JP6641687B2 - Method for manufacturing color filter and method for manufacturing black matrix substrate - Google Patents

Description

  The present invention relates to a color filter and a black matrix substrate used for a display device such as a liquid crystal display device and an organic EL display device.

In recent years, with the development of display devices, demand for flat panel displays such as liquid crystal display devices and organic EL display devices has been increasing. In recent years, in addition to televisions and personal computers, multifunctional terminals such as smartphones and tablet terminals have become popular, and the market for flat panel displays has been expanding.
In such a situation, high quality members are desired for the members constituting the flat display. In particular, in a flat panel display, since the quality of a color filter affects display quality itself, high quality and design are required.

A general color filter has a transparent substrate, a light-shielding layer formed in a pattern on the transparent substrate, and a coloring layer formed in an opening of the light-shielding layer. When incorporating a color filter into a flat panel display, for example, the color filter is arranged such that the transparent substrate of the color filter is on the viewer side. Flat panel displays have a problem that they are easily affected by external light and visibility is reduced due to external light reflection.
Therefore, it has been proposed to use a light-shielding resin layer in which a black color material such as carbon black or titanium black is dispersed in a binder resin as the low-reflection light-shielding layer. However, the reflectance of the light-shielding resin layer is limited, and the effect of reducing external light reflection is not sufficient.

  Recently, high definition has been demanded, and miniaturization of pixels has been required. As the definition increases, the ratio of the area occupied by the light-shielding layer in the display area increases, and accordingly, the influence of external light reflection on the light-shielding layer increases.

  Patent Documents 1 and 2 propose to provide a reflection control layer between a transparent substrate and a light-shielding resin layer for the purpose of reducing external light reflection in the light-shielding layer. Patent Literature 1 proposes using a coloring layer constituting a color filter as a reflection control layer, and Patent Literature 2 uses a coloring layer containing a blue color material or a black color material as a reflection control layer. It has been proposed. Further, in Patent Document 3, for the purpose of improving the tightness of the black of the frame light-shielding portion in the non-display area indoors and outdoors, under indoor light, and under sunlight and giving a sense of quality, a resin is used as the frame light-shielding portion. It has been proposed to use a light-shielding resin layer in which a pigment is dispersed as a component, and to form a chrome-based antireflection film between a transparent substrate and a chrome-based light-shielding layer in a frame light-shielding portion.

  However, in recent years, it has been required that the light-shielding layer display a tighter black color, and there is a limit in reducing the reflectance of the light-shielding resin layer and the coloring layer (reflection control layer). Further, as the definition increases, it is required to reduce the line width of the light-shielding layer. However, depending on the type of the coloring layer (reflection control layer), it may be difficult to reduce the line width.

  It should be noted that reduction of external light reflection in the light-shielding layer is not limited to the color filter, but is similarly required, for example, in a black matrix substrate having a transparent substrate and a light-shielding layer and used for a display device for monochrome display. ing.

WO 2013/008679 pamphlet JP 2014-25986 A JP 2013-130677 A

  In view of the above circumstances, the present inventors have conducted intensive research. In a conventional color filter, one of the causes of external light reflection on the light-shielding layer is that the refractive index of the light-shielding layer is higher than the refractive index of the transparent substrate, and the refractive index difference is large. Therefore, the present inventors have attempted to form a predetermined refractive index adjusting layer between the transparent substrate and the light-shielding layer, and reduce the reflection of external light by utilizing the light interference effect.

As the refractive index adjusting layer, for example, an organic layer containing a resin can be considered. The organic layer used for the refractive index adjusting layer needs to be formed to have a thickness on the order of nanometers in order to impart desired optical characteristics such as a refractive index.
However, when the refractive index adjusting layer is formed on the entire surface of the transparent substrate, that is, when the refractive index adjusting layer is formed in the opening of the light shielding layer, the transmittance of the pixel of the color filter is reduced, and the desired color filter It has been found that it is difficult to exhibit the display characteristics of.

  Then, the present inventors tried to form a refractive index adjustment layer composed of an organic layer in a pattern only between the transparent substrate and the light shielding layer by using a photolithography method. However, in this case, the coating of the resin composition for the refractive index adjustment layer containing the photocurable resin composition needs to be thinned, so that during pattern exposure, the coating is cured with oxygen on the coating surface. There is a problem that inhibition occurs and patterning is difficult.

  Therefore, the present invention provides a color filter having a refractive index adjustment layer containing a photocurable resin, a black matrix substrate, a display device using the same, and a refractive index adjustment layer containing a photocurable resin, which is formed in a pattern. It is a main object of the present invention to provide a method for manufacturing a color filter and a method for manufacturing a black matrix substrate, which can be performed.

  In order to achieve the above object, the inventors of the present invention conducted further intensive studies, and found that the entire surface of the coating film of the resin composition for the refractive index adjusting layer was exposed to light in the atmosphere to adjust the refractive index, which was semi-cured. By forming the layer forming layer, even if the light-shielding layer resin composition is applied on the coating film, the constituent components are not mixed, and further, the coating film of the light-shielding layer resin composition is subjected to pattern exposure. After that, when developing, it was found that the layer for forming the refractive index adjusting layer at the opening of the light-shielding layer could be removed using the light-shielding layer as a mask, and the present invention was completed.

  That is, the present invention includes a transparent substrate and a photocurable resin formed in a pattern on the transparent substrate and cured by a photocurable resin composition, and the curing of the photocurable resin composition is inhibited by oxygen. A refractive index adjustment layer having a thickness to be produced, a light shielding layer formed on the refractive index adjustment layer in the same pattern as the refractive index adjustment layer, containing a binder resin and a black color material, and A color filter comprising: a color layer formed in an opening of a light-shielding portion.

  According to the present invention, since the refractive index adjustment layer and the light shielding layer are formed in the same pattern, a color filter having a refractive index adjustment layer formed in a pattern and including a photocurable resin can be obtained. it can. Further, the color filter of the present invention can reduce the reflection of external light on the light-shielding layer, and can improve the transmittance at the pixel.

  The present invention includes a transparent substrate and a photocurable resin which is formed in a pattern on the transparent substrate and in which the photocurable resin composition is cured, and in which the curing of the photocurable resin composition is inhibited by oxygen. A black matrix comprising: a refractive index adjustment layer having: and a light shielding layer formed on the refractive index adjustment layer in the same pattern as the refractive index adjustment layer and containing a binder resin and a black color material. Provide a substrate.

  According to the present invention, since the refractive index adjustment layer and the light shielding layer are formed in the same pattern, the black matrix substrate is formed in a pattern and has a refractive index adjustment layer containing a photocurable resin. Can be. Further, the black matrix substrate of the present invention can reduce the reflection of external light on the light-shielding layer, and can improve the transmittance of the pixels.

  The present invention includes a transparent substrate and a photocurable resin which is formed in a pattern on the transparent substrate and in which the photocurable resin composition is cured, and in which the curing of the photocurable resin composition is inhibited by oxygen. A light-shielding layer formed in the same pattern as the refractive-index adjustment layer on the refractive-index adjustment layer, containing a binder resin and a black color material, and the light-shielding portion on the transparent substrate And a color filter having a coloring layer formed in the opening of the display device.

  According to the present invention, a display device capable of performing high-quality display can be provided by including the above color filter.

  The present invention includes a transparent substrate and a photocurable resin which is formed in a pattern on the transparent substrate and in which the photocurable resin composition is cured, and in which the curing of the photocurable resin composition is inhibited by oxygen. Having a black matrix substrate having a light-shielding layer formed on the refractive index adjustment layer in the same pattern as the refractive index adjustment layer and containing a binder resin and a black color material. A display device is provided.

  According to the present invention, a display device capable of performing high-quality display can be provided by including the black matrix substrate.

  The present invention provides a coating film having a thickness in which curing of the photocurable resin composition is inhibited by applying the resin composition for a refractive index adjustment layer containing the photocurable resin composition on a transparent substrate. Forming, the entire surface of the coating film is exposed in the air, a refractive index adjustment layer forming layer forming step of forming a semi-cured refractive index adjustment layer forming layer of the photocurable resin composition, A light-shielding layer composition containing a photosensitive resin composition and a black coloring material is applied on the refractive index adjusting layer-forming layer to form a light-shielding layer-forming layer, and then the light-shielding layer-forming layer is formed. An exposure step of pattern exposure, and by continuously developing the exposed light-shielding layer forming layer and the refractive index adjusting layer forming layer, form a light-shielding layer and a refractive index adjusting layer in the same pattern. A patterning step and an opening of the light-shielding layer on the transparent substrate To provide a method for manufacturing a color filter; and a colored layer forming step of forming a colored layer.

According to the present invention, a layer for forming a refractive index adjustment layer in which a photocurable resin composition is semi-cured can be obtained by having a step of forming a layer for forming a refractive index adjustment layer. Accordingly, the light-shielding layer forming layer can be formed by applying the light-shielding layer resin composition on the refractive index adjusting layer forming layer, and the developed light-shielding layer is developed when the pattern-exposed light-shielding layer forming layer is developed. Unnecessary portions of the layer for forming the refractive index adjusting layer can be developed using the layer as a mask.
Therefore, the refractive index adjusting layer can be formed in a pattern using the photocurable resin composition.

  The present invention provides a coating film having a thickness in which curing of the photocurable resin composition is inhibited by applying the resin composition for a refractive index adjustment layer containing the photocurable resin composition on a transparent substrate. Forming, the entire surface of the coating film is exposed in the air, a refractive index adjustment layer forming layer forming step of forming a semi-cured refractive index adjustment layer forming layer of the photocurable resin composition, A light-shielding layer composition containing a photosensitive resin composition and a black coloring material is applied on the refractive index adjusting layer-forming layer to form a light-shielding layer-forming layer, and then the light-shielding layer-forming layer is formed. An exposure step of pattern exposure, and by continuously developing the exposed light-shielding layer forming layer and the refractive index adjusting layer forming layer, form a light-shielding layer and a refractive index adjusting layer in the same pattern. Black mat having a patterning step To provide a method of manufacturing a box board.

According to the present invention, a layer for forming a refractive index adjustment layer in which a photocurable resin composition is semi-cured can be obtained by having a step of forming a layer for forming a refractive index adjustment layer. Accordingly, the light-shielding layer forming layer can be formed by applying the light-shielding layer resin composition on the refractive index adjusting layer forming layer, and the developed light-shielding layer is developed when the pattern-exposed light-shielding layer forming layer is developed. Unnecessary portions of the layer for forming the refractive index adjusting layer can be developed using the layer as a mask.
Therefore, the refractive index adjusting layer can be formed in a pattern using the photocurable resin composition.

  In the present invention, a color filter and a black matrix substrate having a refractive index adjustment layer formed in a pattern and including a photocurable resin can be obtained.

FIG. 2 is a schematic sectional view illustrating an example of the color filter of the present invention. FIG. 4 is a schematic plan view illustrating another example of the color filter of the present invention. FIG. 1 is a schematic sectional view illustrating an example of a black matrix substrate of the present invention. It is a flowchart showing an example of a manufacturing method of a color filter of the present invention. It is a flowchart showing an example of a manufacturing method of a black matrix substrate of the present invention.

  Hereinafter, the color filter, the black matrix substrate, the display device, the method for manufacturing the color filter, and the method for manufacturing the black matrix substrate of the present invention will be described in detail.

A. Color filter The color filter of the present invention includes a transparent substrate and a photocurable resin formed in a pattern on the transparent substrate and cured by a photocurable resin composition. A refractive index adjustment layer having a thickness at which curing inhibition occurs, a light shielding layer formed on the refractive index adjustment layer in the same pattern as the refractive index adjustment layer, and containing a binder resin and a black color material, and the transparent substrate And a colored layer formed in the opening of the light-shielding portion above.

Here, the “thickness at which the curing of the photocurable resin composition is inhibited by oxygen” means the thickness of the coating film of the photocurable resin composition that can be developed after being exposed in the atmosphere. More specifically, “the thickness at which curing of the photocurable resin composition is inhibited by oxygen” means that the coating film of the photocurable resin composition formed on the transparent substrate is an ultrahigh pressure mercury lamp of 2.0 kW. Refers to the thickness of the coating film capable of removing the photocurable resin composition on the transparent substrate when exposed with an exposure amount of 100 mJ / cm ² and then developed with a 0.05 wt% aqueous solution of potassium hydroxide. .
In addition, when the coating film of the photocurable resin composition is exposed and developed under the above-described exposure conditions and development conditions, the thickness of the coating film in which a residue of the photocurable resin composition remains on the transparent substrate, or on the transparent substrate. The thickness of the coating film on which the photocurable resin layer is formed is a thickness that does not inhibit curing of the photocurable resin composition by oxygen.

The color filter of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. As shown in FIG. 1, a color filter 1 of the present invention contains a transparent substrate 2 and a photocurable resin formed in a pattern on the transparent substrate 2 and cured by a photocurable resin composition. A refractive index adjusting layer 3 having a thickness at which curing of the resin composition is inhibited by oxygen, and a light-shielding layer formed on the refractive index adjusting layer 3 in the same pattern as the refractive index adjusting layer and containing a binder resin and a black color material. It has a layer 4 and a coloring layer 5 formed in the opening of the light shielding layer 4 on the transparent substrate 2 and having a red coloring layer 5R, a green coloring layer 5G and a blue coloring layer 5B. Further, the light-shielding layer 4 includes a pixel-partitioning light-shielding part 6 formed in the display area 11 for dividing the pixels P, and a frame light-shielding part 7 formed in the non-display area 12.
When such a color filter 1 is used in a display device, the transparent substrate 2 of the color filter 1 is arranged so as to be on the viewer side, and external light enters from the transparent substrate 2 side.

  Here, the “display area” refers to an area used for displaying an image when the color filter of the present invention is used for a display device. The “non-display area” refers to an area arranged on the outer periphery of the display area. For example, as shown in FIG. 2, the color filter has a display area 11 and a non-display area 12 arranged on the outer periphery of the display area 11.

  According to the present invention, since the refractive index adjustment layer and the light shielding layer are formed in the same pattern, a color filter having a refractive index adjustment layer formed in a pattern and including a photocurable resin can be obtained. it can.

As described above, when the refractive index adjusting layer is formed on the entire surface of the transparent substrate, there is a problem that the transmittance of the pixel is reduced by the refractive index adjusting layer formed in the opening of the light shielding layer. Then, the present inventors tried to form a refractive index adjustment layer composed of an organic layer in a pattern only between the transparent substrate and the light shielding layer by using a photolithography method. Photolithography is a method suitable for forming a high-definition thin-film resin layer in a pattern.
However, in this case, for the coating film of the resin composition for the refractive index adjustment layer containing the photocurable resin composition, since it is necessary to make the thickness thereof thinner than that of the conventional resin layer, at the time of pattern exposure, There is a problem that curing is inhibited by oxygen on the surface of the coating film and patterning is difficult.

  As a method of suppressing curing inhibition by oxygen, for example, pattern exposure may be performed in an inert gas atmosphere such as a nitrogen atmosphere. In this case, dedicated equipment is required and the pattern exposure process is complicated. Problem.

  As a method of simultaneously patterning the refractive index adjusting layer and the light shielding layer, for example, after forming a coating film of the resin composition for the refractive index adjusting layer, forming a coating film of the resin composition for the light shielding layer, It is also conceivable to pattern-expose and develop the coating of the layer. However, in this case, there is a problem that the components of the coating films of the respective layers are mixed, and it becomes difficult for the refractive index adjusting layer and the light shielding layer to exhibit sufficient functions.

In order to solve such a problem, the inventors of the present invention have conducted intensive studies, and found that the entire surface of the coating film of the resin composition for a refractive index adjustment layer was exposed to light in the atmosphere, and the refractive index adjustment was performed by semi-curing. By forming the layer forming layer, even if the light-shielding layer resin composition is applied on the coating film, the constituent components are not mixed, and further, the coating film of the light-shielding layer resin composition is subjected to pattern exposure. After that, it was found that the layer for forming the refractive index adjusting layer at the opening of the light-shielding layer can be removed by using the light-shielding layer as a mask when developing.
That is, in the present invention, the thin film refractive index adjusting layer containing the photocurable resin can be formed by a simple process without requiring dedicated equipment. Therefore, an inexpensive color filter can be obtained. In addition, since the interface between the light-shielding layer and the refractive index adjusting layer can be favorably provided, the function of each layer can be sufficiently imparted.

  Hereinafter, each configuration of the color filter of the present invention will be described.

1. Refractive index adjusting layer The refractive index adjusting layer in the present invention is formed in a pattern on a transparent substrate, contains a photocurable resin obtained by curing a photocurable resin composition, and curing the photocurable resin composition with oxygen. It has a thickness that causes inhibition.

  The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the transparent substrate, and particularly preferably higher than the refractive index of the transparent substrate and lower than the refractive index of the light shielding layer. Further, it is preferable that the refractive index of the refractive index adjusting layer is adjusted so that reflection of external light is reduced by an interference effect of light. For example, when the refractive index adjusting layer is a single layer, it is preferable that the optical thickness of the refractive index adjusting layer is adjusted to be に な る wavelength. Specifically, the refractive index of the refractive index adjusting layer is preferably in the range of 1.55 to 1.85. When the refractive index adjusting layer has the above-described refractive index, external light reflection on the light-shielding layer can be reduced.

  Here, the “refractive index” of each member refers to the refractive index for light having a wavelength of 550 nm. The method of measuring the refractive index is not particularly limited, and examples thereof include a method of calculating from a spectral reflection spectrum, a method of using an ellipsometer, and an Abbe method. The ellipsometer includes UVSEL manufactured by Joban-Evon. Specifically, the reflectance and the transmittance can be measured with DF1030R manufactured by Techno Synergy, and the spectrum can be analyzed using a dielectric function model to determine the refractive index.

The refractive index adjusting layer preferably has light transmittance. Regarding the light transmittance of the refractive index adjusting layer, the total light transmittance is preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more.
Here, the total light transmittance of the refractive index adjusting layer can be measured according to JIS K7361-1 (test method for total light transmittance of plastic-transparent material).

Further, the reflectance of the refractive index adjusting layer can be appropriately selected according to the use of the color filter, and is not particularly limited, but the average reflectance in a wavelength region of 380 nm to 780 nm is in a range of 4% to 12%. It is preferable that it is within the range of 4% to 10%, and it is particularly preferable that it is within the range of 4% to 8%.
The average reflectance of the transparent refractive index adjusting layer in the wavelength range of 380 nm to 780 nm can be measured by a reflectance measuring method based on the SCI method.
The SCI method is a method widely used when measuring an object color. As another method of measuring the reflectance, there is also a method of measuring the specular reflection at a specific angle (for example, 5 °). However, when we look at an object, we are looking at the light of every angle component. It is preferable to use an SCI type spectrophotometer. As the spectrophotometer, OSP-SP2000 (manufactured by OLYMPUS Corporation) can be used as a microspectrophotometer.
The average reflectance of the above-mentioned wavelength region of the refractive index adjusting layer can be measured by forming a refractive index adjusting layer, which will be described later, on a transparent substrate, and applying a black tape to the refractive index adjusting layer side of the transparent substrate as a sample. it can.

  As the refractive index adjusting layer, having the above-described refractive index, it is only necessary to contain a photocurable resin, an organic layer containing only the photocurable resin, or an organic layer containing a binder resin and high refractive index fine particles. Can be mentioned.

  When the refractive index adjusting layer contains only a photocurable resin, an ultraviolet curable resin is usually used. As the ultraviolet curable resin, for example, polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, Epoxy resins, polyurethane resins, polyester resins, maleic acid resins, polyamide resins, polyester resins, polyolefin resins, urea resins, phenol resins, silicone resins, rubber resins, epoxy resins, and the like can be given. Further, the ultraviolet curable resin may contain a wax composition, a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, a methylolated or alkylolated urea-based crosslinking agent, acrylamide, polyamide, or the like.

  When the refractive index adjusting layer contains a binder resin and high refractive index fine particles, it contains a photocurable resin as the binder resin. Specifically, examples of the binder resin include those used for a high refractive index layer described in JP-A-2013-142817, JP-A-2012-150226, JP-A-2011-170208, and the like. it can.

The high refractive particles used for the refractive index adjusting layer are not particularly limited as long as the refractive index is higher than that of the binder resin and a refractive index adjusting layer satisfying the above refractive index can be obtained. Among them, the refractive index of the high refractive index fine particles is preferably in the range of 1.5 to 2.8.
Examples of such high refractive index fine particles include zirconium oxide (ZrO ₂ , refractive index: 2.00 to 2.10), antimony oxide (Sb ₂ O ₅ , refractive index: 1.79 to 2.04), Antimony tin oxide (ATO, refractive index: 1.75 to 2.05), indium tin oxide (ITO, refractive index: 1.95 to 2.00), phosphorus tin compound (PTO, refractive index: 1.75) １1.85), β-Al ₂ O ₅ (refractive index: 1.63 to 1.76), γ-Al ₂ O ₅ (refractive index: 1.63 to 1.76), barium titanate (BaTiO ₃₎ , Refractive index: 2.4), titanium oxide (TiO ₂ , refractive index: 2.3 to 2.7), cerium oxide (CeO ₂ , refractive index: 1.95 to 2.20), tin oxide (SnO ₂₎ , Refractive index: 2.00), aluminum zinc oxide (AZO, refractive index: 1.9) 2.00), gallium zinc oxide (GZO, refractive index: 1.90 to 2.00), zinc antimonate (ZnSb ₂ O _6, refractive index: 1.9 to 2.0), zinc oxide (ZnO , Refractive index: 1.90), yttrium oxide (Y ₂ O ₃ , refractive index: 1.87), and the like. These high refractive index fine particles may be used alone or in combination of two or more.

Further, the high refractive index fine particles may be surface-treated. By subjecting the high-refractive-index fine particles to a surface treatment, the affinity with the binder resin and the solvent is improved, the dispersion of the high-refractive-index fine particles becomes uniform, and the aggregation of the high-refractive-index fine particles hardly occurs. It is possible to suppress a decrease in light transmittance of the layer, a coating property of the resin composition for a refractive index adjustment layer, and a decrease in coating strength of the resin composition for a refractive index adjustment layer.
Examples of the surface-treated high refractive index fine particles include those described in JP-A-2013-142817.

  The high refractive index fine particles may be reactive fine particles having a photocurable group on the surface.

The average particle size of the high-refractive-index fine particles may be such that a refractive-index adjusting layer having a uniform thickness can be formed, and is preferably, for example, in the range of 5 nm to 200 nm, and particularly in the range of 5 nm to 100 nm. It is particularly preferable to be within the range of 10 nm to 80 nm. When the average particle diameter of the high refractive index fine particles is within the above range, a good dispersion state of the high refractive index fine particles can be obtained without impairing the light transmittance of the refractive index adjusting layer. If the average particle size of the high refractive index fine particles is within the above range, the average particle size may be any of the primary particle size and the secondary particle size, and the high refractive index fine particles are connected in a chain. You may.
Here, the average particle diameter of the high refractive index fine particles means an average value of 20 particles observed by a transmission electron microscope (TEM) photograph of a cross section of the refractive index adjusting layer.

  The shape of the high refractive index fine particles is not particularly limited, and examples thereof include a spherical shape, a chain shape, and a needle shape.

  The contents of the binder resin and the high refractive index fine particles in the refractive index adjusting layer are appropriately set so that the refractive index of the entire refractive index adjusting layer satisfies the above refractive index. For example, by adjusting the content of the high refractive index fine particles, the refractive index of the entire refractive index adjusting layer can be adjusted.

The refractive index adjusting layer may contain a photopolymerization initiator. The photopolymerization initiator can be appropriately selected from common ones.
Further, the refractive index adjusting layer may contain various additives depending on desired physical properties. Examples of the additives include a dispersing aid, a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, an infrared absorber, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, and a cup. Examples include a ring agent, a plasticizer, an antifoaming agent, and a filler.

  The refractive index adjusting layer may be a single layer or two organic layers having different refractive indexes. When the refractive index adjusting layer is two organic layers having different refractive indexes, the thickness of each organic layer only needs to have a thickness that causes oxygen inhibition in the photocurable resin composition.

The thickness of the refractive index adjusting layer is not particularly limited as long as the photocurable resin composition has a thickness at which curing is inhibited by oxygen.
The thickness of the refractive index adjustment layer can be appropriately selected according to the type of the photocurable resin composition, and is not particularly limited, but is usually 100 nm or less, particularly in the range of 20 nm to 95 nm, and particularly in the range of 30 nm to 85 nm. It is preferable that it is within the range. If the thickness of the refractive index adjusting layer is too small, it may be difficult to obtain a uniform layer.

  Here, the “thickness” of each member refers to a thickness obtained by a general measuring method. Examples of the method of measuring the thickness include a stylus method of calculating the thickness by tracing the surface with a stylus and detecting unevenness, and an optical method of calculating the thickness based on a spectral reflection spectrum. Can be. Specifically, the thickness can be measured using a stylus-type film thickness meter P-15 manufactured by KLA Tencor Corporation. As the thickness, an average value of the thickness measurement results at a plurality of locations of the target member may be used.

  The pattern shape of the refractive index adjusting layer is the same as the pattern shape of the light shielding layer described later.

  As a method for forming the refractive index adjusting layer, a method that can be formed in the same pattern as the light shielding layer is used. The details of the refractive index adjusting layer will be described in the section “D. Method for manufacturing color filter” described later.

2. Light Shielding Layer The light shielding layer in the present invention is formed on the refractive index adjusting layer in the same pattern as the refractive index adjusting layer, and contains a binder resin and a black coloring material.

As the light shielding layer, a material in which a black color material is dispersed in a binder resin can be used.
As the binder resin, for example, a photosensitive resin having a reactive vinyl group such as acrylate, methacrylate, polyvinyl cinnamate, or cyclized rubber is used.

Examples of the black color material include those generally used for a light-shielding layer of a color filter, and any of a pigment and a dye can be used. For example, carbon black, titanium black and the like can be mentioned.
The content of the black color material in the light-shielding layer may be the same as that of a general light-shielding layer in a color filter as long as a desired light-shielding property can be obtained.

As the optical density of the light-shielding layer, the optical density at a unit thickness of 1 μm is usually 3.0 or more.
As a method of measuring the optical density, for example, a method of measuring the spectral reflectance using a spectral colorimeter, calculating the Y value from the spectral reflectance, and calculating the optical density based on the Y value may be used. it can. As the spectral colorimeter, for example, a spectral colorimeter manufactured by Olympus Corporation can be used.

  The light-shielding layer is formed in the display area, and has a pixel-partitioning light-shielding part for dividing pixels, and a frame light-shielding part formed in the non-display area.

  The thickness of the light-shielding layer can be the same as the thickness of a general light-shielding layer in a color filter, and can be set, for example, in the range of 0.5 μm to 2.0 μm.

  The shape of the opening of the light-shielding layer is not particularly limited, and examples thereof include those in which the arrangement of the colored layers is changed such as a stripe shape, a V-shape, and a delta arrangement.

  The light-blocking layer can be formed by a photolithography method. The details of the method for forming the light-shielding layer will be described in the section “D.

3. Colored Layer The colored layer in the invention is formed on the transparent substrate at the opening of the light-shielding portion. Further, it usually has a plurality of colored layers.

  The coloring layer has, for example, three coloring layers of red, green, and blue. The color of the coloring layer may include at least three colors of red, green, and blue. For example, three colors of red, green, and blue, four colors of red, green, blue, and yellow, or red, Five colors of green, blue, yellow, and cyan may be used.

The coloring layer is, for example, a material in which a coloring material is dispersed in a binder resin.
Examples of the coloring material include pigments and dyes of each color. Examples of the red coloring material used in the red coloring layer include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. Examples of the green coloring material used for the green coloring layer include phthalocyanine pigments such as halogen-substituted phthalocyanine pigments and halogen-substituted copper phthalocyanine pigments, triphenylmethane-based basic dyes, isoindoline-based pigments, and isoindolinones. And the like. Examples of the blue coloring material used for the blue coloring layer include copper phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, and dioxazine pigments. These pigments and dyes may be used alone or as a mixture of two or more.
As the binder resin, for example, a photosensitive resin having a reactive vinyl group such as an acrylate type, a methacrylate type, a polyvinyl cinnamate type, or a cyclized rubber type is used.
The colored layer may contain a photopolymerization initiator, and if necessary, a sensitizer, a coating improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like.

The arrangement of the coloring layers is not particularly limited, and may be a known arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.
There may or may not be a gap between adjacent colored layers.

The thickness of the coloring layer can be the same as the thickness of a general coloring layer in a color filter, and can be set, for example, in the range of 1 μm to 5 μm.
As a method for forming the colored layer, any method may be used as long as a plurality of colored layers can be arranged on the same plane, and examples thereof include a photolithography method, an inkjet method, and a printing method.

In addition, a white layer that does not contain the coloring material but contains the binder resin and transmits light from a light source of a display device may be formed on the same plane on which the coloring layer is formed.
The thickness and forming method of the white layer are the same as those of the colored layer.

4. Transparent substrate The transparent substrate in the present invention supports the above-mentioned refractive index adjusting layer, light-shielding layer, coloring layer, and the like.
As the transparent substrate, those generally used for color filters can be used. For example, inorganic substrates having no flexibility such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, and transparent substrates can be used. A flexible resin substrate such as a resin film or an optical resin plate can be used. Among them, an inorganic substrate is preferably used, and among the inorganic substrates, a glass substrate is preferably used. Further, among the glass substrates, it is preferable to use a non-alkali type glass substrate. Alkali-free type glass substrates have excellent dimensional stability and workability in high-temperature heat treatment, and do not contain alkali components in the glass. Therefore, they are suitable for use as color filters for liquid crystal display devices of the active matrix type. Because it can be.

5. Other Configurations In addition to the transparent substrate, the refractive index adjusting layer, the light shielding layer, and the coloring layer, the color filter of the invention may have other configurations as needed.

In the present invention, an overcoat layer may be formed on the colored layer. The color filter surface can be planarized by the overcoat layer.
The material of the overcoat layer is not particularly limited as long as it can flatten the surface on which the colored layer is formed, and can be the same as the overcoat layer generally used for a color filter. Any of an organic material and an inorganic material can be used. When the overcoat layer is made of an inorganic material, a barrier property can be imparted.
The thickness and the method of forming the overcoat layer can be the same as those of the overcoat layer generally used for a color filter.

  Further, for example, a transparent electrode layer or an alignment film may be formed on the overcoat layer, and a spacer may be formed on the inter-pixel light-shielding portion. The transparent electrode layer, the alignment film, and the spacer can be the same as those generally used in a liquid crystal display device.

6. Use The color filter of the present invention can reduce external light reflection, and can be suitably used for, for example, a liquid crystal display device and an organic EL display device.
In the case of a liquid crystal display device, high contrast can be obtained while reducing external light reflection by the refractive index adjusting layer.
In the case of an organic EL display device, since external light reflection can be reduced by the refractive index adjusting layer, it is not necessary to use a circularly polarizing plate to reduce external light reflection. Therefore, it is possible to suppress a decrease in light use efficiency due to the circularly polarizing plate, and to achieve high luminance.

B. Black matrix substrate The black matrix substrate of the present invention includes a transparent substrate, a photocurable resin formed by curing the photocurable resin composition formed in a pattern on the transparent substrate, and the photocurable resin composition. A refractive index adjustment layer having a thickness at which curing inhibition by oxygen occurs, and a light shielding layer formed on the refractive index adjustment layer in the same pattern as the refractive index adjustment layer and containing a binder resin and a black color material. It is characterized by the following.

The black matrix substrate of the present invention will be described with reference to the drawings.
FIG. 3 is a schematic sectional view showing an example of the black matrix substrate of the present invention. As shown in FIG. 3, a black matrix substrate 10 of the present invention contains a transparent substrate 2 and a photocurable resin formed in a pattern on the transparent substrate 2 and cured by a photocurable resin composition. Refractive index adjustment layer 3 having a thickness at which curing inhibition by the oxygen of the reactive resin composition occurs, and is formed on refractive index adjustment layer 3 in the same pattern as the refractive index adjustment layer, and contains a binder resin and a black color material. And a light shielding layer 4. Further, the light-shielding layer 4 includes a pixel-partitioning light-shielding part 6 formed in the display area 11 for dividing the pixels P, and a frame light-shielding part 7 formed in the non-display area 12.
When such a black matrix substrate 10 is used for a display device, the transparent substrate 2 of the black matrix substrate 10 is arranged so as to be on the viewer side, and external light enters from the transparent substrate 2 side.

  Here, the “display area” refers to an area used for displaying an image when the black matrix substrate of the present invention is used for a display device. The “non-display area” refers to an area arranged on the outer periphery of the display area.

  According to the present invention, since the refractive index adjustment layer and the light shielding layer are formed in the same pattern, the black matrix substrate is formed in a pattern and has a refractive index adjustment layer containing a photocurable resin. Can be.

Further, in the present invention, the thin film refractive index adjusting layer containing the photocurable resin can be formed by a simple process without requiring special equipment. Therefore, an inexpensive black matrix substrate can be obtained. In addition, since the interface between the light-shielding layer and the refractive index adjusting layer can be favorably provided, the function of each layer can be sufficiently imparted.
The reason for the above-mentioned effect is the same as that described in the above section “A. Color Filter”, and thus the description thereof is omitted here.

  The refractive index adjusting layer, the light shielding layer, the transparent substrate, and other configurations of the black matrix substrate of the present invention can be the same as those described in the above section “A. Color Filter”.

C. Display Device The display device of the present invention includes the above-described color filter or black matrix substrate.

  According to the present invention, a display device capable of performing high-quality display can be provided by including the color filter or the black matrix substrate.

When the display device of the present invention is a liquid crystal display device, the liquid crystal display device includes, for example, the above-described color filter or black matrix substrate, a counter substrate, and a liquid crystal layer disposed between the color filter or black matrix substrate and the counter substrate. And A transparent electrode layer and an alignment film can be formed on the respective opposing surfaces of the color filter or the black matrix substrate and the opposing substrate. Further, a TFT element or the like can be formed on the opposite substrate. The counter substrate is appropriately selected depending on the driving method of the liquid crystal display device and the like. The liquid crystal used for the liquid crystal layer includes, for example, a nematic liquid crystal and a smectic liquid crystal, and is appropriately selected according to a driving method of the liquid crystal display device.
Each member constituting the liquid crystal display device can be the same as a general liquid crystal display device.

When the display device of the present invention is an organic EL display device, the organic EL display device has, for example, the above-described color filter or black matrix substrate, and an organic EL element substrate having an organic EL element formed on a support substrate. It is. The organic EL element has, for example, a back electrode layer formed on a support substrate, an organic EL layer formed on the back electrode layer and including at least a light emitting layer, and a transparent electrode layer formed on the organic EL layer. . The organic EL layer can include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and the like, in addition to the light emitting layer. The space between the color filter or the black matrix substrate and the organic EL element substrate can be filled with, for example, a resin.
Each member constituting the organic EL display device can be the same as a general organic EL display device.

  When the display device of the present invention has a color filter, color display can be performed with high quality. When the display device of the present invention has a black matrix substrate, monochrome display can be performed with high quality.

D. Method for Producing Color Filter The method for producing a color filter of the present invention comprises applying a resin composition for a refractive index adjustment layer containing a photocurable resin composition on a transparent substrate, Forming a coating film having a thickness that inhibits curing by oxygen, and exposing the entire surface of the coating film under air to form a layer for forming a refractive index adjustment layer in which the photocurable resin composition is semi-cured. A layer forming step for forming a refractive index adjusting layer, and applying a resin composition for a light shielding layer containing a photosensitive resin composition and a black colorant onto the layer for forming a refractive index adjusting layer; After forming, the light-shielding layer forming layer is subjected to pattern exposure, and the exposed light-shielding layer forming layer and the refractive index adjustment layer forming layer are continuously developed to form a light-shielding layer and Form the refractive index adjusting layer in the same pattern A manufacturing method comprising a patterning step and a colored layer forming step of forming a colored layer in an opening of the light shielding layer on the transparent substrate.

  "The layer for forming a refractive index adjustment layer in which the photocurable resin composition is semi-cured" refers to the entire surface of the coating film of the resin composition for a refractive index adjustment layer containing the photocurable resin composition, which is exposed in the air. And a layer which has not been subjected to a baking treatment after the above exposure.

The method for manufacturing a color filter of the present invention will be described with reference to the drawings.
FIGS. 4A to 4E are process diagrams showing an example of a method for manufacturing a color filter of the present invention. In the method for manufacturing a color filter according to the present invention, as shown in FIG. 4A, a resin composition for a refractive index adjustment layer containing a photocurable resin composition is applied on a transparent substrate 2 to form A coating film 3 ″ having a thickness at which curing of the curable resin composition is inhibited by oxygen is formed. Next, the entire surface of the coating film 3 ″ is exposed to the exposure light L1 in the atmosphere to expose the coating film 3 ″. As shown in (b), the photocurable resin composition is partially cured to form the refractive index adjusting layer forming layer 3 ′ (refractive index adjusting layer forming layer forming step). Next, as shown in FIG. 4C, a light-shielding layer resin composition containing a photosensitive resin composition and a black colorant is applied on the refractive index adjusting layer forming layer 3 ′ to form a light-shielding layer. After the formation of the layer for use 4 ′, the light-shielding layer forming layer 4 ′ is subjected to pattern exposure by irradiating exposure light L2 through the photomask M (exposure step). Next, although not shown, by continuously developing the exposed light shielding layer forming layer and the refractive index adjusting layer forming layer, as shown in FIG. The layer 3 is formed in the same pattern (patterning step). Next, as shown in FIG. 4E, the colored layers 5 of the red colored layer 5R, the green colored layer 5G, and the blue colored layer 5B are formed in the openings of the light shielding layer 4 on the transparent substrate 2 (colored layer). Forming step). Through the steps described above, the color filter 1 can be manufactured.

According to the present invention, a layer for forming a refractive index adjustment layer in which a photocurable resin composition is semi-cured can be obtained by having a step of forming a layer for forming a refractive index adjustment layer. Accordingly, the light-shielding layer forming layer can be formed by applying the light-shielding layer resin composition on the refractive index adjusting layer forming layer, and the developed light-shielding layer is developed when the pattern-exposed light-shielding layer forming layer is developed. Unnecessary portions of the layer for forming the refractive index adjusting layer can be developed using the layer as a mask.
Therefore, the refractive index adjusting layer can be formed in a pattern using the photocurable resin composition.

  Further, as described in the above section “A. Color filter”, after forming a coating film of the resin composition for the refractive index adjusting layer and a coating film of the resin composition for the light-shielding layer, pattern exposure and development are performed. Compared to the case, the components of each layer can be suppressed from being mixed. Further, since a dedicated process is not required and the manufacturing process can be simplified, a color filter can be manufactured at low cost.

  Hereinafter, each step in the method for manufacturing a color filter of the present invention will be described.

1. Refractive index adjusting layer forming layer forming step In the present invention, the refractive index adjusting layer forming layer forming step, a refractive index adjusting layer resin composition containing a photocurable resin composition, coated on a transparent substrate, Forming a coating film having a thickness at which curing inhibition by oxygen occurs in the photocurable resin composition, exposing the entire surface of the coating film in the atmosphere, and the refractive index of the photocurable resin composition being semi-cured This is a step of forming a layer for forming an adjustment layer.

  The transparent substrate can be the same as the content described in the section of “A. Color filter” described above, and thus the description is omitted here.

The resin composition for a refractive index adjusting layer contains a photocurable resin composition. The photocurable resin composition contains, for example, a resin component, various additives, a photopolymerization initiator, and a solvent. The photocurable resin composition may be one that can be developed with the same developer as the photosensitive resin composition contained in the resin composition for a light-shielding layer described below, or one that can be developed with a different developer. However, it is preferable that they can be developed with the same developer.
Further, the resin composition for a refractive index adjusting layer may contain high refractive index fine particles as necessary. The solvent is not particularly limited as long as each component can be dissolved or dispersed.

  The method for applying the resin composition for a refractive index adjusting layer is not particularly limited as long as a coating film having a desired thickness can be formed, and examples thereof include a die coating method, a spin coating method, a dip coating method, and a roll coating method. Can be mentioned.

  After application of the resin composition for a refractive index adjusting layer, the resin composition may be dried to remove the solvent.

  Examples of the method of exposing the coating film include a method of irradiating the entire coating film with ultraviolet rays. In addition, as an irradiation method of ultraviolet rays, for example, irradiation can be performed using a metal halide lamp. Further, as the exposure method, the exposure may be performed while transporting the transparent substrate. The exposure is performed in the atmosphere.

  The layer for forming a refractive index adjusting layer has a thickness at which curing of the photocurable resin composition is inhibited by oxygen. The thickness of the layer for forming a refractive index adjustment layer is appropriately determined according to the type of the photocurable resin composition, but is preferably 110 nm or less, particularly in the range of 20 nm to 105 nm, and particularly in the range of 30 nm to 95 nm. Is preferred. If the thickness of the refractive index adjusting layer forming layer is too thin, it may be difficult to obtain a uniform layer.

2. Exposure Step In the exposure step in the present invention, a light-shielding layer resin composition containing a photosensitive resin composition and a black colorant is applied on the refractive index adjusting layer forming layer to form a light-shielding layer forming layer. After that, this is a step of pattern-exposing the light-shielding layer forming layer.

  The resin composition for the light-shielding layer is not particularly limited as long as it contains the photosensitive resin composition and the black colorant, and can be the same as the material of the resin light-shielding layer in a general color filter.

  The method for applying the light-shielding layer resin composition is not particularly limited as long as the light-shielding layer forming layer can be formed on the refractive index adjusting layer, and may be any method as long as a coating film having a desired thickness can be formed. , A die coating method, a spin coating method, a dip coating method, a roll coating method, and the like.

  The method of exposing the light-shielding layer forming layer is not particularly limited as long as the exposure can be performed in a desired pattern, and can be the same as the pattern exposure method used in a general photolithography method. Specifically, a method of irradiating ultraviolet rays through a photomask can be used.

3. Patterning step In the patterning step of the present invention, the light shielding layer and the refractive index adjustment layer are formed into the same pattern by continuously developing the exposed light shielding layer forming layer and the refractive index adjustment layer forming layer. This is the step of forming.

  In this step, it is sufficient that the exposed light-shielding layer forming layer and the refractive index adjusting layer forming layer can be continuously developed, and the developer of the light-shielding layer forming layer and the refractive index adjusting layer forming layer may be used. The developer of the layer may be the same or different, but it is more preferably the same.

  Examples of the developing solution include those used in a general photolithography method, and examples thereof include a potassium hydroxide aqueous solution and a sodium hydroxide aqueous solution.

  In this step, it is preferable that after development, the transparent substrate on which the light shielding layer and the refractive index adjusting layer are formed is subjected to a baking treatment. This is because the crosslink density of the resin contained in the light shielding layer and the refractive index adjusting layer can be increased, and the strength can be increased.

4. Colored Layer Forming Step The colored layer forming step in the present invention is a step of forming a colored layer in the opening of the light shielding layer on the transparent substrate.
The method for forming the colored layer and the obtained colored layer can be the same as those described in the above section “A. Color Filter”, and thus the description is omitted here.

5. Other Steps In addition to the above steps, the method for manufacturing a color filter of the present invention can be performed by appropriately selecting necessary steps. Examples of such a step include a step of forming an overcoat layer.

6. Color Filter The color filter manufactured by the manufacturing method of the present invention can be the same as the content described in the above section “A. Color Filter”, and the description is omitted here.

E. FIG. Method for producing a black matrix substrate The method for producing a black matrix substrate of the present invention comprises applying a resin composition for a refractive index adjustment layer containing a photocurable resin composition on a transparent substrate, Forming a coating film having a thickness in which curing inhibition by oxygen in the product occurs, exposing the entire surface of the coating film in the atmosphere, and forming a refractive index adjustment layer forming layer in which the photocurable resin composition is semi-cured. Forming a layer for forming a refractive index adjusting layer, and applying a resin composition for a light shielding layer containing a photosensitive resin composition and a black coloring material onto the layer for forming a refractive index adjusting layer, thereby forming a light shielding layer. After the formation of the light-shielding layer, the light-shielding layer-forming layer is subjected to pattern exposure, and the exposed light-shielding layer-forming layer and the refractive index adjusting layer-forming layer are successively developed, whereby light is shielded. Layer and refractive index adjustment layer have the same pattern. And a patterning step of forming the electrodes in a loop shape.

The method for manufacturing a black matrix substrate of the present invention will be described with reference to the drawings.
FIGS. 5A to 5D are process diagrams illustrating an example of a method for manufacturing a black matrix substrate according to the present invention. In the method for producing a black matrix substrate of the present invention, as shown in FIG. 5A, a resin composition for a refractive index adjustment layer containing a photocurable resin composition is applied on a transparent substrate 2, A coating film 3 ″ having a thickness at which curing of the photocurable resin composition is inhibited by oxygen is formed. Next, the entire surface of the coating film 3 ″ is exposed to exposure light L1 in the atmosphere to expose the film. As shown in FIG. 5 (b), the photocurable resin composition is formed into a semi-cured refractive index adjusting layer forming layer 3 ′ (refractive index adjusting layer forming layer forming step). Next, as shown in FIG. 5C, a light-shielding layer resin composition containing a photosensitive resin composition and a black colorant is applied on the refractive index adjusting layer forming layer 3 ′ to form a light-shielding layer. After the formation of the layer for use 4 ′, the light-shielding layer forming layer 4 ′ is subjected to pattern exposure by irradiating exposure light L2 through the photomask M (exposure step). Next, although not shown, by continuously developing the exposed light shielding layer forming layer 4 'and the refractive index adjusting layer forming layer 3', as shown in FIG. Then, the refractive index adjusting layer 3 is formed in the same pattern (patterning step). Through the above steps, the black matrix substrate 10 can be manufactured.

According to the present invention, a layer for forming a refractive index adjustment layer in which a photocurable resin composition is semi-cured can be obtained by having a step of forming a layer for forming a refractive index adjustment layer. Accordingly, the light-shielding layer forming layer can be formed by applying the light-shielding layer resin composition on the refractive index adjusting layer forming layer, and the developed light-shielding layer is developed when the pattern-exposed light-shielding layer forming layer is developed. Unnecessary portions of the layer for forming the refractive index adjusting layer can be developed using the layer as a mask.
Therefore, the refractive index adjusting layer can be formed in a pattern using the photocurable resin composition.

  The layer forming step for forming the refractive index adjusting layer, the exposing step, and the patterning step in the method for producing a black matrix substrate of the present invention are the same as those described in the above section “D. Method for producing color filter”. The obtained black matrix substrate can be the same as the content described in the above section “B. Black matrix substrate”, and the description is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the claims of the present invention, and any device having the same function and effect can be realized by the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
A color filter having the form illustrated in FIG. 1 was produced by the following procedure. Specifically, the following photocurable resin composition A, resin composition for a refractive index adjusting layer, red light curable resin composition for forming a color filter, green light curable resin composition, blue light curable resin A composition and a resin composition for a light-shielding layer are prepared, and a photolithography method is performed using the same to form a refractive index adjustment layer, a light-shielding layer having a light-shielding portion for pixel division and a frame light-shielding portion, and each colored layer of a color filter. Was formed. In Example 1, after forming the layer for forming the refractive index adjusting layer, the refractive index adjusting layer and the light shielding layer were simultaneously formed. Thereafter, a red coloring layer, a green coloring layer, and a blue coloring layer of the color filter in the display area were formed by photolithography.
Hereinafter, the details will be described.

(Preparation of photocurable resin composition A)
Photocurable resin composition A was prepared by the following procedure.
63 parts by mass of methyl methacrylate (MMA), 12 parts by mass of acrylic acid (AA), 6 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 88 parts by mass of diethylene glycol dimethyl ether (DMDG) are charged in a polymerization tank. After stirring and dissolving, 7 parts by mass of 2,2′-azobis (2-methylbutyronitrile) was added and uniformly dissolved.
Thereafter, the mixture was stirred at 85 ° C. for 2 hours under a nitrogen stream, and further reacted at 100 ° C. for 1 hour.
To the obtained solution, 7 parts by mass of glycidyl methacrylate (GMA), 0.4 parts by mass of triethylamine, and 0.2 parts by mass of hydroquinone were further added, and the mixture was stirred at 100 ° C. for 5 hours. (50% solids).

Next, the following materials were stirred and mixed at room temperature to obtain a photocurable resin composition A.
<Composition of photocurable resin composition A>
-The above copolymer resin solution (solid content: 50%): 16 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
: 24 parts by mass. Orthocresol novolak type epoxy resin (Eicoat 180S70, Yuka Shell Epoxy Co., Ltd.): 4 parts by mass. 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one: 4 parts by mass. Parts: diethylene glycol dimethyl ether: 52 parts by mass

(Preparation of resin composition for refractive index adjusting layer)
The following components were mixed and sufficiently dispersed in a bead mill to prepare a high refractive particle dispersion.
<Composition of high refractive particle dispersion>
-Oxidized zirconia (TECNAPOW-ZRO2, manufactured by TECCNAN): 20 parts by mass-Polymer dispersant (Bik Chemie Japan Co., Ltd. Disperbyk 163)
: 5 parts by mass ・ Solvent (diethylene glycol dimethyl ether): 75 parts by mass

Next, the following components were sufficiently mixed to obtain a resin composition for a refractive index adjusting layer.
<Composition of resin composition for refractive index adjusting layer>
-High refractive particle dispersion liquid: 1.4 parts by weight-Photocurable resin composition A: 0.6 parts by weight-Diethylene glycol dimethyl ether: 98 parts by weight

The resin composition for a refractive index adjusting layer was applied on a transparent substrate by a spin coater, and dried at 100 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was exposed at an exposure amount of 100 mJ / cm ² using a 2.0 kW ultra-high pressure mercury lamp to form a layer for forming a refractive index adjusting layer.
The thickness of the layer for forming a refractive index adjusting layer was 40 nm.
A black tape was applied to the film surface of the formed layer for forming a refractive index adjustment layer, and the average reflectance of the transparent refractive index adjustment layer in a wavelength region of 380 nm to 780 nm was measured. The average reflectance was 5.1%. Was.
A sample having a thickness of 1.0 μm was prepared for the measurement of the refractive index using the resin composition for a refractive index adjusting layer, and the refractive index was calculated. The refractive index at 550 nm was 1.64. The refractive index was calculated by measuring the reflectance and the transmittance with DF1030R manufactured by Techno Synergy, and performing spectrum analysis using a dielectric function model.

(Formation of light shielding layer)
The following components were mixed and sufficiently dispersed in a bead mill to prepare a black pigment dispersion.
<Composition of black pigment dispersion>
・ Resin-coated carbon black (MS18E manufactured by Mitsubishi Chemical Corporation): 20 parts by mass ・ Polymer dispersion material (Bic Chemie Japan Co., Ltd. Disperbyk 163)
: 5 parts by mass ・ Solvent (diethylene glycol dimethyl ether): 75 parts by mass

Next, the following components were sufficiently mixed to obtain a light-shielding layer resin composition.
<Composition of resin composition for light-shielding layer>
-Black pigment dispersion: 43 parts by mass-Photocurable resin composition A: 19 parts by mass-Diethylene glycol dimethyl ether: 38 parts by mass

The resin composition for a light-shielding layer was applied on a layer for forming a refractive index layer formed on a transparent substrate by a spin coater, and dried at 100 ° C. for 3 minutes to form a layer for a light-shielding layer.
A photomask is arranged at a distance of 100 μm from the light-shielding layer forming layer, and exposed by a proxy writer with a 2.0 kW ultra-high pressure mercury lamp at an exposure amount of 60 mJ / cm ² , and then a 0.05 wt% aqueous solution of potassium hydroxide is used. Then, the substrate is left under an atmosphere of 230 ° C. for 30 minutes to perform a heat treatment, and a light-shielding layer having a light-shielding portion for pixel division and a frame light-shielding portion, and transparency. Was formed.
The width of the light-shielding portion for pixel division was 6 μm, and the aperture ratio was 60%.
The thickness of the light-shielding layer in the light-shielding portion for pixel division and in the frame light-shielding portion was 1.3 μm.
The above resin-coated carbon black (MS18E manufactured by Mitsubishi Chemical Corporation) has an average particle size of 25 nm. The above average particle diameter is measured using a laser Doppler scattered light analysis particle size analyzer (trade name “Microtrac 934UPA”) manufactured by Nikkiso Co., Ltd., and diluted with a solvent (referred to as a diluting solvent) contained in the coloring composition. The particle diameter at which the cumulative particle diameter accounts for 50% was defined as a 50% average particle diameter, and the value was measured and determined.
By the above procedure, a black matrix substrate was obtained.

(Formation of red coloring layer)
A red photocurable resin composition having the following composition was applied on the light-shielding layer of the black matrix substrate by spin coating, and then dried in an oven at 70 ° C. for 3 minutes.
Next, a photomask is arranged at a distance of 100 μm from the coating film of the red light-curable resin composition, and only a region corresponding to the formation region of the red coloring layer is formed using a 2.0 kW ultra-high pressure mercury lamp by a proximity liner. Ultraviolet rays were irradiated at an exposure amount of 60 mJ / cm ² .
Next, the film was immersed in a 0.05 wt% aqueous solution of potassium hydroxide (liquid temperature: 23 ° C.) for 1 minute to carry out alkali development, thereby removing only the uncured portion of the coating film of the red photocurable resin composition.
Thereafter, the transparent substrate was left in an atmosphere of 230 ° C. for 15 minutes to perform a heat treatment to form a red colored layer (red pixel pattern) in a display area.
The formed film thickness of the red coloring layer was 2.0 μm.

<Composition of red light-curable resin composition>
・ C. I. Pigment Red 177: 3 parts by mass. I. Pigment Red 254: 4 parts by mass, polysulfonic acid type polymer dispersant: 3 parts by mass, photocurable resin composition A: 23 parts by mass, 3-methoxybutyl acetate: 67 parts by mass

(Formation of green coloring layer)
Next, using a green photocurable resin composition having the following composition, in the same process as the formation of the red coloring layer, the coating film thickness was changed so that the formed film thickness became 2.0 μm, A layer was formed in the display area.

<Composition of green light-curable resin composition>
・ C. I. Pigment Green 58: 7 parts by mass. I. Pigment Yellow 138: 1 part by mass • Polysulfonic acid type polymer dispersant: 3 parts by mass · Photocurable resin composition A: 22 parts by mass · -3-methoxybutyl acetate: 67 parts by mass

(Formation of blue colored layer)
Further, using a blue light-curable resin composition having the following composition, in the same process as the formation of the red coloring layer, the coating film thickness was changed so that the formed film thickness became 2.0 μm, Was formed in the display area.

<Composition of blue light curable resin composition>
・ C. I. Pigment Blue 15: 6: 5 parts by mass • Polysulfonic acid type polymer dispersant: 3 parts by mass · Photocurable resin composition A: 25 parts by mass · -3-methoxybutyl acetate: 67 parts by mass

  Thus, the color filter shown in FIG. 1 was produced.

[Example 2]
The thickness of the refractive index adjusting layer was 80 nm, the average reflectance in the wavelength region of 380 nm to 780 nm was 6.1%, and a color filter was produced in the same manner as in Example 1 except that the refractive index adjusting layer was formed.

[Example 3]
A color filter was produced in the same manner as in Example 1 except that a resin composition for a refractive index adjusting layer having the following composition was used.
<Composition of resin composition for refractive index adjustment layer>
-The high refractive particle dispersion liquid: 2.5 parts by mass-The photocurable resin composition A: 0.5 parts by mass-Diethylene glycol dimethyl ether: 97 parts by mass The refractive index of the refractive index adjusting layer is calculated according to the method described above. As a result, the refractive index at 550 nm was 1.72. The average reflectance of the refractive index adjusting layer in the wavelength range of 380 nm to 780 nm was 5.8%.

[Example 4]
A color filter was produced in the same manner as in Example 1 except that a resin composition for a refractive index adjusting layer having the following composition was used.
<Composition of resin composition for refractive index adjusting layer>
-High refractive particle dispersion liquid: 1.2 parts by weight-Photocurable resin composition A: 0.8 parts by weight-Diethylene glycol dimethyl ether: 98 parts by weight Calculate the refractive index of the refractive index adjusting layer according to the method described above. As a result, the refractive index at 550 nm was 1.60. The average reflectance of the refractive index adjusting layer in a wavelength range of 380 nm to 780 nm was 4.9%.

[Comparative Example 1]
An attempt was made to fabricate a black matrix substrate in the same manner as in Example 1 except that the thickness of the refractive index adjusting layer was changed to 110 nm. In the development step at the time of forming the light-shielding layer having the pixel-shading light-shielding portion and the frame light-shielding portion, In addition, residues of the resin composition for a refractive index adjusting layer containing the photocurable resin composition A were generated. Therefore, a black matrix substrate and a color filter could not be manufactured.

[Comparative Example 2]
An attempt was made to manufacture a black matrix substrate in the same manner as in Example 3 except that the thickness of the refractive index adjustment layer was changed to 105 nm. In the development step at the time of forming the light-shielding layer having the pixel-shading light-shielding portion and the frame light-shielding portion, In addition, residues of the resin composition for a refractive index adjusting layer containing the photocurable resin composition A were generated. Therefore, a black matrix substrate and a color filter could not be manufactured.

DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Transparent substrate 3 ... Refractive index adjustment layer 4 ... Light shielding layer 5 ... Coloring layer 5R ... Red coloring layer 5G ... Green coloring layer 5B ... Blue coloring layer 6 ... Light shielding part for pixel division 7 ... Frame light shielding part 10 … Black matrix substrate 11… display area 12… non-display area

Claims (2)

A resin composition for a refractive index adjustment layer containing a photocurable resin composition is applied on a transparent substrate to form a coating film having a thickness at which curing inhibition by oxygen in the photocurable resin composition occurs. Exposure of the entire surface of the coating film in the atmosphere, a refractive index adjustment layer forming layer forming step of forming a semi-cured refractive index adjustment layer forming layer of the photocurable resin composition,
A light-shielding layer resin composition containing a photosensitive resin composition and a black colorant is applied on the refractive index adjusting layer forming layer to form a light-shielding layer forming layer, and then the light-shielding layer forming layer An exposure step of pattern-exposing the
By continuously developing the exposed light shielding layer forming layer and the refractive index adjusting layer forming layer, a patterning step of forming the light shielding layer and the refractive index adjusting layer in the same pattern,
Forming a colored layer in an opening of the light-shielding layer on the transparent substrate. A resin composition for a refractive index adjustment layer containing a photocurable resin composition is applied on a transparent substrate to form a coating film having a thickness at which curing inhibition by oxygen in the photocurable resin composition occurs. Exposure of the entire surface of the coating film in the atmosphere, a refractive index adjustment layer forming layer forming step of forming a semi-cured refractive index adjustment layer forming layer of the photocurable resin composition,
A light-shielding layer resin composition containing a photosensitive resin composition and a black colorant is applied on the refractive index adjusting layer forming layer to form a light-shielding layer forming layer, and then the light-shielding layer forming layer An exposure step of pattern-exposing the
A patterning step of forming the light-shielding layer and the refractive-index adjustment layer in the same pattern by continuously developing the exposed light-shielding layer formation layer and the refractive index adjustment layer formation layer. A method for manufacturing a black matrix substrate.

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