a blue resin composition. [0154]
The resin black matrix 9 processed in Example 9 was coated with a red paste was coated such that the thickness of the film after dried was 2.0 μm, and the resultant was subjected to pre-baking to form a polyimide precursor red color film. Using a positive photoresist, with the same method as described above, red pixels were formed and heat curing was carried out at 290°C. hi the same manner, a green paste was coated to form green pixels and the heat curing was carried out at 290°C. Continuously, a blue paste was coated to form blue pixels and the heat curing was carried out at 290°C. [0155]
The thus obtained color filter was a color filter 1 having the resin black matrix in the frame portion, an OD value of as high as 4.07, and having an excellent flatness such that the highest step of the surface pixel of the color filter was not more than O.lSμm. [0156] Production of the liquid crystal display
The obtained color filter 1 was washed with a neutral detergent, coated with an alignment layer constituting a polyimide resin by the printing method, and heated in a hot plate at a temperature of ISCC for ten minutes. The film thickness was 0.07 ^m. Subsequently, a color filter substrate was subjected to rubbing treatment, coated a sealing agent by the dispense method, and heated in a hot plate at 90''C for ten minutes. Meanwhile, a substrate with TFT array being formed on a glass was washed in the same manner, coated with an alignment layer and heated. Subsequently, the resultant was sprayed with a ball spacer with a diameter of 5.5 μm, overlapped with a color filter substrate coated with a sealing agent, heated under increased pressure at a temperature of 16Q°C for 90 minutes to cure the sealing agent. This cell was left to stand at a temperature of 120°C under a pressure of 13.3 Pa for four hours. Then it was left to stand in nitrogen for 0.5 hours and liquid crystal
injection was again carried out under vacuum. The cell was placed in a chamber and the pressure was reduced to 13.3 Pa at room temperature. Subsequently, the liquid crystal injection port was immersed in liquid crystals and the pressure was recovered to ordinary pressure with nitrogen, thereby carrying out liquid ci7stal injection. After the liquid crystal injection, the liquid crystal injection port was closed with a UV curing resin. Subsequently, a polarizing plate was adhered to the outside of two glass substrates of the cell, thereby completing the cell. Further, the obtained cell was modularized to complete liquid crystal display 1. Observation of the obtained liquid crystal display 1 found that there were no display defects. Contrast was excellent due to high light shielding of the resin black matrix. One hundred liquid crystal displays were prepared in the same procedure. Because adhesion of the resin black matrix was high, there were not any defects including peeling in the sealing portion during liquid crystal injection at all. [0157] Comparative Example 3
The same procedure as in Example 13 was carried out to form a color filter except that black matrix 13 was used as a black matrix to be used. Obtained was a color filter 2 having the resin black matrix in the edge portions, the OD value of 4.09 and the height of the surface pixel steps of 0.35μm at maximum. [0158]
The same procedure as in Example 13 was carried out to obtain liquid crystal display 2 except that the color filter 2 was used. Observation of the liquid crystal display 2 revealed that there were display defects due to the defective alignment of the liquid crystal resulted from a large pixel surface steps/flatness.
1. A black resin composition comprising at least a light shielding agent, a resin
and a solvent, said light shielding agent containing at least titanium nitride compound
particles, wherein the angle of diffraction 29 of the peak originated from (200) plane
of said titanium nitride compound particles when CuKa line is used as the X-ray
source is not less than 42,5° and not more than 42.8".
2. The black resin composition according to claim 1, wherein said angle of
diffraction 29 originated from the (200) plane of said titanium nitride compound
particles when CuKa line is used as the X-ray source is not less than 42.5° and less
than 42.7°.
3. The black resin composition according to claim 1 or 2, wherein the crystallite
size determined from half bandwidth of the peak originated from the (200) plane
when CuKa line is used as the X-ray source is not more than 50 nm.
4. The black resin composition according to any one of claims 1 to 3, wherein
the specific surface area of said titanium nitride compound particles determined by
BET method is not less than 5 m2/g and not more than 100m2/g.
5. The black resin composition according to any one of claims 1 to 4, wherein the amount of oxygen atoms contained in said titanium nitride compound particles is not more than 12 % by weight.
6. The black resin composition according to any one of claims 1 to 5, wherein said titanium nitride compound particles are prepared by thermal plasma method.
7. A resin black matrix formed of a coated film of said black resin composition
according to any one of claims 1 to 6, which resin black matrix has an optical density
(OD value) of not less than 4.0 per 1.0μm of film thickness.
8. A color filter comprising said resin black matrix according to claim 7.
9. A liquid crystal display comprising said color filter according to claim 8.