JP6318699B2 - Black photosensitive resin composition, black matrix, black matrix substrate, color filter, liquid crystal display device, and organic electroluminescence display device - Google Patents

Description

The present invention relates to a black photosensitive resin composition, a black matrix, a black matrix substrate, a color filter, a liquid crystal display device, and an organic electroluminescence display device.

  A liquid crystal display device and an organic electroluminescence display device are indispensable parts as a display unit of information electronic equipment such as a television receiver, a notebook computer, a monitor, a mobile phone, and a tablet terminal.

  Here, in the liquid crystal display device, a substrate having an active element such as a TFT (thin film transistor) and a color filter substrate having a colored pixel and a black matrix partitioning them are bonded to face each other, and liquid crystal is injected into the gap. Later, it is manufactured in combination with a polarizing plate and a backlight unit. Then, by controlling the voltage applied to the liquid crystal layer, the transmittance of each colored pixel is adjusted, and full color display becomes possible.

  On the other hand, an organic electroluminescence display device is obtained by laminating a self-luminous organic compound on a substrate having an active element. For full-color display, a method in which red, green, and blue organic compounds are separately applied and a method in which a white light-emitting organic compound and a color filter are combined are known.

  By the way, in order to improve the visibility of a liquid crystal display device and an organic electroluminescence display device (hereinafter abbreviated as “display device”), investigations for higher brightness, higher contrast, and higher definition have been made. However, the reduction of external light reflection, which is a major factor that impairs visibility, is still in the developing stage. In particular, there is a strong demand for improvement in applications to devices that are often handled outdoors, such as mobile phones and tablet terminals.

  External light reflection of the display device will be described using a liquid crystal display device as an example. Part of the external light incident on the liquid crystal display device is reflected at the interface between air and the outermost surface, that is, the polarizing plate. In order to reduce external light reflection on the outermost surface, it is known that it is effective to provide an antireflection layer on the polarizing plate surface.

  On the other hand, the light transmitted through the polarizing plate is reflected by the color filter, glass or TFT substrate. In particular, since the reflection between the black matrix of the color filter and the glass interface has a high strength, a countermeasure for reducing it is required.

  In addition, a metal thin film such as chromium has been conventionally used as the material of the black matrix of the color filter. However, since the metal thin film has a high environmental load in addition to a high reflectance, a resin black matrix in which a black pigment such as carbon black is dispersed in the resin has become mainstream. In addition, in the black matrix which used the black pigment for the light shielding material, it is known that the reflectance of a glass interface can be reduced by reducing the content of the black pigment.

  For example, in Patent Document 1, carbon black coated with resin is used as a light shielding material, and an optical density (OD value) per unit film thickness that is an index of light shielding properties is 3.1 to 3.3. It was shown that the reflectance in the SCI method (abbreviation of “Special Components Include method”, indicating the sum of specular reflection light and diffuse reflection light) can be adjusted to 5.4 to 5.9 by adjusting the pigment concentration. Yes.

  Although it is possible to reduce external light reflection by the above proposal, it is not sufficient to obtain good visibility. In order to further reduce the reflectance, it is necessary to lower the pigment concentration. In this case, however, there is a problem that the light blocking property, which is the original function of the black matrix, is insufficient. That is, there is a problem that there is a trade-off relationship between reducing the reflectance of the black matrix and improving the light shielding property.

  Therefore, in order to achieve both the low reflectance and the high light shielding property of the black matrix, for example, techniques of Patent Documents 2 to 4 have been proposed. Specifically, Patent Document 2 proposes to laminate a first light-shielding layer mainly composed of a black pigment and a photosensitive resin and a second light-shielding layer mainly composed of graphite. In this technique, the reflectance is suppressed by keeping the pigment concentration of the first light shielding layer low, and the light shielding property is imparted by using graphite having a strong shielding power for the second light shielding layer.

  Japanese Patent Application Laid-Open No. H10-228561 proposes to sequentially stack a light absorption layer and a light reflection layer containing metal fine particles on a substrate. In this proposal, the light reflecting layer containing metal fine particles has both the property of reflecting light and the property of absorbing light, so that the light from the observer side can be practically acceptable with a relatively thin light absorbing layer. It is described that reflection can be prevented.

  Japanese Patent Application Laid-Open No. 2004-228561 proposes to sequentially stack a low optical density layer and a high optical density layer on a transparent substrate. This proposal describes that the internal reflection of the light shielding layer can be suppressed by appropriately selecting the optical density (OD value) of the low optical density layer and the refractive index of the high optical density layer.

JP 2013-130677 A JP-A-9-297209 Japanese Patent No. 4694157 Japanese Patent No. 5209603

  However, with the techniques disclosed in Patent Documents 2 to 4, it is possible to achieve both low reflectance and high light-shielding properties. However, it is necessary to form a black matrix having a multilayer structure, which increases the number of processes. There was a problem of incurring an increase in cost. In addition, as liquid crystal display devices and the like have become higher in definition, there has been a problem that the black matrix alignment accuracy between the lower layer and the upper layer is required.

The present invention has been made in view of such circumstances, and a black photosensitive resin composition that is a raw material for a black matrix that can achieve both high light-shielding properties and low reflectance without using a multilayer structure at low cost. , black matrix, the black matrix substrate, a color filter, a liquid crystal display device, and an object thereof is to provide an organic electroluminescent display device.

In order to solve the above problems, the present invention employs the following configuration.
(1) (A) carbon black, (B) hydrophobic silica fine particles, (C) a dispersant, (D) an alkali-soluble resin, (E) a polymerizable monomer, (F) a photoinitiator, (G) A black photosensitive resin composition containing at least a solvent, wherein the weight ratio (A) / (B) of the (A) carbon black to the (B) hydrophobic silica fine particles is 1. as well as a range of 5 to 9.0, wherein (C) dispersing agent, Ri urethane dispersant der satisfying either or both of the Sp value 12.0 or higher and molecular weight of 6,000 or more, the (B ) Either one or both of hydrophobic silica fine particles, a silyl group capable of condensing with a silanol group on the silica surface, and a silyl group capable of forming a functional group capable of condensing with a silanol group on the silica surface by hydrolysis. One or more silyl groups in one molecule Black photosensitive resin composition, characterized in der Rukoto those surface-treated with a compound that.

(2) The black photosensitive resin composition as described in (1), wherein the carbon black (A) is coated with a resin.

( 3 ) A black matrix formed using the black photosensitive resin composition according to (1) or ( 2) .

( 4 ) A black matrix substrate comprising a transparent substrate and the black matrix according to (3) formed on the transparent substrate, wherein the optical density (OD value) is 3.0 / μm or more. In addition, when formed on a transparent substrate, the reflectance measured using a microspectroscope from the transparent substrate side is 1.0% or less, and a spectrocolorimeter is used from the transparent substrate side. reflectance measured SCI method Te has a characteristic to be 5.0% or less, of, features and be Lube rack matrix substrate that has one or both of properties.

( 5 ) A color filter comprising a transparent substrate and the black matrix according to ( 3 ) provided on the transparent substrate.

( 6 ) A liquid crystal display device comprising the color filter according to ( 5 ).

( 7 ) The organic electroluminescence display device according to ( 6 ).

According to the present invention, a black photosensitive resin composition, a black matrix, a black matrix substrate, which is a raw material for a black matrix that can achieve both high light-shielding properties and low reflectance at low cost without using a multilayer structure , a color filter, a liquid crystal display device, and it is possible to provide an organic electroluminescent display device.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a color filter which is an embodiment to which the present invention is applied. FIG. 2 is a schematic cross-sectional view showing an example of the configuration of the liquid crystal display device according to the first embodiment to which the present invention is applied. FIG. 3 is a schematic cross-sectional view showing an example of the configuration of an organic electroluminescence display device according to a second embodiment to which the present invention is applied.

<First Embodiment>
Hereinafter, the liquid crystal display device according to the first embodiment to which the present invention is applied is combined with a color filter used in the liquid crystal display device, a black matrix used in the color filter, and a black photosensitive resin composition as a raw material for the black matrix. This will be described in detail with reference to the drawings.
In addition, in the drawings used in the following description, in order to make the features easy to understand, there are cases where the portions that become the features are enlarged for the sake of convenience, and the dimensional ratios of the respective components are not always the same as the actual ones. Absent.

(Black photosensitive resin composition)
First, the structure of the black photosensitive resin composition which is one embodiment to which the present invention is applied will be described. The black photosensitive resin composition of the present embodiment is used as a raw material for a black matrix constituting a color filter. Specifically, the black photosensitive resin composition of the present embodiment includes (A) carbon black, (B) hydrophobic silica fine particles, (C) a dispersant, (D) an alkali-soluble resin, and (E ) A polymerizable monomer, (F) a photoinitiator, and (G) a solvent.

Further, in the black photosensitive resin composition of the present embodiment, the weight ratio (A) / (B) of the (A) carbon black and the (B) hydrophobic silica fine particles is 1.5 to 9.0. And (C) the dispersant is a urethane-based dispersant satisfying one or both of an Sp value of 12.0 or more and a molecular weight of 6,000 or more. .
Details will be described below.

"(A) Carbon black"
In the black photosensitive resin composition of the present embodiment, carbon black is used as the black color material. The type of carbon black that can be applied is not particularly limited, and can be appropriately selected according to physical properties such as optical density in a target black matrix.

  In consideration of the storage stability of the composition, the primary particle size is usually preferably 20 to 100 nm, more preferably 20 to 60 nm, and still more preferably 20 to 30 nm. is there.

  Here, when the primary particle diameter of carbon black is less than 20 nm, dispersibility and dispersion stability are lowered, which is not preferable. On the other hand, when the primary particle diameter exceeds 100 nm, the surface smoothness and pattern shape of the resulting black matrix are deteriorated, which is not preferable. On the other hand, when the primary particle diameter is within the above range, a black matrix having excellent dispersibility and dispersion stability and excellent surface smoothness and pattern shape can be obtained.

  In addition, the primary particle diameter in the present specification is obtained from an average value after taking several tens of thousands of photographs with an electron microscope method, that is, an electron microscope photograph, and measuring several thousand pieces. More specifically, for example, the measurement may be performed using a fully automatic image processing apparatus “MKSIPS-1000” manufactured by Mitsubishi Chemical Corporation.

  The DBP (Dibutylylphthalate) oil absorption of carbon black is not particularly limited, but is preferably 140 ml / 100 g or less, and more preferably 120 ml / 100 g or less. Here, when the DBP oil absorption amount of carbon black is larger than 140 ml / 100 g, the blackness of carbon black is lowered, and the density feeling when used in a black matrix is not preferable. Moreover, since the viscosity of a carbon black dispersion liquid or a photosensitive resin composition becomes high and the smoothness of a coating film falls, it is not preferable. In addition, the DBP oil absorption amount of carbon black in the present specification is measured by a method defined in JIS K6221 (1982).

  The pH of the carbon black is not particularly limited, but is preferably in the range of 2.5 to 4.5, and more preferably in the range of 2.6 to 3.8. Here, when the pH of the carbon black is within the above range, it is preferable because good dispersibility and glass adhesion can be obtained. The pH of the carbon black is, for example, 20 g of carbon black added to distilled water (pH 7.0), boiled for 5 minutes, cooled to room temperature, and then the pH of the muddy carbon black was measured with a glass electrode pH meter. It can be determined by measuring.

  The ash content of carbon black is not particularly limited, but an ash content of 1.0% by weight or less, particularly 0.5% by weight or less is particularly preferable because of excellent dispersibility. The ash content of carbon black can be calculated from the amount of ash remaining when carbon black is baked in air at 750 ° C. for 5 to 6 hours, for example.

  By the way, a technique is known in which carbon black is coated with an insulating component such as a resin to provide insulation and increase resistance. Further, known patent documents (for example, Japanese Patent Application Laid-Open No. 2001-106938, Japanese Patent Application Laid-Open No. 2001-152048, Japanese Patent Application Laid-Open No. 9-95625, etc.) disclose resin coating means. Therefore, in the black photosensitive resin composition of the present embodiment, the component (A) carbon black is preferably coated with a resin. By using carbon black coated with a resin as a component of the black photosensitive resin composition, compatibility with components such as hydrophobic silica fine particles and alkali-soluble resin in the photosensitive resin composition can be enhanced.

  The degree of resin coating of carbon black is not particularly limited, but the powder resistance value increases by coating carbon black with resin, so an indicator of the degree of resin coating A powder resistance value can be used. In applications where high resistance carbon black is required, it is usually preferable to coat the carbon black with a resin so that the powder resistance is 4 Ω · cm or more.

The powder resistance value can be measured by, for example, putting a 2 g sample in a polytetrafluoroethylene (PTFE) container having an inner diameter of 2 cm with a brass electrode attached at the bottom and a PTFE rod with a brass electrode at the tip. After closing the lid, a load is applied at a rate of 0.2 mm / min with Tensilon, and the resistance at 50 kg / cm ² is measured with a tester. Then, the volume resistivity of the powder can be calculated from the bulk and resistance of the powder resistance under the load by the following formula.
Powder resistance value (Ω · cm) = Cross sectional area of carbon black powder (cm ² )
× Resistance value (Ω) / Bulkiness of carbon black powder (cm)

  The black photosensitive resin composition of the present embodiment may be used in combination of a plurality of types of carbon black, and of course, carbon black having different primary particle diameter, DBP oil absorption, and pH may be used in combination. Absent.

  The carbon black content in the solid content of the black photosensitive resin composition is preferably in the range of 35 to 55 percent by weight, and more preferably in the range of 40 to 50 percent by weight. Here, when the content of carbon black in the solid content is less than 35%, it is not preferable because the light shielding property is insufficient when the black matrix is formed. On the other hand, when the content exceeds 55%, the reflectance is high when a black matrix is formed, and the visibility when used in a display device is not preferable. On the other hand, when the content of carbon black in the solid component is within the above range, it is possible to achieve both high light shielding properties and low reflectance when a black matrix is formed.

“(B) Hydrophobic silica fine particles”
The black photosensitive resin composition of the present embodiment is characterized by using hydrophobic silica fine particles. Here, the silica fine particles need only have silica, that is, SiO _{2 as} a main component, and may contain alumina, titanium, or the like. Further, the hydrophobic silica fine particles refer to silica fine particles that are not compatible with water. Specifically, for example, it can be made hydrophobic by introducing a hydrophobic group into the surface of silica fine particles.

  The hydrophobic silica can be identified qualitatively by, for example, a method of adding silica fine particles to water. That is, the hydrophobic silica in the present specification means a material that floats on water when silica is added to water. To determine whether it is hydrophobic, for example, take a sample of 1.5 g of silica, put it in a glass bottle with 23.5 ml of water, cover it, shake it several times by hand, and shake the entire sample. Is left in contact with water for 10 minutes. If it is hydrophobic, it is not compatible with water and can be confirmed because the silica floats on the water.

  Samples that are not in powder form and are stably dispersed in an aqueous medium do not meet the above definition of hydrophobicity, but those that are dispersed in other dispersion media are filtered and dispersed. And can be confirmed by the above method by making a dry powder. As a general method for removing the solvent of the silica particle dispersion, for example, a method of removing the solvent by filtration, centrifugation, distillation, etc., and then drying by a vacuum dryer, a shelf dryer, etc., a fluidized bed dryer And a method of directly drying the slurry with a spray dryer, etc.

  Silica fine particles can be produced by flame hydrolysis of silicon tetrachloride or an organosilicon compound in an oxyhydrogen flame, silicon-containing materials such as silica sand, and granular silicon such as pulverized silicon single crystals in an arc furnace. Hydrolysis condensation of organosilicon compounds that can be hydrolyzed and condensed, such as alkoxysilanes, precipitated by the reaction of silicic acid and water glass, such as the method of obtaining silica particles by oxidation and oxidation It is known to be due to a liquid phase reaction such as generation of particles by reaction. In the present embodiment, the method for producing silica fine particles is not particularly limited, but a method using a gas phase reaction is preferable in that the sphericity is high, the particle size is uniform, the cohesiveness is small, and the dispersibility is excellent. Since it is excellent also in the effect at the time of using the black photosensitive resin composition or black matrix of this embodiment, it is preferable. The shape of the silica particles is not particularly limited, but a substantially spherical shape is preferable from the viewpoint of low cohesiveness and excellent dispersibility, and further, the black photosensitive resin composition or the black matrix of the present embodiment. This is also preferable because it is excellent in effect.

  As described above, the fine silica particles obtained by the above-described normal production method usually have a hydrophilic surface due to the hydroxyl group on the powder surface. Here, it is difficult for the inventors of the present application to obtain a resin composition capable of forming a black matrix having both high light-shielding properties and low reflectance with such normal silica fine particles (comparison described later). (See Example 4), and found that the surface characteristics of the silica fine particles have a great influence on the compatibility between high light-shielding properties and low reflectance. Furthermore, the inventors of the present application unexpectedly obtain a resin composition that can form a black matrix that achieves both high light-shielding properties and low reflectance by using hydrophobic silica and further using a specific dispersant described later. We have found that this is possible and have reached the present invention.

  Hydrophobic silica fine particles used as a component of the black photosensitive resin composition of the present embodiment can be obtained by hydrophobizing the surface of the hydrophilic silica fine particles obtained by the usual production method as described above. . Attempts to adjust the surface properties by hydrophobizing the silica surface are well known. Specifically, silane compounds such as silane coupling agents and other coupling agents, polymer materials such as silicone oil, and the like are known as hydrophobizing agents (for example, JP-A-2005-536613, JP-A-2003-36513). 2005-536611 gazette, special table 2010-195680 gazette, special table 2010-534617 gazette, JP, 2012-236752, etc.). Further, ceramic powder such as silica is converted into 20 to 100 mol%, 0 to 30%, 0 to 50%, and 0 with tetrafunctional, trifunctional, bifunctional, and monofunctional organosilicon compounds as monomer units, respectively. It has also been proposed to coat with a siloxane star graft polymer obtained by polymerizing 10% (for example, JP 2000-508684A). More specifically, organosilane, haloorganosilane, silazane, polysiloxane, silicone oil, and siloxane star polymer described in these known documents can be used as a hydrophobizing agent for hydrophilic silica fine particles.

  Specific examples of the silicone oil include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, and methacryl-modified silicone. Oil, mercapto-modified silicone oil, phenol-modified silicone oil, one-end reactive modified silicone oil, different functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil , Hydrophilic specially modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid-containing modified silica N'oiru include modified silicone oils such as fluorine-modified silicone oil. Any one of these silicone oils may be used, or two or more kinds may be mixed and used. The viscosity of the silicone oil is usually 10 to 500 cs, more preferably 30 to 100 cs.

  Silica powder is treated with these hydrophobizing agents, and a hydrophobic group such as dimethyl group, trimethyl group, dimethylsiloxane group, alkyl group or methacryl group is introduced to the surface of silica powder, or the surface of silica powder is coated. The surface of the silica particles can be hydrophobized by the presence of a hydrophobic substance such as by the above method. These hydrophobic groups are sufficient if the silica particles can be made hydrophobic as described above, regardless of whether they are chemically bonded to the silica surface or physically bonded.

  Further, the hydrophobizing method is not particularly limited as long as the above-described hydrophobic silica can be obtained, and various conventionally known processing methods can be used. For example, using an organosilane such as an alkylsilyl compound such as dimethyldichlorosilane and monomethyltrichlorosilane, the silica particles are sprayed into a mixer together with water or an organosilane or sequentially, mixed, and heated at 100 to 160 ° C. A method (see JP 2005-536613 A, JP 2005-536611 A, etc.), one or more organic silicon compounds such as halosilane, alkoxysilane, silazane, siloxane, etc. A method in which a silylating agent is sprayed on the particles and heat treated at 105 to 400 ° C., or the silica particles are treated with a silylating agent in a vapor state and heat treated at 200 to 800 ° C. (see JP-T-2010-195680), stirring Put silica fine powder in a container equipped with dredging equipment and stir under nitrogen atmosphere. Coupling agent, silicone oil, silazane, hydrophobizing agent alone, or by dropping or spraying hydrophobizing agent and charge adjusting agent together with solvent as necessary, or hydrophobizing agent etc. is heated and vaporized, and silica fine powder As a method of heating after sufficiently dispersing and then cooling, a method of coating silica fine particles with silicone oil, for example, a method of spraying and spraying silicone oil while stirring silica particles, while fluidizing in a fluidized bed Various methods such as a method of introducing silicone oil, one or more compounds having a functional group such as vinyl group, vinylsilyl group, trimethylsilyl group, dimethylsilyl group, monomethylsilyl, etc., and a hydrophobic group on the silica surface Method of fixing (Japanese Patent Publication No. 2007-526374), in this case, protective gas such as nitrogen How to lower 囲気, and a method of further modifying the structure was pulverized by a ball mill or the like. When using a siloxane star graft polymer, a solvent and silica fine particles are added into a container, argon pressure substitution is performed, an ASTB solution is added, a siloxane star graft polymer is added, and high shear mixing is performed for coating ( JP 2000-508684A) can also be employed.

  As described above, various hydrophobizing agents can be used. A compound having at least one silyl group condensable with a silanol group on the silica surface in one molecule, or such a silyl group by hydrolysis. It is particularly preferable to treat the surface with either a compound having at least one group capable of forming a group in one molecule or a compound having at least one group in one molecule.

  Specific examples of such compounds include various halosilanes, alkoxysilanes, silazanes, and siloxanes, and specific examples include various silylating agents or siloxane star polymers. These molecules have one or more functional groups that can be dehydrated and condensed with silanol groups on the silica surface in one molecule, or can be generated by hydrolysis, so that by polycondensation reaction with the silanol groups on the silica particle surface. It is assumed that the silica particles can be sufficiently fixed on the surface.

  As specific examples of such compounds, for example, various materials are also described in known literature (Japanese Patent Application Laid-Open No. 2010-195680), and more preferably those having an alkylsilyl group, particularly dimethylsilyl. Group having a lower alkylsilyl group, such as a methylsilyl group such as a trimethylsilyl group, in particular, a dimethylsilyl group or a trimethylsilyl group, particularly preferably dimethyldichlorosilane or hexamethyldisilazane. It is preferable because of its excellent point. Probably, the introduction of such functional groups on the surface of the silica fine particles prevents aggregation of the silica fine particles and at the same time does not hinder the affinity with other components such as carbon black. This is presumably because a suitable state can be formed.

  As a method of hydrophobizing silica fine particles using these compounds, the above-described hydrophobizing method may be appropriately selected. However, a method of preparing and using a hydrolyzed solution in advance, and various methods in the case of a compound that is hardly soluble in water. A known method such as adjusting the pH with an organic acid may be used as appropriate.

  The hydrophobic silica fine particles used as a component of the black photosensitive resin composition of the present embodiment can be obtained by subjecting the commercially available silica fine particles to the hydrophobic treatment described above, and are also commercially available as hydrophobic silica particles. Therefore, it can be appropriately selected and used in consideration of various physical properties described below.

  The average primary particle diameter of the hydrophobic silica fine particles is not particularly limited, but is preferably in the range of 5 to 100 nm, and more preferably in the range of 5 to 40 nm. Here, it is not preferable that the average primary particle diameter of the hydrophobic silica fine particles is larger than 100 nm because the pattern shape of the black matrix tends to be lowered when the black matrix is formed, such as deterioration of surface roughness. On the other hand, an average primary particle size of less than 5 nm is not preferable because dispersion becomes difficult. The primary particle size of the hydrophobic silica fine particles can be measured, for example, by measuring a particle size of 2500 random particles or more from a silica fine particle sample on a transmission electron microscope image, and averaging the average primary particle size by number average. Can be used.

The specific gravity of the silica fine particles (hydrophobic silica fine particles) is not particularly limited, but is preferably 1.1 or less, and more preferably 1.0 or less. When the specific gravity of the silica fine particles is within the above range, the effect of the present invention is particularly remarkable.
The specific surface area of the silica fine particles (hydrophobic silica fine particles) is not particularly limited, is preferably 25~500m ² / g in BET specific surface area, more preferably from 40 to 400 ² / g 50 to 380 m ² / g is more preferable. When the specific surface area of the silica fine particles is within the above range, the effect of the present invention is particularly remarkable.
The purity of the silica is not particularly limited, and may contain other components as described above, but is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more. When the purity of the silica is 80% or more, the effect of the present invention is particularly remarkable.

  By using the hydrophobic silica fine particles described above as a component of the black photosensitive resin composition of the present embodiment, a black resin capable of achieving both high light shielding properties and low reflectance without using a multilayer structure when a black matrix is formed. A composition can be obtained. By the way, a photosensitive resin composition itself containing silica fine particles, carbon black, and a polymer dispersant has been conventionally known. However, the present inventors have found that the surface physical properties of the granular silica used and the type or physical properties of the polymer dispersant are important factors that have a great influence on the compatibility between high light-shielding properties and low reflectance. It is.

  The content of silica fine particles (hydrophobic silica fine particles) in the solid content of the black photosensitive resin composition is preferably in the range of 3.9 to 36.7 weight percent, and 4.4 to 33.3 weight percent. More preferably, it is the range. Here, when the content of the silica fine particles in the solid content is less than 3.9 weight percent, it is not preferable because it is very difficult to achieve a low reflectance when a black matrix is formed. On the other hand, when the content exceeds 36.7 weight percent, the developability of the black photosensitive resin composition tends to be insufficient, and pattern linearity and cross-sectional shape are liable to be deteriorated. On the other hand, if the content of the silica fine particles in the solid content is within the above range, it is preferable because it is easy to achieve a low reflectance when a black matrix is formed.

  Furthermore, in the black photosensitive resin composition of the present embodiment, the weight ratio (A) / (B) of the (A) carbon black and the (B) hydrophobic silica fine particles is 1.5 to 9.0. A range is preferable. Here, when the weight ratio (A) / (B) is less than 1.5, the developability of the black photosensitive resin composition tends to be insufficient, and pattern linearity and cross-sectional shape are liable to be deteriorated. . On the other hand, when the weight ratio (A) / (B) exceeds 9.0, it is not preferable because it is very difficult to achieve a low reflectance when a black matrix is formed. On the other hand, when the weight ratio (A) / (B) is within the above range, it is preferable because it is easy to achieve a low reflectance when a black matrix is formed.

“(C) Dispersant”
The black photosensitive resin composition of the present embodiment is characterized by using a urethane-based dispersant as a dispersant. Here, in this specification, the urethane-based dispersant is a compound composed of a polymer having at least a polyurethane skeleton, and has a function of facilitating dispersion of solid particles such as carbon black.

  In general, the urethane-based dispersant can be prepared by reacting a polyisocyanate compound and a polyol to generate a main chain having a urethane bond. Polyurethanes having various structures can be obtained by selecting a polyisocyanate compound, a polyol, and reaction conditions. Moreover, the urethane type dispersing agent which introduce | transduced the desired functional group by reaction with the compound which has a specific functional group can be obtained. For example, JP-A-4-210220, JP-T 2000-506436, JP-T 2007-502903, JP-T 2008-542523, JP-A-4-210220 are disclosed in JP-A-4-210220. It can also be obtained by the methods described in, for example, 2010-235945 and JP-T 2010-509165.

  Moreover, a commercial item can be used as a urethane type dispersing agent. Specifically, for example, Lubrizol Solsperse series (76500), Big Chemie Disperbyk series (161, 162, 163, 164, 165, 166, 167, 170, 174, 182, 183, 184, 185, 2150) 2155, 2163, 2164) and Efka series (4015, 4046, 4047, 4050, 4055, 4061, 4080) manufactured by BASF.

  The polymer structure of the dispersant is not particularly limited, but a comb shape is preferable. Here, in the present specification, the polymer having a comb-shaped structure refers to a polymer having a structure in which a linear polymer is a trunk and a large number of linear polymers are branched into branches. Such a comb-shaped polymer is known to be excellent in surface adhesion of carbon black. For example, JP-T-2008-542523 discloses a polyurethane dispersant in which a solvent-solubilized chain such as a polyether chain or a polyester chain is grafted to a polyurethane skeleton. A polyurethane-based dispersant having an aromatic ring introduced into the main chain by using an aromatic isocyanate compound is also known (Japanese Patent Laid-Open No. 2011-164647).

  As the dispersant which is a component of the black photosensitive resin composition of the present embodiment, a dispersant having a polyurethane main chain as a comb polymer and further containing a nitrogen atom in a functional group is particularly preferable. As the form of the nitrogen atom, an amino group, a quaternary ammonium salt and the like are preferable. This is because these functional groups usually have basicity so that they can easily coordinate with acidic groups such as pigments and pigment derivatives, thereby contributing to dispersion stabilization. The amine value of the dispersant is usually 2 mg-KOH / g or more, preferably 3 mg-KOH / g or more, and usually 100 mg-KOH / g or less, preferably 80 mg-KOH / g or less. If the amine value is too low, the basicity is insufficient and the dispersion stability is poor, and if the amine value is too high, the voltage holding ratio of the liquid crystal may be reduced when used in a liquid crystal display device, resulting in poor display. It becomes easy to cause. A dispersing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Specifically, the polyurethane dispersant has (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) an active hydrogen and a tertiary amino group in the same molecule. A compound can be used as a raw material.

(1) Polyisocyanate compound Specific examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1. , 5-diisocyanate, tolidine diisocyanate and other aromatic diisocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'- Alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane, xylylene diene Aliphatic diisocyanates having aromatic rings such as socyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4- Isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), triisocyanate such as tris (isocyanatephenyl) thiophosphate, and their trimers, water adducts, And these polyol adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing the above-mentioned trimer of organic diisocyanate, the above polyisocyanate is used with an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. A method of obtaining a desired isocyanate group-containing polyisocyanate by partial trimerization of isocyanate groups and stopping the trimerization by adding a catalyst poison and then removing unreacted polyisocyanate by solvent extraction and thin-film distillation. Can be mentioned.

(2) Compound having one or two hydroxyl groups in the same molecule Specific examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin Examples thereof include glycols and the like, and those compounds in which one end hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms. These may be used alone or in combination of two or more.

  Examples of the polyether glycol include polyether diol, polyether ester diol, and a mixture of two or more of these. Specific examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyethylene. And oxyoctamethylene glycol, and mixtures of two or more thereof. Specifically, the polyether ester diol is obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or reacting polyester glycol with an alkylene oxide. Examples thereof include poly (polyoxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Specific examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (ethylene glycol, diethylene glycol, triglyceride). Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5- Pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 5-pentanediol, 1,6-hexanediol, 2-methyl 2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1, Aliphatic glycols such as 8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, bishydroxyethoxybenzene, etc. Of N-alkyldialkanolamines such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, Or the diols or carbon 1-25 monovalent polylactone diols obtained alcohol used as initiator or polylactone monool, such as polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule has a lower limit of usually 300 or more, preferably 500 or more, more preferably 1,000 or more, and an upper limit of usually 10,000 or less. , Preferably 6,000 or less, more preferably 4,000 or less.

(3) Compound having active hydrogen and tertiary amino group in the same molecule As active hydrogen, that is, hydrogen atom directly bonded to oxygen atom, nitrogen atom or sulfur atom, specifically, for example, hydroxyl group, The hydrogen atom in functional groups, such as an amino group and a thiol group, is mentioned, Especially, the hydrogen atom of an amino group, especially primary amino group is preferable.

  The tertiary amino group is not particularly limited. Specifically, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like. A group in which an amino group is linked to form a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done. Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  A preferable blending ratio of the urethane-based dispersant raw material is (1) 100 parts by weight of the polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule has a lower limit of usually 10 parts by weight or more, Preferably it is 20 parts by weight or more, more preferably 30 parts by weight or more, and the upper limit is usually 200 parts by weight or less, preferably 190 parts by weight or less, more preferably 180 parts by weight or less. (3) Active hydrogen in the same molecule The compound having a tertiary amino group has a lower limit of usually 0.2 parts by weight or more, preferably 0.3 parts by weight or more, and an upper limit of usually 25 parts by weight or less, preferably 24 parts by weight or less.

  Production of the urethane-based dispersant, which is a component of the black photosensitive resin composition of the present embodiment, is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. Specifically, for example, tin such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, iron such as iron acetylacetonate and ferric chloride, triethylamine, triethylenediamine and the like 3 Secondary amine type and the like can be mentioned.

  The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is 2 mg-KOH / g or more, particularly 3 mg-KOH / g or more, and 100 mg-KOH / g in terms of amine value of the dispersant after the reaction. In the following, it is particularly preferable to control within the range of 80 mg-KOH / g or less. If the amine value is less than the above range, the dispersibility tends to decrease, and if it exceeds the above range, the developability tends to decrease, which is not preferable. In the case where the isocyanate group remains in the dispersion resin by the above-described reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the temporal stability of the dispersant becomes high.

  Here, in the black photosensitive resin composition of the present embodiment, the urethane dispersant is an aspect having a Sp value of 12.0 or more (first aspect) and an aspect having a molecular weight of 6,000 or more (second aspect). Of these, one of the aspects is satisfied, or both aspects are satisfied.

[First Aspect of Urethane Dispersant]
The urethane-based dispersant of the first aspect that can be used for the black photosensitive resin composition of the present embodiment has a Sp (Solubility Parameter) value of 10.0 or more. Moreover, as a urethane type dispersing agent of a 1st aspect, an Sp value is more preferable than 11.5, It is further more preferable to use an Sp value of 12.5 or more. Here, when the Sp value is out of the above range, the silica fine particles are not unevenly distributed on the glass interface of the substrate, and the effect of reducing the reflectance cannot be obtained well. Therefore, a black matrix capable of achieving both high light shielding properties and low reflectance. Can't get. In contrast, by using a urethane-based dispersant having an Sp value in the above range, the affinity between the dispersant adsorbed on the silica fine particles and the glass is high, and the silica fine particles are likely to be unevenly distributed on the glass side. Since the compatibility with the material carbon black is also excellent, a black matrix capable of achieving both high light-shielding properties and low reflectance can be obtained without using a multilayer structure.

  By the way, in general, the Sp value of a resin is dissolved in a good solvent having a known Sp value, and turbidity titration is performed with a poor solvent having a high Sp value and a poor solvent having a low Sp value. It is known that the value can be determined (Reference 1: CM Hansen J. Paint. Tech., 39 [505], 104 (1967) and Reference 2: Toshikatsu Kobayashi Colorant, 77 [4], 188-192 (2004)).

  On the other hand, in this embodiment, the value obtained by the following measuring method shall be used for Sp value of a urethane type dispersing agent. The method for measuring the Sp value of the urethane-based dispersant is not particularly limited to the measurement method described below as long as an equivalent value can be obtained, and a method different from the following method may be used. .

・ Measurement temperature: 20 ℃
Sample: Weigh 0.5 g of resin into a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
Good solvent: Acetone (Sp value by Hansen measurement: δg = 9.77)
-Poor solvent: hexane (Sp value: δpl = 7.24), deionized water (Sp value: δph = 23.50)
Turbidity measurement: A poor solvent was dropped using a 50 ml burette, hexane was dropped into the titration mixture, hexane volume fraction φpl at which turbidity occurred, and deionized water was dropped into the titration mixture, Record the deionized volume fraction φph at the point where turbidity occurred.

The Sp values δml (following formula 1) and δmh (following formula 2) of the mixing state at the turbidity produced by dropwise addition of hexane or deionized water can be expressed by volume averages of the Sp values of the poor solvent and the good solvent, respectively. .
(Formula 1): δml = φpl δpl + (1−φpl) δg
(Formula 2): δmh = φph δph + (1-φph) δg

Since the Sp value δpoly of the resin is an intermediate value between δml and δmh, it can be determined by the following equation 3.
(Formula 3): δpoly = (δml + δmh) / 2

  The urethane-based dispersant having the specific Sp value described above can be obtained by selecting various conditions in the manufacturing method described above, and by selecting the Sp value from each of the above-mentioned commercially available urethane-based dispersants. It can also be used.

[Second form of urethane-based dispersant]
The urethane dispersant of the second aspect that can be used in the black photosensitive resin composition of the present embodiment has a polystyrene-equivalent weight average molecular weight measured by GPC (Gel Permeation Chromatography) of 6,000 or more. Is. Moreover, as a urethane type dispersing agent of a 2nd aspect, it is more preferable to use a polystyrene conversion weight average molecular weight of 7,000 or more. Here, when the weight average molecular weight in terms of polystyrene of the urethane-based dispersant is out of the above range, the silica fine particles are not unevenly distributed on the glass interface of the substrate, and the effect of reducing the reflectance cannot be obtained well. In both cases, it is impossible to obtain a black matrix that can achieve both high light-shielding properties and low reflectance. In contrast, by using a urethane-based dispersant having a weight average molecular weight within the above range, the affinity between the dispersant adsorbed on the silica fine particles and the glass is high, and the silica fine particles are likely to be unevenly distributed on the glass side. Because of its excellent affinity with carbon black, it is possible to obtain a black matrix that can achieve both high light shielding properties and low reflectance without using a multilayer structure.

  The upper limit of the molecular weight of the urethane-based dispersant of the second aspect is not particularly limited, but is usually 200,000 or less, preferably 100,000 or less, more preferably 20,000 or less. . Here, if the upper limit of the molecular weight exceeds 200,000, the solubility is lowered, the dispersibility is inferior, and at the same time, the control of the reaction becomes difficult. For measurement of the weight average molecular weight of the urethane-based dispersant, HPLC 1515 and RI2114 manufactured by Nippon Waters can be used as a measuring device. As measurement conditions, shodex GPC KF803L 8 mm × 300 mm was used for the column, the column temperature was 40 ° C., the eluent was 1.0 ml / min of tetrahydrofuran (THF), and the injection amount of the sample to the column was 200 μl (dilution: 0. 1%), RI can be used as a detector.

  The urethane-based dispersant having the specific weight-average molecular weight described above can be obtained by selecting various conditions in the above-described production method, and the weight-average molecular weight is selected from each of the above-mentioned commercially available urethane-based dispersants. It can also be used.

  As described above, in the black photosensitive resin composition of the present embodiment, the specific silica fine particles and the specific urethane-based dispersant are contained in the black matrix-forming resin composition containing carbon black. The inventors of the present application have found that it is possible to achieve both high light-shielding properties and low reflectance for the first time by using such a specific urethane-based dispersant, and have reached the present invention. Actually, in Comparative Example 2 described later, an acrylic dispersant is used, but the effect of the present invention is not obtained. Note that polymer dispersants have various properties and physical properties such as the basic skeleton and polarity of the structure, and it is very difficult to predict the selection of combinations that can obtain specific performance, and a great deal of labor is required. Therefore, the combination of the present invention is quite unexpected.

"(D) Alkali-soluble resin"
Specific examples of the alkali-soluble resin of the black photosensitive resin composition of the present embodiment include, for example, alkyl such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. A resin synthesized with a molecular weight of about 5000 to 100,000 using about 3 to 5 types of monomers from acrylate or alkyl methacrylate, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene, or the like can be used. In addition, a resin in which an unsaturated double bond is added to a part of an acrylic resin is obtained by reacting a compound such as the above acrylic resin, an isocyanate group having an isocyanate group and at least one vinyl group, or methacryloyl isocyanate. The obtained photosensitive copolymer having an acid value of 50 to 150 can be preferably used from the viewpoint of heat resistance, developability and the like.

  Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting epoxy resin such as dihydroxybenzene type epoxy resin and (meth) acrylic acid can also be used. In particular, it is more preferable to use a cardo resin excellent in patterning characteristics and heat resistance. Examples of the cardo resin include V259-ME (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

"(E) polymerizable monomer"
Specific examples of the photopolymerizable monomer of the black photosensitive resin composition of the present embodiment include ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol. Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate Glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. These components may be used alone or as a mixture. Various modified (meth) acrylates, urethane (meth) acrylates, and the like can also be used. Among these, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, which have a small double bond equivalent and can achieve high sensitivity, are preferably used.

  The content of the photopolymerizable monomer is preferably in the range of 5 to 20% by weight and more preferably in the range of 10 to 15% by weight in the solid content of the black photosensitive resin composition. Here, when the content of the photopolymerizable monomer is less than 5% by weight, the sensitivity of the black photosensitive resin composition is insufficient, which is not preferable. On the other hand, when the content of the photopolymerizable monomer is in the above range, the sensitivity and the development speed of the black photosensitive resin composition can be adjusted to a level suitable for production, which is preferable.

"(F) Photopolymerization initiator"
As the photopolymerization initiator of the black photosensitive resin composition of the present embodiment, conventionally known compounds can be used as appropriate, but the sensitivity is increased even when used in a black photosensitive resin composition that does not transmit light. It is preferable to use an oxime ester compound that can achieve the above.

  Specific examples of the oxime ester compound include Irgacure OXE01, Irgacure OXE02 (trade names, both manufactured by BASF Japan), NCI-831 (trade names, manufactured by ADEKA), and the like.

  In the black photosensitive resin composition of the present embodiment, other photopolymerization initiators can be used in combination with the oxime ester-based compound. Specific examples of other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Acetophenone compounds such as 4-morpholinophenyl) -butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid Benzophenone compounds such as til, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6- Bis (trichloromethyl) ) -S-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl Triazine compounds such as-(piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4 Phosphine compounds such as 1,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquino And quinone compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. These photopolymerization initiators can be used alone or as a mixture of two or more at any ratio as required. Moreover, it is preferable that content of another photoinitiator is 0.1 to 1 weight% in solid content of a black photosensitive resin composition, and it is the range of 0.2 to 0.5 weight%. Is more preferable.

"(G) Solvent"
Specific examples of the solvent for the black photosensitive resin composition of the present embodiment include methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n amyl acetate, and propylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Nobutyl ether acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl Examples include ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactic acid ester, and ethyl ethoxypropionate.

"Other additives"
In the black photosensitive resin composition of the present embodiment, a surfactant for further improving the coating property, a silane coupling agent for improving the adhesion to the substrate, and the like can be used in combination.

  Specific examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic series such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates. Surfactants, cationic surfactants such as higher amine halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants A surfactant such as an agent and a silicone-based surfactant can be used. These may be used alone or in combination of two or more.

  Specific examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyldimethoxy. Epoxy silanes such as silane, methacryl silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-amino Aminosilanes such as propyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Isocyanate silanes such as preparative triethoxysilane and the like.

(Black matrix)
Next, the configuration of a black matrix as an embodiment to which the present invention is applied will be described. The black matrix of this embodiment is formed using the above-described black photosensitive resin composition.

  Further, the black matrix of the present embodiment has an optical density (ODD) of 3.0 / μm or more, and when formed on the transparent substrate, the micromatrix device is used from the transparent substrate side. And the reflectance of the SCI (measured by using a spectrocolorimeter from the transparent substrate side) measured with a spectrocolorimeter from the transparent substrate side is 5%. It is characterized by having either one or both of the characteristics of 0.0% or less. When the reflectance is less than or equal to these values, good display characteristics with little reflection due to external light can be obtained. When the reflectance is high, the reflection due to external light is remarkable, and the visibility of the display device is lowered.

  The film thickness of the black matrix is preferably in the range of 1.3 to 1.5 μm, and more preferably in the range of 1.35 to 1.45 μm. Here, when the thickness of the black matrix is less than 1.3 μm, the light shielding property is insufficient, which is not preferable. On the other hand, when the film thickness of the black matrix exceeds 1.5 μm, the flatness of the color filter is deteriorated, which may cause problems such as liquid crystal alignment failure and contrast reduction. On the other hand, when the film thickness of the black matrix is within the above range, it is preferable because a high light shielding property of OD3.9 or more can be obtained without impairing the flatness of the color filter.

  The black matrix of the present embodiment has an OD value of 3.0 / μm or more, and has a high light shielding property of OD 4.0 or more in a film thickness range of 1.3 to 1.5 μm, but has a reflectivity. It is characterized by being low. As described above, the hydrophobic silica having a lower refractive index than carbon black can be obtained by optimizing the surface properties and primary particle size of the carbon black and the hydrophobic silica fine particles, and further selecting the dispersant. The fine particles can be unevenly distributed to the interface with the glass to some extent, and the reflectance is considered to be reduced by reducing the difference in refractive index between the glass and the black matrix.

  The substrate for forming the black matrix is not particularly limited, but a substrate having a certain transmittance with respect to visible light is preferable, and a substrate (transparent substrate) having a transmittance of 80% or more is more preferable. preferable. Specific examples of such a substrate include various glass substrates such as quartz glass, borosilicate glass, and aluminosilicate glass, and various plastic substrates such as polyester resins and polyolefin resins.

  Next, the manufacturing method of the black matrix of this embodiment is demonstrated. Formation of the black matrix of this embodiment is performed as follows. First, a coating film of the black photosensitive resin composition of the present embodiment described above is formed on a substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like.

  Next, after removing the residual solvent in the coating film by drying under reduced pressure and pre-baking treatment, exposure is performed through a photomask having a predetermined pattern. As the exposure light source, for example, a conventionally known light source such as an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used.

  Next, it develops using the developing solution which consists of alkaline aqueous solution. Examples of the developer comprising the alkaline aqueous solution include a potassium carbonate aqueous solution, a sodium carbonate aqueous solution, or a sodium hydrogen carbonate aqueous solution, and those obtained by adding an appropriate surfactant to these aqueous solutions. After development, the substrate is washed with water, dried and baked to obtain a black matrix substrate on which a predetermined pattern is formed.

(Color filter)
Next, the configuration of a color filter that is an embodiment to which the present invention is applied will be described. The color filter of the present embodiment includes a transparent substrate and the above-described black matrix provided on the transparent substrate. More specifically, the color filter of the present embodiment includes a black matrix substrate composed of a transparent substrate and a black matrix, and red, green, and blue colored pixels formed in the openings of the black matrix. Features.

  Here, FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a color filter which is an embodiment to which the present invention is applied. As shown in FIG. 1, the color filter 12 of the present embodiment has a black matrix 2 formed on a transparent substrate 1. Further, red colored pixels 3 (R), green colored pixels 3 (G), and blue colored pixels 3 (B) are respectively formed in the openings of the black matrix 2. Note that a transparent protective film (not shown) may be provided on the colored pixels 3 as necessary.

  Specific examples of the red pigment used for forming the red colored pixel (red pixel) 3 (R) include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 279 and the like. It is also possible to use a yellow pigment and an orange pigment in combination in order to adjust the hue of the red pixel.

  Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214, and the like.

  Specific examples of the orange pigment include C.I. I. Pigment orange 38, 43, 66, 68, 69, 71, 73 and the like.

  Specific examples of the green pigment used for forming the green colored pixel (green pixel) 3 (G) include C.I. I. Pigment green 7, 10, 36, 37, 58, and the like. It is also possible to use a yellow pigment in combination to adjust the hue of the green pixel. As a yellow pigment, what was illustrated as a yellow pigment for adjusting the hue of the said red pixel can be used suitably.

  Specific examples of the blue pigment used for forming the blue colored pixel (blue pixel) 3 (B) include C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Further, a purple pigment can be used in combination to adjust the hue of the blue pixel.

  Specific examples of purple pigments include C.I. I. Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.

  Various dyes can be used to adjust the hue of the red, green, and blue pixels.

  Next, the manufacturing method of the color filter 12 of this embodiment is demonstrated. The production of the color filter of this embodiment can be performed as follows. First, a coating film of a colored photosensitive resin composition containing a pigment corresponding to each colored pixel of a color filter is formed on the black matrix substrate. After drying, exposure is performed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. By performing a series of operations using, for example, a colored photosensitive resin composition containing red, green, and blue color materials, a color filter having red, green, and blue pixels can be manufactured.

(Liquid crystal display device)
Next, a configuration of a liquid crystal display device according to an embodiment to which the present invention is applied will be described. The liquid crystal display device of the present embodiment includes the above-described color filter.

  Here, FIG. 2 is a schematic cross-sectional view showing an example of the configuration of a liquid crystal display device which is an embodiment to which the present invention is applied. As shown in FIG. 2, the liquid crystal display device 4 of the present embodiment includes a pair of transparent substrates (a first transparent substrate 5 and a second transparent substrate 6) arranged to face each other and sealed between them. The liquid crystal compound 7 is generally configured.

  Specific examples of the liquid crystal compound 7 include TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertically Aligned), and OCB (Optically Bold). . Among these, those corresponding to each liquid crystal alignment mode can be used as appropriate.

  As shown in FIG. 2, TFT elements 8 are arranged on the inner surface of the first transparent substrate 5, that is, the surface facing the second transparent substrate 6, and a transparent element made of, for example, ITO is formed thereon. An electrode layer 9 is formed. Furthermore, an alignment film 10 is provided on the transparent electrode layer 9. On the other hand, a polarizing plate 11 is formed on the outer surface of the transparent substrate 5, that is, on the surface opposite to the surface facing the second transparent substrate 6.

  On the other hand, the color filter 12 according to the present embodiment described above is formed on the inner surface of the second transparent substrate 6, that is, the surface facing the first transparent substrate 5. A transparent protective film (not shown) is formed so as to cover the color filter 12, and further, a transparent electrode layer 13 made of, for example, ITO is formed thereon, and the alignment film 14 covers the transparent electrode layer 13. Is provided. On the other hand, a polarizing plate 15 is formed on the outer surface of the transparent substrate 6, that is, the surface opposite to the surface facing the first transparent substrate 5. As shown in FIG. 2, a backlight unit 16 is provided below the polarizing plate 11.

  As described above, according to the liquid crystal display device of the present embodiment, the color filter used in the liquid crystal display device, the black matrix used in the color filter, and the black photosensitive resin composition used as a raw material for the black matrix, a multilayer structure is used. Black photosensitive resin composition, black matrix, color filter using the same, and liquid crystal using them, as a raw material for a black matrix capable of achieving both high light-shielding properties and low reflectivity without cost A display device can be provided.

  Further, according to the liquid crystal display device of this embodiment, the reflectance of the black matrix of the color filter is low, and thus visibility is not deteriorated by reflection of external light. In addition, since the optical density of the black matrix is high and it has sufficient light-shielding properties, good display characteristics with high contrast can be obtained.

  Furthermore, according to the black photosensitive resin composition of this embodiment, since it can be applied to a conventional color filter manufacturing process, the productivity is high and the manufacturing cost can be reduced.

<Second Embodiment>
Next, an organic electroluminescence display device according to a second embodiment to which the present invention is applied will be described. In the organic electroluminescence display device of this embodiment, the liquid crystal display device of the first embodiment and the color filter have the same configuration. For this reason, the same reference numerals are assigned to the color filters that are the same components as in the first embodiment, and descriptions thereof are omitted.

(Organic electroluminescence display)
FIG. 3 is a schematic cross-sectional view showing an example of the configuration of an organic electroluminescence display device according to a second embodiment to which the present invention is applied. As shown in FIG. 3, the organic electroluminescence display device 17 of the present embodiment has an anode 18, a hole transport layer 19, an organic layer 20, an electron transport layer 21, and an anode 22 stacked in this order on the transparent substrate 1. The organic electroluminescent element, the transparent substrate 5 on which the color filter 12 is formed, and the sealing material 23 are schematically configured. Moreover, the organic electroluminescent display device 17 of this embodiment seals the said organic electroluminescent element with the transparent substrate 5 in which the sealing agent 23 and the color filter 12 were formed.

  The electroluminescence display device 17 according to the present embodiment has a low reflectance due to external light reflection because the black matrix of the color filter 12 has a low reflectance as in the liquid crystal display device 4 according to the first embodiment described above. There is nothing. In addition, since the black matrix has sufficient light shielding properties, good display characteristics with high contrast can be obtained.

  The technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Black photosensitive resin composition No. used for the Example and the comparative example. 1-No. 10 was adjusted as follows. In addition, black photosensitive resin composition No. 1-No. Tables 1 and 2 show the blending ratios of the ten colorants.

<Adjustment of black pigment dispersion>
[Black pigment dispersion No. Adjustment of 1]
16 parts by weight of carbon black A (with resin coating, average primary particle size 24 nm, DBP oil absorption 57 ml / 100 g, pH 3.5, powder resistance 10.6), hydrophobic silica (average primary particle size 12 nm, purity> 99) .9%, specific surface area 200 m ² / g) 4 parts by weight, dispersant A (Sp value 8.6, polyurethane polymer, solid conversion amine value 25 mgKOH / g, weight average molecular weight about 7300) 5. 0 parts by weight (in terms of solid content) and 75.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and stirred using a bead mill, and a black pigment dispersion No. 1 containing carbon black and hydrophobic silica was added. 1 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%).

[Black pigment dispersion No. Adjustment of 2]
18 parts by weight of carbon black A, 2 parts by weight of hydrophobic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), and 5.0 parts by weight of dispersant A (in terms of solid content) ), Propylene glycol monomethyl ether acetate was added to 75.0 parts by weight, mixed and stirred using a bead mill, and black pigment dispersion No. 1 containing carbon black and hydrophobic silica. 2 (solid content 25.0%, carbon black weight concentration in solid content 72.0%, silica fine particle weight concentration 8.0%) was obtained.

[Black pigment dispersion No. Adjustment of 3]
14 parts by weight of carbon black A, 6 parts by weight of hydrophobic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), and 5.0 parts by weight of dispersant A (in terms of solid content) ), Propylene glycol monomethyl ether acetate was added to 75.0 parts by weight, mixed and stirred using a bead mill, and black pigment dispersion No. 1 containing carbon black and hydrophobic silica. 3 (solid content 25.0%, carbon black weight concentration in solid content 56.0%, silica fine particle weight concentration 24.0%) was obtained.

[Black pigment dispersion No. Adjustment of 4]
Carbon black B (no resin coating, average primary particle size 29 nm, DBP oil absorption 64 ml / 100 g, pH 3.5, powder resistance 2.2) 16 parts by weight, hydrophobic silica (average primary particle size 12 nm, purity> 99 0.9%, specific surface area 200 m ² / g) is added to 4 parts by weight, dispersant A is added to 5.0 parts by weight (in terms of solid content), and propylene glycol monomethyl ether acetate is added to 75.0 parts by weight. The black pigment dispersion No. containing carbon black and hydrophobic silica was mixed and stirred. 4 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%).

[Black pigment dispersion No. Adjustment of 5]
16 parts by weight of carbon black A, 4 parts by weight of hydrophobic silica (average primary particle size 40 nm, purity> 99.9%, specific surface area 50 m ² / g), and 5.0 parts by weight of dispersant A (in terms of solid content) ), Propylene glycol monomethyl ether acetate was added to 75.0 parts by weight, mixed and stirred using a bead mill, and black pigment dispersion No. 1 containing carbon black and hydrophobic silica. 5 (solid content: 25.0%, carbon black weight concentration in solid content: 64.0%, silica fine particle weight concentration: 16.0%).

[Black pigment dispersion No. Adjustment of 6]
16 parts by weight of carbon black A, 4 parts by weight of hydrophobic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), dispersant B (Sp value is 13.0, polyurethane type) Polymer compound, solid conversion amine value 33 mgKOH / g, weight average molecular weight about 2600) is added to 5.0 parts by weight (solid conversion), propylene glycol monomethyl ether acetate is added to 75.0 parts by weight, and mixed using a bead mill. The black pigment dispersion No. containing carbon black and hydrophobic silica was stirred. 6 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%) was obtained.

[Black pigment dispersion No. Adjustment of 7]
Carbon black A is added to 20 parts by weight, Dispersant A is added to 5.0 parts by weight (in terms of solid content), and propylene glycol monomethyl ether acetate is added to 75.0 parts by weight. Black pigment dispersion No. 7 (solid content 25.0%, carbon black weight concentration in solid content 80.0%) was obtained.

[Black pigment dispersion No. Adjustment of 8]
16 parts by weight of carbon black A, 4 parts by weight of hydrophobic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), and 5 of dispersant C (polyacrylic polymer compound) 0.0 part by weight (in terms of solid content) and 75.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and stirred using a bead mill, and the black pigment dispersion No. 1 containing carbon black and hydrophobic silica was added. 8 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%) was obtained.

[Black pigment dispersion No. 9 adjustment]
16 parts by weight of carbon black A, 4 parts by weight of hydrophilic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), 5.0 parts by weight of dispersant A (in terms of solid content) ), Propylene glycol monomethyl ether acetate was added to 75.0 parts by weight, mixed and stirred using a bead mill, and black pigment dispersion No. 1 containing carbon black and hydrophilic silica. 9 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%) was obtained.

[Black pigment dispersion No. Adjustment of 10]
16 parts by weight of carbon black B, 4 parts by weight of hydrophilic silica (average primary particle size 12 nm, purity> 99.9%, specific surface area 200 m ² / g), and 5.0 parts by weight of dispersant A (in terms of solid content) ), Propylene glycol monomethyl ether acetate was added to 75.0 parts by weight, mixed and stirred using a bead mill, and black pigment dispersion No. 1 containing carbon black and hydrophilic silica. 10 (solid content 25.0%, carbon black weight concentration in solid content 64.0%, silica fine particle weight concentration 16.0%).

<Adjustment of black photosensitive resin composition>
[Black photosensitive resin composition No. Adjustment of 1]
Dipentaerythritol penta / hexaacrylate mixture (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) for 5.08 g of bisphenolfluorene type epoxy resin (“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd. 56.5%) 0 .92 g, 0.40 g of photopolymerization initiator (“NCI-831” manufactured by ADEKA), 1.00 g of 1% propylene glycol monomethyl acetate solution of surface conditioner (“BYK-323” manufactured by Big Chemie), black pigment dispersion No. No. 1 39.20 g and propylene glycol monomethyl ether acetate 53.40 g were added and stirred well. 100 g (solid content: 14.0%, carbon black weight concentration in solid content: 44.8%, silica fine particle weight concentration: 11.2%) was obtained.

[Black photosensitive resin composition No. Adjustment of 2]
Dipentaerythritol penta / hexaacrylate mixture (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) for 5.85 g of bisphenolfluorene type epoxy resin (“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd. 56.5%) 0 .98 g, 0.43 g of photopolymerization initiator (“NCI-831” manufactured by ADEKA), 1.00 g of 1% propylene glycol monomethyl acetate solution of surface conditioner (“BYK-323” manufactured by Big Chemie), black pigment dispersion No. No. 2 of 37.10 g and propylene glycol monomethyl ether acetate 54.64 g were added and stirred well. 2 (solid content 14.0%, carbon black weight concentration in solid content 47.7%, silica fine particle weight concentration 5.3%) was obtained.

[Black photosensitive resin composition No. Adjustment of 3]
Dipentaerythritol penta / hexaacrylate mixture (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) with respect to 3.82 g of bisphenol fluorene type epoxy resin (“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd. 56.5%) 0 .82 g, 0.36 g of photopolymerization initiator (ADEKA "NCI-831"), 1.00 g of a 1% propylene glycol monomethyl acetate solution of a surface conditioner ("BYK-323" manufactured by Big Chemie), black pigment dispersion No. 3 and 42.63 g of propylene glycol monomethyl ether acetate were added and stirred well. 3 (solid content 14.0%, carbon black weight concentration in the solid content 42.6%, silica fine particle weight concentration 18.3%).

[Black photosensitive resin composition No. Adjustment of 4]
As the black pigment dispersion, black pigment dispersion No. 4 except that black photosensitive resin composition No. 4 is used. 1 and the black photosensitive resin composition No. 4 (solid content: 14.0%, carbon black weight concentration in the solid content: 44.8%, silica fine particle weight concentration: 11.2%) was obtained.

[Black photosensitive resin composition No. Adjustment of 5]
As the black pigment dispersion, black pigment dispersion No. Except for using No. 5, the black photosensitive resin composition No. 1 and the black photosensitive resin composition No. 5 (solid content: 14.0%, carbon black weight concentration in the solid content: 44.8%, silica fine particle weight concentration: 11.2%).

[Black photosensitive resin composition No. Adjustment of 6]
As the black pigment dispersion, black pigment dispersion No. Except for using the black photosensitive resin composition no. 1 and the black photosensitive resin composition No. 6 (solid content: 14.0%, carbon black weight concentration in the solid content: 44.8%, silica fine particle weight concentration: 11.2%).

[Black photosensitive resin composition No. Adjustment of 7]
Dipentaerythritol penta / hexaacrylate mixture (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) 1 against 7.90 g of bisphenol fluorene type epoxy resin (“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd. 56.5%) 1 .15 g, 0.50 g of photopolymerization initiator (“NCI-831” manufactured by ADEKA), 1.00 g of 1% propylene glycol monomethyl acetate solution of a surface conditioner (“BYK-323” manufactured by Big Chemie), black pigment dispersion No. No. 7 (31.50 g) and propylene glycol monomethyl ether acetate (57.95 g) were added and stirred well. 7 (solid content 14.0%, carbon black pigment concentration in the solid content 45.0%) was obtained.

[Black photosensitive resin composition No. Adjustment of 8]
As the black pigment dispersion, black pigment dispersion No. Except for using the black photosensitive resin composition no. 1 and the black photosensitive resin composition No. 8 (solid content 14.0%, carbon black weight concentration in the solid content 44.8%, silica fine particle weight concentration 11.2%) was obtained.

[Black photosensitive resin composition No. 9 adjustment]
As the black pigment dispersion, black pigment dispersion No. Except for using No. 9, the black photosensitive resin composition No. 1 and the black photosensitive resin composition No. 9 (solid content: 14.0%, carbon black weight concentration in the solid content: 44.8%, silica fine particle weight concentration: 11.2%) was obtained.

[Black photosensitive resin composition No. Adjustment of 10]
As the black pigment dispersion, black pigment dispersion No. Except for using the black photosensitive resin composition no. 1 and the black photosensitive resin composition No. 100 g (solid content 14.0%, carbon black weight concentration in the solid content 44.8%, silica fine particle weight concentration 11.2%) was obtained.

<Production of black matrix substrate>
Using a spin coater, the number of rotations was adjusted so that the film thickness after baking was 1.35 μm, and the above black photosensitive resin composition No. 1 coating film was formed. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, 100 mJ / cm ² of ultraviolet light was applied to the coating film of the black photosensitive resin composition using a super high pressure mercury lamp (illuminance 26 mW / cm ² ) through a photomask having a predetermined pattern. Subsequently, development was performed with a 2.5 wt% sodium carbonate aqueous solution, and baking was performed in a clean oven at 230 ° C. for 20 minutes, thereby producing a black matrix substrate 1. The same operation was repeated for the black photosensitive resin composition No. 2-No. 10 were used to prepare black matrix substrates 2 to 10.

[Adjustment of red photosensitive resin composition]
To 9.33 g of propylene glycol monomethyl ether acetate solution (solid content 20.0%) of acrylic resin, 3.82 g of dipentaerythritol penta / hexaacrylate mixture (“M402” manufactured by Toagosei Co., Ltd.), photopolymerization initiator 1 ( BASF Japan “IRGACURE 379”) 0.88 g, photopolymerization initiator 2 (Nippon Kayaku “KAYACURE DETX-S”) 0.15 g, C.I. I. Pigment Red 254 in propylene glycol monomethyl ether acetate dispersion (solid content 20.0%, pigment concentration in solid content 70.0% by weight) 16.81 g, C.I. I. Pigment Red 177 propylene glycol monomethyl acetate dispersion (solid content 20.0%, pigment concentration in solid content 60.0% by weight) 19.60 g and propylene glycol monomethyl ether acetate 49.41 g were added and stirred well. 100 g (solid content: 14.0%, pigment concentration: 33.6% by weight) of the photosensitive resin composition was obtained.

[Adjustment of green photosensitive resin composition]
To 13.57 g of a propylene glycol monomethyl ether acetate solution (solid content 20.0%) of acrylic resin, 2.06 g of a dipentaerythritol penta / hexaacrylate mixture (“M402” manufactured by Toagosei Co., Ltd.), photopolymerization initiator 1 ( BASF Japan "IRGACURE 379") 0.90g, photopolymerization initiator 2 (ADEKA "Adekaoptomer N-1919") 0.10g, C.I. I. Pigment Green 36 propylene glycol monomethyl ether acetate dispersion (solid content 20.0%, pigment concentration in solid content 75.0% by weight) 35.28 g, C.I. I. Pigment Yellow 150 propylene glycol monomethyl acetate dispersion (solid content: 20.0%, pigment concentration in solid content: 50.0% by weight) 5.85 g and propylene glycol monomethyl ether acetate 42.24 g were added and stirred well. 100 g (solid content: 14.0%, pigment concentration: 42.0% by weight) of the photosensitive resin composition was obtained.

[Adjustment of blue photosensitive resin composition]
3.99 g of dipentaerythritol penta / hexaacrylate mixture (“M402” manufactured by Toagosei Co., Ltd.), photopolymerization initiator 1 (13.96 g of propylene glycol monomethyl ether acetate solution (solid content 20.0%) of acrylic resin, BASF Japan "IRGACURE 379") 1.40 g, photopolymerization initiator 2 (Nippon Kayaku "KAYACURE DETX-S") 0.35 g, C.I. I. Pigment Blue 15: 6 propylene glycol monomethyl ether acetate dispersion (solid content 20.0%, pigment concentration in solid content 70.0% by weight) 23.00 g, C.I. I. 4.35 g of a propylene glycol monomethyl acetate dispersion of Pigment Violet 23 (solid content 20.0%, pigment concentration 50.0 wt% in solid content) and 52.96 g of propylene glycol monomethyl ether acetate were added and stirred well. 100 g (solid content: 14.0%, pigment concentration: 26.1% by weight) of the photosensitive resin composition was obtained.

<Manufacture of color filters>
A coating film of the red photosensitive resin composition was formed on the black matrix substrate 1 by spin coating. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, 100 mJ / cm ² of ultraviolet light is applied to the red photosensitive resin composition coating film using a super high pressure mercury lamp (illuminance 26 mW / cm ² ) through a photomask having a pattern corresponding to the opening of the black matrix. Irradiated. Subsequently, development was performed with a 2.5% by weight aqueous sodium carbonate solution, and baking was performed in a clean oven at 230 ° C. for 20 minutes to form red pixels on the black matrix substrate 1. A color filter 1 in which red, green, and blue colored pixels are formed on the black matrix substrate 1 is obtained by performing the same operation using the green and blue photosensitive resin compositions. Red, green and blue colored pixels were formed on the black matrix substrates 2 to 10 in the same manner to obtain color filters 2 to 10.

<Manufacture of liquid crystal display devices>
An ITO transparent electrode was formed on the film surface of the obtained color filter 1 by a sputtering method, and a polyimide alignment film was formed thereon and subjected to rubbing treatment. Subsequently, a polyimide alignment film was similarly formed on the counter glass substrate on which the TFT array and the pixel electrode were formed, and a rubbing process was performed. The color filter and the counter glass substrate were bonded together with a sealant leaving the liquid crystal injection port, and the liquid crystal composition was injected from the injection port. After the injection, the injection port was sealed. A polarizing plate was attached to both sides of the obtained liquid crystal cell, and a backlight unit was attached to obtain a liquid crystal display device 1. The same operation was performed using the color filters 2 to 10 to obtain liquid crystal display devices 2 to 10.

<Evaluation method>
(OD value evaluation)
The OD values of the black matrix substrates 1 to 10 were measured with a microspectrophotometer (“LCF-1100” manufactured by Otsuka Electronics Co., Ltd.). The OD value per 0 μm was calculated.
(Reflectance evaluation)
The reflectance from the glass surfaces of the black matrix substrates 1 to 10 was measured with a microspectrophotometer. The reflectance of SCI (indicating the sum of regular reflection light and diffuse reflection light) was measured for the same substrate using a spectrocolorimeter (“CM-2500D” manufactured by Konica Minolta). The measurement conditions were illumination / light receiving optical system: d / 8 ° and measurement diameter: Φ8 mm. The evaluation results are shown in Table 3 and Table 4, respectively.

  From Tables 3 and 4, it can be seen that a black matrix substrate having a high light-shielding property and a low reflectance was obtained by the present invention. It was confirmed that the liquid crystal display device and the organic electroluminescence display device using the color filter provided with the black matrix substrate had little external light reflection and good visibility was obtained.

DESCRIPTION OF SYMBOLS 1, 5, 6 ... Transparent substrate 2 ... Black matrix 3 ... Colored pixel 4 ... Liquid crystal display device 7 ... Liquid crystal compound 8 ... TFT element 9, 13 ... Transparent electrode 10 , 14 ... Alignment films 11, 15 ... Polarizing plate 12 ... Color filter 16 ... Backlight unit 17 ... Organic electroluminescence display device 18 ... Anode 19 ... Hole transport layer 20 ... Organic light emitting layer 21 ... Electron transport layer 22 ... Cathode 23 ... Sealant

Claims (7)

(A) carbon black;
(B) hydrophobic silica fine particles;
(C) a dispersant;
(D) an alkali-soluble resin;
(E) a polymerizable monomer;
(F) a photoinitiator;
(G) a black photosensitive resin composition containing at least a solvent,
The weight ratio (A) / (B) between the (A) carbon black and the (B) hydrophobic silica fine particles is in the range of 1.5 to 9.0,
Wherein (C) dispersing agent, Ri urethane dispersant der satisfying either or both of the Sp value 12.0 or higher and molecular weight of 6,000 or more,
The (B) hydrophobic silica fine particles are
A silyl group capable of condensing with a silanol group on the silica surface;
A surface treated with a compound having one or more silyl groups in one molecule, among silyl groups capable of forming functional groups capable of condensing with silanol groups on the silica surface by hydrolysis. black photosensitive resin composition characterized Rukoto Oh.   The black photosensitive resin composition according to claim 1, wherein the (A) carbon black is coated with a resin. A black matrix formed using the black photosensitive resin composition according to claim 1 . A black matrix substrate comprising: a transparent substrate; and the black matrix according to claim 3 formed on the transparent substrate,
The optical density (OD value) is 3.0 / μm or more,
When formed on a transparent substrate,
The reflectance measured using a microspectroscope from the transparent substrate side is 1.0% or less,
Reflectance of SCI system was measured using a colorimeter spectral from the transparent substrate side, and characteristics to be 5.0% or less, of, features and be Lube to have one or both of properties Rack matrix substrate . A transparent substrate;
A color filter comprising: the black matrix according to claim 3 provided on the transparent substrate. A liquid crystal display device comprising the color filter according to claim 5 . An organic electroluminescence display device comprising the color filter according to claim 5 .

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