CN106233164A - Substrate with light-shielding material, color filter, liquid crystal display device, and colored resin composition for forming the light-shielding material - Google Patents

Abstract

The invention provides a substrate with a light shielding material, which has good productivity and can realize excellent low reflectivity. The substrate of the present invention is a substrate with a light-shielding material, which has a light-shielding material on a transparent substrate, wherein the light-shielding material contains (A) a color material and (B) an organic binding material, and satisfies the following (1) and (2). (1) The light-shielding material contains (C) fine particles having a refractive index of 1.2 to 1.8; (2) the concentration of the fine particles in the light-shielding material is different in a thickness direction, and the concentration of the fine particles on the side opposite to the transparent substrate is lower than the concentration of the fine particles on the side of the transparent substrate, compared to the side of the transparent substrate.

Description

Substrate with light-shielding material, color filter, liquid crystal display device, and for forming the Colored resin composition for light-shielding material

technical field

The invention relates to a substrate with a light-shielding material, a color filter and a liquid crystal display device. Specifically, it relates to a substrate with a light-shielding material having low reflectance and excellent light-shielding properties, a colored resin composition for forming the light-shielding material, and a color filter and a liquid crystal display device having the light-shielding material.

Background technique

Conventionally, as a method of manufacturing a color filter using a pigment, a dyeing method, an electrodeposition method, an inkjet method, a pigment dispersion method, and the like are known.

In the case of producing a color filter by the pigment dispersion method, it is generally carried out as follows: a binder resin, a photopolymerization initiator, a photopolymerizable monomer are added to a colored resin composition obtained by dispersing a pigment with a dispersant or the like etc. to obtain a photosensitive colored resin composition, and apply the composition on a glass substrate and dry it, then expose it using a mask and develop it to form a colored pattern, and then heat it, thereby making the pattern Fix to form pixels. These processes are repeated for each color, thereby forming a color filter.

Light-shielding materials used for color filters are required to have various qualities such as light-shielding properties, patternability, and electrical characteristics, and one of them includes reflective properties. In a liquid crystal panel, the pixels of the color filter and the light-shielding material are usually viewed through glass, and the lower the reflectivity of the surface, the less the reflection from the outside, and the better an image can be obtained. In general, pixels and light-shielding materials are formed of a mixture of a color material and resin, or a fired product thereof, and reflection occurs due to a difference in refractive index between glass, pixels, and light-shielding materials. The refractive index of glass and resin is about 1.5, but the refractive index of color materials is usually higher than them. For example, the refractive index of carbon black is about 2.0, so the higher the content, the higher the reflectivity. .

In recent years, liquid crystal display devices have been required to have higher light-shielding properties, and accordingly, the amount of color materials needs to be increased, and as a result, reflectivity also tends to increase. Patent Document 1 describes a light-shielding layer in which a metal thin film layer is provided on a photocurable resin layer. However, vapor deposition of metals such as chromium also has problems in that the manufacturing process is long, the productivity is low, the cost is high, and environmental problems are caused by waste liquid of etching treatment and the like.

In addition, Patent Document 2 describes that by forming a light-shielding layer including two or more resin layers on a substrate, the first layer of the light-shielding layer on the substrate side is a light-absorbing layer, and the second and subsequent layers are light-shielding layers. A reflective layer that achieves high shading to reduce reflectivity when viewed from the observer's side.

In addition, Patent Document 3 describes that by forming a colored resin layer on a substrate and further forming a black resin layer thereon, a material having low light reflectance in the entire visible wavelength region and excellent light-shielding properties can be obtained.

On the other hand, some literatures have already described the technique of compounding granular silica etc. in the photosensitive resin composition. For example, Patent Document 4 describes a technique of adding an organosilane to a protective film in order to achieve adhesion of an electrodeposited layer. Moreover, patent document 5 describes the technique of adding granular silica to the photosensitive composition for black matrices for the purpose of improving pattern formability.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3367173

Patent Document 2: Japanese Patent Laid-Open No. 2006-11180

Patent Document 3: Japanese Patent Application Laid-Open No. 8-146410

Patent Document 4: Japanese Patent Application Laid-Open No. 5-288926

Patent Document 5: Japanese Patent Laid-Open No. 2008-304583

Contents of the invention

The problem to be solved by the invention

The inventors of the present invention found that the substrate with a light-shielding material described in Patent Document 2 has a problem that it is difficult to further reduce the reflectance because the second and subsequent layers are light reflection layers.

In addition, the substrate with a light-shielding material described in Patent Document 3 has a problem of insufficient wavelength dependence of reflectance because a colored resin layer is formed on the substrate.

A first object of the present invention is to provide a substrate with a light-shielding material that has good productivity and can realize excellent low reflectivity.

A second object of the present invention is to provide a substrate with a light-shielding material capable of achieving excellent low reflectivity and having a small wavelength dependence of reflectivity.

A third object of the present invention is to provide a colored resin composition for forming a substrate with a light-shielding material capable of achieving excellent low reflectivity with high productivity.

way of solving the problem

The inventors of the present invention conducted intensive studies to solve the above-mentioned first problem. As a result, they found that by adding specific fine particles to the light-shielding material and controlling the concentration distribution of the fine particles in the thickness direction, good productivity and excellent low reflection can be realized. sex.

In addition, as a result of intensive research to solve the above-mentioned second problem, it has been found that excellent low reflectivity can be achieved by adding a specific color material to the transparent substrate side and the opposite side of the light-shielding material and controlling the OD value in the thickness direction. , and can reduce the wavelength dependence of reflectivity.

Furthermore, as a result of intensive research to solve the above-mentioned third problem, it has been found that a substrate with a light-shielding material capable of achieving excellent low reflectivity can be formed with high productivity by including a specific amount of specific particles in the colored resin composition .

That is, the present invention takes the following [1] to [18] as main technical means.

[1] A substrate with a light-shielding material, which is a substrate with a light-shielding material having a light-shielding material on a transparent substrate, wherein,

The light-shielding material includes (A) color material and (B) organic binding material, and satisfies the following (1) and (2),

(1) The light-shielding material contains (C) fine particles having a refractive index of 1.2 or more and 1.8 or less.

(2) The concentration of the particles in the light-shielding material is different in the thickness direction, and the concentration of the particles on the side opposite to the transparent substrate is lower than the concentration of the particles on the side of the transparent substrate.

[2] The substrate with a light-shielding material according to the above [1], wherein the OD value per 1 μm of the light-shielding material is different in the thickness direction, and the OD value on the side opposite to the transparent substrate is higher than that of the transparent substrate side OD value.

[3] The substrate with a light-shielding material according to [1] or [2] above, wherein the (C) fine particles are inorganic fine particles.

[4] The substrate with a light-shielding material according to the above [3], wherein the inorganic fine particles are silica particles.

[5] The substrate with a light-shielding material according to any one of [1] to [4] above, wherein the (A) color material contains one or more selected from carbon black, titanium black, and organic coloring pigments.

[6] A substrate with a light-shielding material, which is a substrate with a light-shielding material having a light-shielding material on a transparent substrate, wherein,

The light-shielding material includes (A) color material and (B) organic binding material, and satisfies the following (3)-(5)

(3) The transparent substrate side of the light-shielding material contains a black pigment as the (A) color material.

(4) The side of the light-shielding material opposite to the transparent substrate contains a pigment as the (A) color material.

(5) The OD value per 1 μm of the light-shielding material differs in the thickness direction, and is higher on the side opposite to the transparent substrate than on the transparent substrate side.

[7] The substrate with a light-shielding material according to any one of [1] to [6] above, wherein the light-shielding material has an OD value per 1 μm of 2.5 or more.

[8] The substrate with a light-shielding material according to any one of [1] to [7] above, wherein the (B) organic binder is a cured product of an alkali-soluble resin.

[9] The substrate with a light-shielding material according to any one of [1] to [8] above, wherein the light-shielding material further contains (E) a photopolymerization initiator.

[10] The substrate with a light-shielding material according to any one of [1] to [9] above, which has a relative reflectance at a wavelength of 550 nm of 1.0% or less.

(The relative reflectance is a value measured by incident light at an incident angle of 5 degrees from the transparent substrate side and using a mirror plate as a reference.)

[11] The substrate with a light-shielding material according to [10] above, wherein the difference between the upper limit and the lower limit of the relative reflectance at a wavelength of 450 to 650 nm is 0.5% or less.

[12] The substrate with a light-shielding material according to any one of [1] to [11] above, wherein the light-shielding material is composed of two or more layers.

[13] A color filter comprising the substrate with a light-shielding material according to any one of [1] to [12] above.

[14] A liquid crystal display device comprising the color filter described in the above [13].

[15] A colored resin composition comprising: (A) a color material, (B') an organic binder, (C) fine particles having a refractive index of 1.2 to 1.8, and (D) an organic solvent,

However, the content of (C) fine particles is 15% by mass or more.

[16] The colored resin composition according to [15] above, wherein the (C) fine particles are inorganic fine particles.

[17] The colored resin composition according to the above [16], wherein the inorganic fine particles are silica particles.

[18] The colored resin composition according to any one of [15] to [17] above, wherein the (A) color material contains one or more selected from carbon black, titanium black, and organic coloring pigments.

The effect of the invention

The substrate with a light-shielding material according to the first embodiment of the present invention has good productivity and can realize excellent low reflectivity.

In addition, the substrate with a light-shielding material according to the second embodiment of the present invention can achieve excellent low reflectivity, and the wavelength dependence of reflectivity is small.

Moreover, the colored resin composition which concerns on 3rd Embodiment of this invention can form the board|substrate with a light-shielding material which can realize excellent low reflectivity with high productivity.

Description of drawings

[FIG. 1] FIG. 1(a) and FIG. 1(b) are schematic views for explaining one embodiment of the substrate with a light-shielding material of the present invention.

[Fig. 2] Fig. 2(a) to Fig. 2(c) are side cross-sectional schematic diagrams illustrating the formation process of the light-shielding material of the present invention, Fig. 2(a) showing the coating process, and Fig. 2(b) showing the exposure process , FIG. 2(c) shows the light-shielding material after development.

[ Fig. 3] Fig. 3(a) and Fig. 3(b) are side cross-sectional schematic diagrams illustrating a method of measuring relative reflectance.

[Fig. 4] Fig. 4(a) and Fig. 4(b) are graphs of the reflectance distribution with respect to the wavelength when the reflectance is measured, and Fig. 4(a) is the reflectance measured with the anti-reflection film in Example 2 Graph 4(b) is a graph of reflectance distribution with respect to wavelength at R1, and FIG.

Symbol Description

1 particle

10 Shading material

11 Transparent Substrate

12 1st shading layer

12A Coating film for the first light-shielding layer

13 2nd shading layer

13A Coating film for the second light-shielding layer

14 Anti-reflection film

15 photomask

16 Determination of the incident light path

17 Determination of reflected light path

detailed description

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and various modifications can be made within a range not exceeding the gist.

In the present invention, the refractive index means a refractive index at a wavelength of 589 nm.

In addition, in this invention, the said "(meth)acryl" means "acryl and/or methacryl", and it is the same about "(meth)acrylate" and "(meth)acryl".

In addition, in the present invention, the "total solid content" means all the components contained in the colored resin composition or the ink described later except for the solvent.

In addition, in this invention, the said weight average molecular weight means the weight average molecular weight (Mw) converted into polystyrene by GPC (gel permeation chromatography). In addition, in this specification, "mass" means "weight".

In addition, in the present invention, unless otherwise specified, the "amine value" means the amine value in terms of effective solid content, and is represented by the mass of KOH equivalent to the amount of alkali per 1 g of solid content of the dispersant. value. In addition, the measuring method is as follows.

In addition, in the present invention, the "light-shielding material" is a light-shielding cured product provided on a transparent substrate, and means a material obtained by applying a colored resin composition, drying it, and forming a film. A material obtained by exposing and/or developing a coated film. The light-shielding material of the present invention also includes a black matrix, a frame, and the like.

<Substrate with light-shielding material according to the first embodiment>

The substrate with a light-shielding material according to the first embodiment of the present invention has a light-shielding material on a transparent substrate, wherein the light-shielding material includes (A) a color material and (B) an organic binder, and satisfies the following (1) and (2).

(1) The light-shielding material contains (C) fine particles having a refractive index of 1.2 or more and 1.8 or less.

(2) The concentration of the particles in the light-shielding material varies in the thickness direction, and the concentration of the particles on the side opposite to the transparent substrate is lower than the concentration of the particles on the side of the transparent substrate.

In this way, by making the concentration of particles (C) having a refractive index of 1.2 to 1.8 in the light-shielding material (hereinafter simply referred to as "(C) particles") vary in the thickness direction, and making the concentration of particles on the side opposite to the transparent substrate The particle concentration is lower than that on the transparent substrate side, and in the case of forming a light-shielding material by applying the colored resin composition multiple times, it may be possible to suppress further application of the colored resin composition on the coated colored resin composition. Since the coated colored resin composition tends to dissolve, which may occur, there is a tendency that the light-shielding material can be easily formed through one exposure and development. Furthermore, there exists a tendency for the reflection of light by (C) microparticles to be suppressed by setting the refractive index of (C) microparticles|fine-particles in a specific range.

As an example of the substrate with a light-shielding material according to the first embodiment of the present invention, as shown in FIG. And (C) a substrate with a light-shielding material having a lower concentration of fine particles 1 on the side opposite to the above-mentioned transparent substrate 11 than on the side of the above-mentioned transparent substrate 11 . In order to obtain such a substrate with a light-shielding material, a method of applying a colored resin composition having a different concentration of (C) fine particles multiple times so that the concentration of (C) fine particles gradually decreases. A colored resin composition containing (C) fine particles may be applied once on a transparent substrate, and a colored resin composition not containing (C) fine particles may be applied thereon. In this case, by constituting the (B) organic binder in various colored resin compositions with the same type or a similar type of material, there is a tendency that the formation of the interface due to multiple coatings can be suppressed.

In addition, as shown in FIG. 1( b ), the light-shielding material 10 is made of two or more layers (the first light-shielding layer 12 and the second light-shielding layer 13 ), and the layer on the opposite side to the transparent substrate 11 is (C) The concentration of microparticles 1 in (C) is lower than that of the substrate with a light-shielding material on the transparent substrate 11 side. For example, in order to obtain such a substrate with a light-shielding material, a method of applying colored resin compositions having different concentrations of (C) fine particles multiple times so that the concentration of (C) fine particles gradually decreases. A colored resin composition containing (C) fine particles may be applied once on a transparent substrate, and a colored resin composition not containing (C) fine particles may be applied thereon. In this case, by constituting (B) the organic binder in various colored resin compositions with different types of materials, there is a tendency that an interface can be formed at the time of multiple application. The laminated structure is not particularly limited, and for example, two or more light-shielding layers may be laminated parallel to the contact surface with the transparent substrate. In addition, the number of laminations is not particularly limited, but when the number of laminations is large, the number of coating steps of the colored resin composition during the formation of the light-shielding material increases and the production efficiency deteriorates. Therefore, it is preferably 2 to 4 layers, more preferably 2 layers. -3 layers, more preferably 2 layers.

In this way, the substrate with a light-shielding material according to the first embodiment of the present invention only needs to include at least as shown in FIG. 1( a ) or FIG. The directions are different, and the concentration of the (C) fine particles on the side opposite to the transparent substrate may be lower than that on the transparent substrate side. For example, by making the light-shielding material include not only the first light-shielding layer and the second light-shielding layer in FIG. A region configured such that the concentration of (C) fine particles is higher on the side opposite to the transparent substrate than on the transparent substrate side is included.

As (C) fine particles, those described below can be preferably used.

Generally, the degree of reflectance at the interface between the transparent substrate and the light-shielding material differs depending on the difference in refractive index between the transparent substrate and the light-shielding material. For example, glass, resin used as a transparent substrate, and resin as a component of a colored resin composition have a refractive index of approximately 1.4 to 1.6. On the other hand, there exists a tendency for the refractive index of (A) color material to be higher than these. For example, the refractive index of carbon black is approximately 2.0-i (complex number). Therefore, as the amount of carbon black in the colored resin composition for forming the light-shielding material increases, the refractive index of the colored resin composition becomes higher, and as a result, the difference in refractive index with the transparent substrate becomes larger, and the interface between the transparent substrate and the light-shielding material increased reflectivity. Therefore, it is difficult to achieve both high light-shielding property and low reflectance.

On the other hand, when multilayering is to be performed with a normal colored resin composition, the colored resin composition for the second layer is applied after the colored resin composition is applied and dried to form a first-layer coating film. In this case, the coating film of the first layer may be dissolved by the solvent of the coating liquid of the second layer.

In order to solve such a problem, the light-shielding material in the substrate with light-shielding material according to the first embodiment contains (C) fine particles. In this invention, as an effect of adding (C) microparticles|fine-particles, including a filling effect, improvement of the solvent resistance of a colored resin composition is mentioned. In addition, solvent resistance can also be improved by reducing the content of the resin component in the colored resin composition. These effects can be obtained to some extent by adding the (A) color material, but for the above reasons, increasing the amount of the (A) color material tends to cause an increase in reflectance.

Examples of (C) microparticles that can be used in the substrate with a light-shielding material according to the first embodiment include silica microparticles, resin microparticles, and the like, but are not limited to these microparticles. (C) The refractive index of the microparticles is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, and 1.8 or less, preferably 1.7 or less, more preferably 1.6 or less. (C) If the refractive index of the fine particles is too large, the refractive index of the light-shielding material tends to increase and the reflectance at the interface between the transparent substrate and the light-shielding material tends to increase. (C) Fine particles may be used alone or in combination of two or more.

As fine particles whose refractive index satisfies the above-mentioned range, for example, inorganic fine particles or resin fine particles are exemplified, and from the viewpoint of easily obtaining a desired particle diameter, inorganic fine particles are preferable, and from the viewpoint of further reducing the particle diameter, more preferably oxide particles.

Examples of oxide particles include silicon oxide (silicon dioxide), aluminum oxide, and zirconium oxide, and more preferably fine particles of silicon oxide (silicon dioxide) from the viewpoint of dispersibility.

As the silica fine particles, dry silica, colloidal silica, or a solvent dispersion thereof may be used. These silica fine particles are preferably used in the preparation of a colored resin composition after being dispersed in an organic solvent and mixed with other components. Alternatively, the (A) color material and silica may be mixed and dispersed, and then added.

(C) The average particle size of the microparticles can be measured by BET method or the like, and is preferably 5 nm or more, more preferably 10 nm or more, and preferably 100 nm or less, more preferably 20 nm or less. (C) If the average particle size of the fine particles is too small, the dispersion stability cannot be maintained, and if it is too large, the planar uniformity of the formed light-shielding material may be damaged.

As an example of silica microparticles that can be used in the present invention, dry silica includes AEROSIL series manufactured by Nippon Aerosil Co., Ltd., and colloidal silica includes SNOWTEX series and ORGANOSILICA SOL series manufactured by Nissan Chemical Co., Ltd. Wait.

Examples of the resin particles include acrylic resin fine particles, but are not limited thereto. When preparing the colored resin composition, the resin fine particles may be used dispersed in (D) organic solvent, or may be co-dispersed after being mixed with (A) color material. For the same reason as the silica fine particles, the average particle diameter of the resin fine particles by the BET method is preferably 20 to 500 nm, more preferably 30 to 300 nm.

In the substrate with a light-shielding material according to the first embodiment, as the (C) fine particles, among the above, silica fine particles are preferable, and a solvent dispersion product of colloidal silica is more preferable.

In addition, the density|concentration of the thickness direction of (C) microparticles|fine-particles in a light-shielding material can be confirmed by the following method, for example.

(1) SEM secondary electron image

Check the SEM secondary electron image of the cross section of the transparent substrate and light-shielding material. For example, in the case of using silica particles, metal oxide particles, etc. as the (C) fine particles, since the strength of the silica particles, metal oxide particles, etc. The intensity of atoms is strong, so the concentration distribution can be confirmed on the cross section.

(2) Elemental analysis based on SEM-EDS

The cross-section of the transparent substrate and the light-shielding material was subjected to elemental analysis by SEM-EDS, and the intensity distribution in the thickness direction was measured (line analysis).

For example, when the transparent substrate is a glass substrate and the (C) particles are silica particles, etc., by measuring the substrate with a light-shielding material of the present invention and the substrate with a light-shielding material not containing silica particles, and The concentration distribution can be confirmed by normalizing to the glass surface and obtaining the intensity distribution in the thickness direction of the differential spectrum.

That is, if the intensity of the differential spectrum is uniform in the thickness direction, it indicates that there is no concentration distribution of (C) fine particles in the thickness direction. On the other hand, if the intensity of the differential spectrum is strong on the transparent substrate side, it indicates that the transparent The concentration of (C) fine particles on the substrate side is high.

The OD value per 1 μm of the light-shielding material according to the first embodiment of the present invention (hereinafter referred to as “unit OD value”, and the unit may be represented by “/μm” in some cases) is preferably 2.5 or more, more preferably 3.0 or more, More preferably, it is 3.5 or more. There exists a tendency for sufficient light-shielding property to be acquired by making this unit OD value more than the said lower limit. On the other hand, the larger the unit OD value, the higher the light-shielding properties of the light-shielding material, which is more preferable. However, if the added amount of the color material is increased in order to further increase the unit OD value, it may cause poor adhesion to the substrate and poor development. Therefore, the unit OD value of the light-shielding material is preferably 5.0/μm or less, more preferably 4.5/μm or less. The OD value per 1 μm can be obtained by converting the OD value of the entire light-shielding material into a value per 1 μm of thickness.

In addition, in the light-shielding material according to the first embodiment of the present invention, it is preferable that the OD value per 1 μm of the light-shielding material is different in the thickness direction, and that the OD value per 1 μm on the side opposite to the transparent substrate is higher than that on the side opposite to the transparent substrate. OD value is lower. With such a configuration, there is a tendency that both high light-shielding properties and low reflectivity can be achieved more easily.

For example, the unit OD value of the light-shielding material on the transparent substrate side is preferably 0.1/μm or more, more preferably 0.5/μm or more, and preferably 1.5/μm or less, more preferably 1.0/μm or less. When it is more than the said lower limit, it exists in the tendency which can suppress the dissolution of the coated colored resin composition at the time of performing multiple coatings, and when it is below the said upper limit, it exists in the tendency which can reduce reflectance. The unit OD value on the transparent substrate side can be obtained, for example, by measuring the OD value within a range of 0.5 μm from the thickness of the transparent substrate and dividing the value by the thickness. In addition, when the light-shielding material consists of two or more layers, the unit OD value of the 1st layer on a transparent substrate can be measured.

On the other hand, the unit OD value on the side opposite to the transparent substrate is preferably 2.5/μm or more, more preferably 3.0/μm or more, and preferably 5.0/μm or less, more preferably 4.5/μm or less. There exists a tendency for the light-shielding material as a whole to realize desired light-shielding property by being in the said range. The unit OD value on the side opposite to the transparent substrate can be obtained, for example, by measuring the OD value within a thickness of 0.5 μm from the upper surface of the light-shielding material and dividing the value by the thickness. In addition, when the light-shielding material consists of two or more layers, the unit OD value of the 2nd layer other than the 1st layer on a transparent substrate can be measured.

In addition, the relative reflectance at a wavelength of 550 nm of the light-shielding material according to the first embodiment of the present invention is preferably 1.0% or less, more preferably 0.7% or less, and usually 0.1% or more. The above-mentioned relative reflectance can be measured with light incident at an incident angle of 5 degrees from the transparent substrate side and using the mirror plate as a reference. In this way, by setting the reflectance between the substrate and the light-shielding material to be equal to or less than the above-mentioned upper limit, a light-shielding material capable of obtaining a good image with little reflection from the outside can be obtained. Moreover, since some reflection occurs by making a light-shielding material contain a coloring material, there exists a tendency for it to become more than the said lower limit.

In addition, the difference between the upper limit and the lower limit of the relative reflectance of the light-shielding material according to the first embodiment of the present invention at a wavelength of 450 to 650 nm is preferably 0.5% or less, more preferably 0.3% or less, and usually 0.01% or less. %above. By being below the said upper limit, there exists a tendency that the color tone of a light-shielding material can be made black, and the color tone at the time of panel production can be made into a desired color tone. In addition, since the reflectance of the color material differs somewhat depending on the wavelength, there is a tendency for the upper and lower limits of 0.01% or more to occur.

The total film thickness of the light-shielding material according to the first embodiment of the present invention is preferably 0.2 μm or more, more preferably 0.5 μm or more, still more preferably 0.8 μm or more, and is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. If the total film thickness of the light-shielding material is too thin, sufficient light-shielding properties may not be obtained, and if it is too thick, there may be a difference in height at the border when disposing color pixels. In some cases, the stacking interval distance serving as a liquid crystal cell gap becomes non-uniform, which may cause a cell gap defect.

When the light-shielding material consists of two or more layers, the film thickness of the first layer on the transparent substrate is preferably 0.2 μm or more, more preferably 0.5 μm or more, and preferably 1.5 μm or less, more preferably 0.8 μm or less. If the film thickness of the first layer is too thin, the reflectance of the layers after the second layer may increase, and if it is too thick, it may not be possible to achieve desired light-shielding properties of the light-shielding material as a whole.

As the transparent substrate, generally, substrates described later in the description of the color filter of the present invention can be used.

As (A) color material used for a light-shielding material, the color material described in the following <(A) color material> can be used preferably. In particular, the color materials described in <Substrate with light-shielding material according to the second embodiment> can be used.

In addition, examples of the (B) organic binder include those obtained by curing the (B') organic binder described later. When using (B') organic binder containing (E) photopolymerization initiator and other components, (E) photopolymerization initiator and other components may be contained in light-shielding material.

The light-shielding material in the substrate with light-shielding material according to the first embodiment can usually be formed using a colored resin composition containing at least (A) color material, (B) organic binder, and if necessary (C) fine particles.

<(A) color material>

The light-shielding material in the substrate with a light-shielding material according to the first embodiment, and the colored resin composition for forming the light-shielding material usually contain the (A) color material. As the (A) color material, dyes and pigments can be used, but pigments are preferred in terms of heat resistance, light resistance, and the like. For example, known pigments assigned C.I. pigment numbers can be mentioned. Particles composed of simple metals are not included in pigments.

The color that the color material exhibits is not particularly limited, but it is preferably black from the viewpoint of realizing high light-shielding properties.

Examples of black color materials include black pigments such as carbon black, titanium black, acetylene black, lamp black, bone char, graphite, aniline black, cyan black, perylene black (BASF K0084, K0086), and iron oxide-based black pigments.

In addition, fine particles mainly composed of silver-tin alloy described in Japanese Patent Application Laid-Open No. 2010-134453 can also be used. In that case, specific photopolymerization initiators are used in combination. In addition, from the viewpoint of forming a desired pattern shape, specific alkali-soluble resins may be used in combination as described in JP-A-2013-130843. Furthermore, from the viewpoint of forming a desired pattern shape, it can also be used in combination with a specific perylene-based black pigment (perylene black) as described in JP-A-2013-134264.

Among these, carbon black and titanium black are preferable from the viewpoint of light-shielding ratio and image characteristics.

As an example of carbon black, the following carbon black is mentioned.

Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44 , #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, # 2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

Made by Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, Printex L, Printex G, Printex P, Printex U, Printex G Black, Printex G Black, Printex VBlack, Printex V5 , SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color BlackFW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 (among these, Printex is a registered trademark)

Cabot公司制：Monarch120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130 , VULCAN XC72R, ELFTEX-8Koronbiyan (among these, Monarch is a registered trademark)

Carbon公司制：RAVEN11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 (among these, RAVEN is a registered trademark)

In order to increase the volume resistance value on the basis of increasing the carbon black content, carbon black coated with resin can also be used. For example, carbon black or the like described in JP-A-09-71733 can be preferably used.

As carbon black to be subjected to coating treatment, it is preferable that the total content of Na and Ca is 100 ppm or less. This is because carbon black usually contains ash on the order of a percentage, and the composition of the ash is: raw material oil, combustion oil (or gas) at the time of manufacture, reaction termination water, granulation water, and furnace material of the reaction furnace Na mixed in, and Ca, K, Mg, Al, Fe, etc. Among them, the contents of Na and Ca are usually several hundreds of ppm or more, but if they exist in large amounts, they may permeate into the transparent electrode (ITO) or other electrodes and cause electrical short circuits.

As a method for reducing the content of ash including these Na and Ca, it is possible to strictly select materials whose contents are as small as possible as raw material oil, fuel oil (or gas) and reaction termination water when producing carbon black, and It is possible to reduce the amount of alkali substance added for structure adjustment.

As another method, there may be mentioned a method in which Na and Ca are dissolved and removed by washing carbon black produced from a furnace with water, hydrochloric acid, or the like.

Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, when a solvent that is poorly soluble in water is added, the carbon black is transferred to the solvent side and completely separated from water. At the same time, the Na, Almost all Ca is dissolved in water or acid and removed.

In order to reduce the total amount of Na and Ca to 100 ppm or less, these two methods can be used in combination to make the total amount of Na and Ca 100 ppm or less more easily.

In addition, the resin-coated carbon black is preferably so-called acid carbon black with a pH of 6 or less. Since such carbon black has a small dispersion diameter (agglomeration diameter) in water, it is possible to coat even finer units, so it is preferable. Furthermore, it is preferable that the resin-coated carbon black has a particle size of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 mL/100 g or less. This is because when the particle size is larger than 40nm and the DBP absorption is larger than 140mL/100g, the dispersibility in the case of making a paste is excellent, but the concentration of the coating film may be insufficient, and there is a problem when the film thickness is about 1 to 2 μm. The hidden danger of insufficient shading.

There is no particular limitation on the method of producing the carbon black coated with the resin, and the following methods can be used. For example, after properly adjusting the amount of carbon black and resin,

1. Mix and stir the resin solution obtained by mixing the resin with solvents such as cyclohexanone, toluene, and xylene, and heating and dissolving it, and the suspension mixed with carbon black and water to separate the carbon black and water, and then remove water and heating and kneading to obtain a composition, forming the composition into a sheet, pulverizing it and then drying it;

2. After mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and resin, the obtained granules are separated and heated to remove the remaining solvent and water;

3. Dissolve carboxylic acids such as maleic acid and fumaric acid in the solvents exemplified above, add carbon black, mix and dry to remove the solvent to obtain carboxylic acid impregnated carbon black, then add resin thereto and carry out dry mixing method;

4. The reactive group-containing monomer components constituting the resin for coating are stirred at high speed with water to prepare a suspension, and then cooled after polymerization to obtain reactive group-containing monomer components from the polymer suspension. After the resin, carbon black is added thereto and kneaded, the carbon black is reacted with the reactive group (grafting the carbon black), and the method of cooling and pulverizing; and the like.

There are no special restrictions on the type of resin used for coating treatment. It is usually a synthetic resin. Further, the resin with a benzene nucleus in the structure has a stronger effect of an amphoteric surfactant, so from the perspective of dispersibility and dispersion stability Consider preferred.

As specific synthetic resins, thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glycerin resins, epoxy resins, and alkylbenzene resins, polystyrene, polycarbonate resins, etc., can be used. ester, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, polyamide-imide, polyimide Imine, polyaminobismaleimide, polyethersulfone polyphenylsulfone, polyarylate, polyetheretherketone and other thermoplastic resins.

The coating amount of the carbon black by the resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the coating amount of the resin is less than 1% by mass, there is a possibility that only the same dispersibility and dispersion stability as untreated carbon black can be obtained. On the other hand, when it exceeds 30% by mass, the binding properties between the resins are strong, and there is a possibility that pellet-like lumps may be formed and dispersion may not be performed.

Carbon black coated with a resin in this way can be used as a light-shielding material for a black matrix by a conventional method, and can be used as a color filter including the black matrix as a component by a conventional method. If such carbon black is used, there is a tendency that a black matrix having a high light-shielding ratio, low surface reflectance, and a thin film thickness can be realized at low cost. It can be speculated that this is because the dispersibility and dispersion stability of carbon black have been significantly improved relative to the resin and solvent constituting the black matrix liquid (if it is traditional carbon black, it is difficult to make the dispersed particle size If it is less than 0.1 μm, even if it is dispersed, its stability will be poor, and a large amount of aggregation will occur over time). In addition, it is presumed that by covering the surface of the carbon black with a resin, it also plays a role of enclosing Ca and Na in the carbon black.

Moreover, as an example of a commercial item of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C etc. by MITSUBISHI MATERIALS Corporation are mentioned.

As the production method of titanium black, including: the method of reducing the mixture of titanium dioxide and metal titanium by heating it in a reducing gas atmosphere (Japanese Patent Application Laid-Open No. 49-5432), and hydrolyzing titanium tetrachloride at high temperature And the method that the obtained ultrafine titanium dioxide is reduced in a reducing gas atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322 communique), the method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. No. 60-65069, Japanese Patent Laying-Open No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. , but not limited to these methods.

In addition, it can also be used as a black pigment by mixing other coloring pigments.

As other coloring pigments, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, and brown pigments can be used. In addition, as its structure, in addition to azos, phthalocyanines, quinacridones, benzimidazolones, isoindolinones, bis In addition to organic pigments such as azines, indanthrones, and perylenes, various inorganic pigments can be used.

Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. It should be noted that terms such as "C.I. Pigment Red 2" listed below represent color index (C.I.).

Examples of red pigments include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53: 1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81: 1, 81:2, 81:3, 81:4, 83, 88, 90:1, 97, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 188, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 230, 231, 232, 233, 235, 236, 237, 238, 239, 240, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is preferably used, and C.I. Pigment Red 177, 209, 224, 254 is more preferably used.

Examples of blue pigments include: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 22 , 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75 , 76, 78, 79. Among them, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferable, and C.I. Pigment Blue 15:6 is more preferable.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, C.I. Pigment Green 7 and 36 are preferably mentioned.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, , 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165 ,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194 , 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferably used, and C.I. Pigment Yellow 83, 138, 139, 150, and 180 are more preferably used.

Examples of orange pigments include: C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55, 59, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, C.I. Pigment Orange 38, 64, and 71 are preferably mentioned.

Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferable, and C.I. Pigment Violet 23 is more preferable.

In addition, barium sulfate, lead sulfate, titanium oxide, lead yellow, iron oxide red, chromium oxide, etc. can also be used as a pigment.

The above-mentioned various pigments can also be used in combination of multiple types. For example, in order to be close to black, the following combinations can be enumerated: blue pigment and red pigment, blue pigment and red pigment and purple pigment, blue pigment and red pigment and purple pigment and yellow pigment, blue pigment and orange pigment, Combinations of blue pigments and red pigments and orange pigments, blue pigments and purple pigments and orange pigments, etc.

It should be noted that these pigments are preferably dispersed so that the average particle diameter is usually 1 μm, preferably 0.5 μm or less, and more preferably 0.25 μm or less.

In addition, in this invention, the average particle diameter of a pigment is the value calculated|required from the particle diameter of the pigment measured by dynamic light scattering DLS. The particle size measurement is performed on a fully diluted colored resin composition (usually diluted to adjust the pigment concentration to about 0.005 to 0.2% by mass, but depending on the measurement equipment, if there is a recommended concentration, follow the concentration.), Measurements were performed at 25°C.

In addition, examples of dyes that can be used as color materials include azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, methine dyes etc.

Examples of azo dyes include: C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Media Red 7, C.I. Media Yellow 5, C.I. Media Black 7, etc.

Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60, etc. .

In addition, as phthalocyanine dyes, for example: C.I. Vat Blue 5 etc.; as quinone imine dyes, for example: C.I. Basic Blue 3, C.I. Basic Blue 9, etc.; For example: C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc.; examples of nitro dyes include: C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, etc.

<(B') Organic Binder>

The light-shielding material in the substrate with a light-shielding material according to the first embodiment contains (B) an organic binder. The (B) organic binder can be obtained, for example, by subjecting the (B') organic binder to polymerization and curing through exposure treatment and thermal curing treatment. Therefore, the colored resin composition used to form the above light-shielding material generally contains (B') an organic binder.

The (B') organic binder used in the present invention is a component that forms a light-shielding material as a binder resin, and is preferably an alkali-soluble resin from the viewpoint of making the ultraviolet unexposed portion easier to develop. In particular, an alkali-soluble resin having an ethylenically unsaturated bond is preferred, and an alkali-soluble resin having a carboxyl group and an ethylenically unsaturated bond is more preferred from the viewpoint of improving the curability of the ultraviolet-exposed portion. Especially preferred are the following alkali-soluble resin (B1) and/or alkali-soluble resin (B2) (hereinafter also referred to as "carboxyl group-containing epoxy (meth)acrylate resin").

<Alkali-soluble resin (B1)>

Alkali-soluble epoxy resin obtained by adding an epoxy resin to an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and then reacting with a polybasic acid and/or its anhydride resin.

<Alkali-soluble resin (B2)>

It can be obtained by adding an epoxy resin to an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and then reacting it with a polyhydric alcohol, a polybasic acid and/or an anhydride thereof. Alkali soluble resin.

As an epoxy resin used as a raw material, for example, a bisphenol A type epoxy resin (for example, "Epikote 828", "Epikote 1001", "Epikote 1002", "Epikote 1004" manufactured by Mitsubishi Chemical Corporation, etc.) can be preferably used. , Epoxy resin obtained by reacting the alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.) , bisphenol F type resin (for example, "Epikote 807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation), alcohol passing through bisphenol F type epoxy resin Epoxy resin obtained by reacting hydroxyl group with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent weight 350, softening point 66°C)), bisphenol S-type epoxy resin, biphenyl Glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EPN-201" manufactured by Mitsubishi Chemical Corporation -152", "EP-154", "DEN-438" manufactured by Dow Chemical Company), (o-, m-, p-)cresol novolak type epoxy resin (for example, "EOCN" manufactured by Nippon Kayaku Co., Ltd. -102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resin (for example, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins ("Celloxide 2021P", "Celloxide EHPE" manufactured by Daicel Chemical Industry Co., Ltd.) , Epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by Dainippon Ink Co., Ltd., "NC-7200" manufactured by Nippon Kayaku Co., Ltd. 7300"), epoxy resins represented by the following general formulas (b1) to (b4), etc. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (b1), Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (b2) "NC-3000" manufactured by Co., Ltd., "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd., which is an epoxy resin represented by the following general formula (b4), and the like.

[chemical formula 1]

(In the above-mentioned general formula (b1), a represents the average value and represents a value within the range of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a ring with 3 to 10 carbon atoms Alkyl, phenyl, naphthyl, or biphenyl. It should be noted that a plurality of R ¹¹ present in one molecule may be the same as or different from each other.)

[chemical formula 2]

(In the above-mentioned general formula (b2), b represents the average value and represents a value within the range of 0 to 10. ^R21 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a ring with 3 to 10 carbon atoms Alkyl, phenyl, naphthyl, or biphenyl. It should be noted that a plurality of R ²¹ present in one molecule may be the same as or different from each other.)

[chemical formula 3]

(In the above general formula (b3), X represents a linking group represented by the following general formula (b3-1) or (b3-2), and the molecular structure contains more than one adamantane structure, and c represents 2 or integer of 3.)

[chemical formula 4]

(In the above general formulas (b3-1) and (b3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group optionally having a substituent, a hydrogen atom, an optionally substituent C1-12 alkyl group or phenyl group optionally having a substituent. * represents the bonding site.)

[chemical formula 5]

(In the above general formula (b4), d and e each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more. It should be noted that when there are multiple ^R43 and ^R44 in the formula, they may be the same or different from each other.)

Among these, epoxy resins represented by general formulas (b1) to (b4) are preferably used.

Examples of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, Vinyl benzoic acid, (meth)acrylic acid α-halogenated alkyl, alkoxy, halogen atom, nitro, cyano substituents and other monocarboxylic acids, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-( Meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-( Meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipate, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)propene Acyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, addition of ε-caprolactone, β-propiolactone, γ-butyrolactone to (meth)acrylic acid esters, δ-valerolactone and other lactones, or succinic acid (anhydride), phthalic acid ( anhydride), maleic acid (anhydride) and other acids (anhydrides), monomers obtained from (meth)acrylic acid dimers, and the like.

Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

A known method can be used as a method of adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, tetramethylammonium chloride, tetraethylammonium chloride, dodecyl Quaternary ammonium salts such as alkyltrimethylammonium chloride, etc.

It should be noted that the epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more Use in combination.

The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents to 1 equivalent of epoxy groups in the epoxy resin, More preferably, it is the range of 0.7-1.1 equivalent.

If the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the introduction amount of unsaturated groups is insufficient, and the next step with polybasic acid and/or its anhydride responses are also inadequate. In addition, it is disadvantageous that a large amount of epoxy groups remain. On the other hand, if the usage-amount is large, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester which has a carboxyl group will remain as an unreacted substance. In either case, it can be considered that the curing property tends to deteriorate.

As the polybasic acid and/or its anhydride, one or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid can be cited. , pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalate, endomethylene tetrahydrophthalic acid, hexachloronorbornene diacid, methyl tetrahydrophthalate Esters, biphenyltetracarboxylic acid and anhydrides of these acids, etc.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides of these acids. Tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride are particularly preferable.

For the addition reaction of polybasic acid and/or its anhydride, a known method can be used, and it can be mixed with α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group with respect to epoxy resin Under the same conditions as the addition reaction, the reaction is continued to obtain the target compound. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, more preferably 20 to 140 mgKOH The amount of the degree in the /g range. When the acid value of the carboxyl group-containing epoxy (meth)acrylate resin is less than the above range, alkali developability tends to be insufficient, and when it exceeds the above range, the tendency for curing performance to deteriorate is confirmed.

It should be noted that, during the addition reaction of the polybasic acid and/or its anhydride, polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added to introduce a multibranched structure.

A carboxyl group-containing epoxy (meth)acrylate resin is usually obtained by mixing a polyvalent After the acid and/or its anhydride, or in the epoxy resin and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, mixed polybasic acid and/or its anhydride and polyfunctional alcohols followed by heating. In this case, the mixing order of the polybasic acid and/or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride will react with the reactants of the epoxy resin and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic ester with carboxyl group and the polyfunctional alcohol Any hydroxyl groups in the mixture undergo addition reactions.

The polystyrene-equivalent weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 1,500 or more, and usually 10,000 or less, Preferably it is 8000 or less, and more preferably 6000 or less. When the weight average molecular weight is small, the solubility in the developing solution is high, and when it is too large, the solubility in the developing solution is low.

The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or as a mixture of two or more resins.

In addition, as far as the (B') organic binder used in the present invention is concerned, without impairing the performance of the present invention, a part of the aforementioned carboxyl-containing epoxy (meth)acrylate resin can also be replaced with Other binder resins. That is, a carboxyl group-containing epoxy (meth)acrylate resin may be used in combination with other binder resins. In this case, the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in the organic binder (B') is preferably 50% by mass or more, particularly preferably 80% by mass or more.

There is no limit to other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin, as long as the performance of the present invention is not impaired, from those commonly used in photosensitive colored resin compositions for color filters You can choose from the available resins.

In addition, any other binder resin may be used individually by 1 type, and may use it in combination of 2 or more types.

<(B) Organic Binder>

The organic binder in the light-shielding material does not necessarily contain the (B') organic binder in the colored resin composition as it is due to polymerization, decomposition, etc. due to exposure, development treatment, and heat curing treatment described later. structure.

For α,β-unsaturated monocarboxylic acid added as a side chain, α,β-unsaturated monocarboxylic acid ester having carboxyl group, polyhydric alcohol, polybasic acid and/or its anhydride, after heat treatment, Its structure may not necessarily remain in most cases.

There is a high possibility that the main skeleton part of the resin remains, and when using the epoxy resins represented by the above general formulas (b1) to (b4), there are structural tendencies.

(from b1 skeleton)

[chemical formula 6]

In the above formula (b1-1), R ¹¹ and a have the same meaning as R ¹¹ and a in the above general formula (b1). * Indicates a bonding site.

[chemical formula 7]

In the above formulas (b1-2) to (b1-4), R ¹¹ has the same meaning as R ¹¹ in the above general formula (b1). * Indicates a bonding site.

(from b2 skeleton)

[chemical formula 8]

In the above formula (b2-1), R ²¹ and b have the same meaning as R ²¹ and b in the above general formula (b2). * Indicates a bonding site.

[chemical formula 9]

In the above formulas (b2-2) to (b2-4), R ²¹ has the same meaning as R ²¹ in the above general formula (b2). * Indicates a bonding site.

(from the b3 skeleton)

[chemical formula 10]

In the above formula (b3-1-1) and formula (b3-2-1), R ³¹ to R ³⁷ have the same meaning as R ³¹ to R ³⁷ in the above general formula (b3). * Indicates a bonding site.

(derived from the b4 skeleton)

[chemical formula 11]

In the above formula (b4-1), R ⁴¹ and R ⁴² have the same meaning as R ⁴¹ and R ⁴² in the above general formula (b4). * Indicates a bonding site.

<(D) Organic solvent>

As described above, the light-shielding material in the substrate with light-shielding material according to the first embodiment can usually use a colored resin composition containing at least (A) a color material, (B) an organic binder, and if necessary (C) fine particles. And formed. Various materials contained in the colored resin composition are usually used in a state of being dissolved or dispersed in (D) an organic solvent.

As (D) the organic solvent, it is preferable to select a solvent having a boiling point in the range of 100 to 300°C. More preferably, it is a solvent which has a boiling point of 120-280 degreeC.

As such an organic solvent, the following solvents are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Glycol monoalkyl ethers such as butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol monomethyl ether;

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, etc. diol dialkyl ethers;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethyl Ester, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol mono Diethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-acetic acid Glycol alkyl ether acetates such as methyl-3-methoxybutyl ester;

Ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate and other glycol diacetates;

Alkyl acetates such as cyclohexyl acetate;

Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethylpentyl ketone Ketones such as methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone;

Ethanol, Propanol, Butanol, Hexanol, Cyclohexanol, Ethylene Glycol, Propylene Glycol, Butylene Glycol, Diethylene Glycol, Dipropylene Glycol, Triethylene Glycol, Methoxymethylpentanol, Glycerin, Benzyl Alcohol Such monoalcohols or polyols;

Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene and dodecane;

Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Amyl Formate, Ethyl Formate, Ethyl Acetate, Butyl Acetate, Propyl Acetate, Amyl Acetate, Methyl Isobutyrate, Glycol Acetate, Ethyl Propionate, Propyl Propionate, Butyl Butyrate ester, isobutyl butyrate, methyl isobutyrate, ethyl caprate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Chain or Cyclic esters;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxymethylpentanone;

Nitriles such as acetonitrile and benzonitrile, etc.

Examples of commercially available solvents equivalent to the above include: Mineral spirit, Varsol#2, Apco#18 solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, ShellTS28solvent, card Must alcohol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol di Diethyl ether (diglyme) (both are trade names, "cellosolve" is a registered trademark) and the like.

These organic solvents may be used alone or in combination of two or more.

In the case of forming the pixels of the color filter or the black matrix by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200° C. solvent. An organic solvent having a boiling point of 120 to 170°C is more preferable. If the boiling point is low, unevenness is likely to occur at the time of drying, and if the boiling point is high, the burden on the drier may be increased, or the residue may remain in the film as a residual solvent.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferable in terms of a good balance of coatability, surface tension, etc., and high solubility of constituent components in the composition.

In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Among these, propylene glycol monomethyl ether is particularly preferable in view of the solubility of the constituent components in the composition. It should be noted that diol monoalkyl ethers have high polarity, and if the added amount is too large, there is a tendency for the pigment to easily aggregate and increase the viscosity of the colored resin composition obtained later, and the storage stability tends to decrease. Therefore, the ratio of the glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

In addition, it is also preferably used in combination with an organic solvent having a boiling point of 150° C. or higher (hereinafter also referred to as “high boiling point solvent”). Use in combination with such a high-boiling-point solvent makes the colored resin composition difficult to dry, but has the effect of preventing the uniform dispersion state of the pigment in the composition from being disrupted by rapid drying. That is, for example, there is an effect of preventing foreign matter defects from being generated at the tip of the slit nozzle due to precipitation and solidification of coloring materials and the like. From the viewpoint that such effects are remarkable, among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable.

The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, particularly preferably 5% by mass to 30% by mass. If the amount of high-boiling-point solvent is too small, there is a possibility that foreign matter defects may be caused by, for example, precipitation and solidification of color materials at the front end of the slit nozzle. In addition, if the amount of high-boiling-point solvent is too large, the drying speed of the composition It is slower, and there are problems such as poor tact in the reduced-pressure drying process and pinhole traces of pre-bake in the color filter manufacturing process described later.

It should be noted that the high boiling point solvent having a boiling point of 150° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, high boiling point solvents having a boiling point of 150° C. boiling point solvent.

As a preferred high-boiling point solvent, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, glycerin triacetate, etc.

In addition, as a preferable example of the high-boiling-point solvent having a boiling point of 180° C. or higher, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, Dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, glycerin triacetate, etc.

In addition, it is also effective to partially contain an organic solvent having a boiling point lower than 180° C. in order to adjust the viscosity of the ink or the colored resin composition described later, or to adjust the solubility of the solid content. As such an organic solvent, an organic solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Among them, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexyl acetate and the like are particularly preferable.

On the other hand, when the organic solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. Therefore, alcohols are preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, in all organic solvents.

<(E) Photopolymerization Initiator>

The light-shielding material in the substrate with a light-shielding material according to the first embodiment, and the colored resin composition for forming the light-shielding material may further contain (E) a photopolymerization initiator.

(E) The photopolymerization initiator is a component having a function of directly absorbing light to cause a decomposition reaction or a dehydrogenation reaction to generate polymerization active radicals. It can also be used by adding additives such as a sensitizing dye as needed.

As the (E) photopolymerization initiator, for example: Japanese Patent Application Laid-Open No. 59-152396, Japanese Patent Application No. 61-151197, metallocene compounds containing titanocene compounds; Japanese Patent Application Laid-Open No. 2000- Hexaaryldiimidazole derivatives described in Gazette No. 56118; Halomethylated derivatives described in JP-A No. 10-39503 Oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylaminoacetic acid, N-aryl-α-amino acid salts, N-aryl-α-amino acids Radical active agents such as esters, α-aminoalkylphenone derivatives, oxime ester derivatives described in JP-A-2000-80068 and JP-A-2006-36750, etc.

Among these, oxime ester derivatives (oxime and ketoxime compounds) are particularly effective from the viewpoint of sensitivity and curability.

Specifically, for example, as titanocene derivatives, biscyclopentadienyl titanium dichloride, biscyclopentadienyl diphenyl titanium, biscyclopentadienyl bis(2,3,4,5 ,6-pentafluorophen-1-yl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophen-1-yl)titanium, dicyclopentadienylbis(2,4,6 -Trifluorophen-1-yl)titanium, biscyclopentadienylbis(2,6-difluorophen-1-yl)titanium, biscyclopentadienylbis(2,4-difluorophen-1-yl) ) titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophen-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6 -difluorophen-1-yl)titanium, biscyclopentadienyl[2,6-difluoro-3-(pyrrol-1-yl)-phen-1-yl]titanium, and the like.

In addition, examples of diimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5- Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl )-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

In addition, as halomethylated Oxadiazole derivatives, such as: 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)ethenyl]-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4- Oxadiazole, 2-trichloromethyl-5-furyl-1,3,4- Oxadiazole etc.

In addition, examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl) Naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, etc.

In addition, examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl Base-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanol Alkan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminobenzene Acetone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

As a photopolymerization initiator, especially in terms of sensitivity, oxime derivatives (oxime and ketoxime compounds) are effective, because the use of alkali-soluble resins containing phenolic hydroxyl groups as (B) organic binders Such cases are disadvantageous in terms of sensitivity, and therefore, such oxime derivatives (oxime and ketoxime compounds) which are particularly excellent in sensitivity are useful.

As an oxime compound, the compound containing the structural part represented by following General formula (6-1) is mentioned, Preferably, the oxime ester compound represented by following General formula (6-2) is mentioned.

[chemical formula 12]

(In formula (6-1), ^R62 represents an optionally substituted alkanoyl group with 2 to 12 carbon atoms, a heteroaryl alkanoyl group with 1 to 20 carbon atoms, and an alkenoyl group with 3 to 25 carbon atoms , cycloalkanoyl with 3 to 8 carbon atoms, alkoxycarbonylalkanoyl with 3 to 20 carbon atoms, phenoxycarbonylalkanoyl with 8 to 20 carbon atoms, heteroaryloxy with 3 to 20 carbon atoms Cylcarbonylalkanoyl, aminoalkylcarbonyl with 2 to 10 carbon atoms, aroyl with 7 to 20 carbon atoms, heteroaroyl with 1 to 20 carbon atoms, alkoxycarbonyl with 2 to 10 carbon atoms, or an aryloxycarbonyl group with 7 to 20 carbon atoms.)

[chemical formula 13]

(In formula (6-2), R ^61a represents a hydrogen atom, or an optionally substituted alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 25 carbon atoms, a heterogeneous group with 1 to 20 carbon atoms Arylalkyl, alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl or heteroaryl with 1 to 20 carbon atoms Thioalkyl, aminoalkyl with 1 to 20 carbon atoms, alkanoyl with 2 to 12 carbon atoms, alkenoyl with 3 to 25 carbon atoms, cycloalkanoyl with 3 to 8 carbon atoms, An aroyl group with 7 to 20 carbon atoms, a heteroaroyl group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, an aryloxycarbonyl group with 7 to 20 carbon atoms, or an aroyl group with 1 to 10 carbon atoms Cycloalkylalkyl.

R ^61b represents any substituent containing an aromatic ring or a heteroaryl ring.

It should be noted that R ^61a and R ^61b can also form a ring together, and the linking group can include an alkylene group with 1 to 10 carbon atoms and a polyvinyl group (-(CH=CH) optionally having a substituent, respectively. _r -), a polyacetylene group (-(C≡C) _r -), or a combination thereof (where r is an integer of 1 to 3).

R ^62a represents an optionally substituted alkanoyl group with 2 to 12 carbon atoms, a heteroaryl alkanoyl group with 1 to 20 carbon atoms, an alkenoyl group with 3 to 25 carbon atoms, and a ring with 3 to 8 carbon atoms. Alkanoyl, alkoxycarbonylalkanoyl with 3 to 20 carbon atoms, phenoxycarbonylalkanoyl with 8 to 20 carbon atoms, heteroaryloxycarbonylalkanoyl with 3 to 20 carbon atoms, 2 carbon atoms Aminocarbonyl with ∼10 carbon atoms, aroyl group with 7 to 20 carbon atoms, heteroaroyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms or aryloxycarbonyl group with 7 to 20 carbon atoms . )

Examples of R ⁶² in the above general formula (6-1) and R ^62a in the above general formula (6-2) include preferably an alkanoyl group having 2 to 12 carbon atoms and a heteroaryl group having 1 to 20 carbon atoms. an alkylalkanoyl group, or a cycloalkanoyl group having 3 to 8 carbon atoms.

Examples of R ^61a in the above general formula (6-2) preferably include unsubstituted methyl, ethyl, propyl, or propyl substituted with N-acetyl-N-acetoxyamino.

In addition, examples of R ^61b in the above general formula (6-2) preferably include an optionally substituted carbazolyl group, an optionally substituted thioxanthone group, or an optionally substituted phenylthio group.

In addition, examples of arbitrary substituents in the above general formulas (6-1) and (6-2) include alkyl groups, aryl groups, alicyclic groups, heterocyclic groups, halogen groups, hydroxyl groups, carboxyl groups, amides Base etc.

Moreover, as a ketoxime compound, the compound containing the structural part represented by the following general formula (6-3) is mentioned, Preferably, the oxime ester compound represented by the following general formula (6-4) is mentioned.

[chemical formula 14]

(In the above general formula (6-3), R ⁶⁴ is synonymous with R ⁶² in the above general formula (6-1).)

[chemical formula 15]

(In the above general formula (6-4), R ^63a represents an optionally substituted phenyl group, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 25 carbon atoms, an alkenyl group with 1 to 20 carbon atoms Heteroarylalkyl, alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, alkylthioalkyl with 2 to 20 carbon atoms, Heteroaryloxycarbonylalkyl or heteroarylthioalkyl with 1 to 20 carbon atoms, aminoalkyl with 1 to 20 carbon atoms, alkanoyl with 2 to 12 carbon atoms, alkenoyl with 3 to 25 carbon atoms, Cycloalkanoyl with 3 to 8 carbon atoms, aroyl with 7 to 20 carbon atoms, heteroaroyl with 1 to 20 carbon atoms, alkoxycarbonyl with 2 to 10 carbon atoms, alkoxycarbonyl with 7 to 20 carbon atoms aryloxycarbonyl, or cycloalkylalkyl having 1 to 10 carbon atoms.

R ^63b represents an arbitrary substituent including an aromatic ring or a heteroaryl ring.

It should be noted that R ^63a and R ^63b can also form a ring together, and the linking group can include an alkylene group with 1 to 10 carbon atoms and a polyvinyl group (-(CH=CH) optionally having substituents respectively. _r -), a polyacetylene group (-(C≡C) _r -), or a combination thereof (r is an integer of 1 to 3).

R ^64a represents an optionally substituted alkanoyl group with 2 to 12 carbon atoms, an alkenoyl group with 3 to 25 carbon atoms, a cycloalkanoyl group with 4 to 8 carbon atoms, and a benzoyl group with 7 to 20 carbon atoms , a heteroaroyl group with 3 to 20 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, an aryloxycarbonyl group with 7 to 20 carbon atoms, a heteroaryl group with 2 to 20 carbon atoms, or a carbon atom Alkylaminocarbonyl with the number 2-20. )

Examples of R ⁶⁴ in the above general formula (6-3) and R ^64a in the above general formula (6-4) include preferably an alkanoyl group having 2 to 12 carbon atoms and a heteroaryl group having 1 to 20 carbon atoms. Alkanoyl group, cycloalkanoyl group having 3 to 8 carbon atoms, or aroyl group having 7 to 20 carbon atoms.

Examples of R ^63a in the above general formula (6-4) preferably include unsubstituted ethyl, propyl, butyl, or ethyl or propyl substituted with methoxycarbonyl.

In addition, examples of R ^63b in the above general formula (6-4) preferably include an optionally substituted carbazolyl group or an optionally substituted phenylthio group.

In addition, examples of arbitrary substituents in the above general formulas (6-3) and (6-4) include alkyl groups, aryl groups, alicyclic groups, heterocyclic groups, halogen groups, hydroxyl groups, carboxyl groups, amides Base etc.

Specific examples of preferred oxime ester compounds and ketoxime ester compounds in the present invention include the compounds exemplified below, but are not limited to these compounds (hereinafter, "Me" means "methyl").

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylanthraquinone , 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and other anthraquinone derivatives; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methyl Benzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives; 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methyl phenylacetone, 1-hydroxy- 1-methylethyl(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2 -Morpholino-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone and other acetophenone derivatives; thioxanthone, 2-ethylthioxanthone, 2- Isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones Ketone derivatives; benzoate derivatives such as ethyl p-(dimethylamino)benzoate and ethyl p-(diethylamino)benzoate; 9-phenylacridine, 9-(p-methoxy Acridine derivatives such as phenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzophenazine; anthrone derivatives such as benzoanthrone, etc.

Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.

In the photopolymerization initiator, a sensitizing dye corresponding to the wavelength of the image exposure light source may be blended as needed for the purpose of improving sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335. The coumarin pigment with a heterocycle described in JP-A-3-239703, the 3-oxocoumarin compound described in JP-A-5-289335, JP-A-6-19240 Methylenepyrrole dyes described, and JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-2-69, JP-A 57-168088 A, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like having a dialkylaminobenzene skeleton.

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable. Particularly preferred are e.g. 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4 Benzophenone compounds such as '-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl) Benzo Azole, 2-(p-diethylaminophenyl) benzo Azole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo Azole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo Azole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Azole, 2-(p-dimethylaminophenyl) benzothiazole, 2-(p-diethylaminophenyl) benzothiazole, 2-(p-dimethylaminophenyl) benzimidazole, 2-( p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p- Diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylamino Phenyl)pyrimidine, etc. to compounds containing dialkylaminophenyl groups, etc.

Of these, 4,4'-dialkylaminobenzophenones are most preferred.

The sensitizing dye may be used alone or in combination of two or more.

<Photopolymerizable compound>

From the viewpoint of sensitivity and the like, it is preferable to further contain a photopolymerizable compound in the colored resin composition for forming the light-shielding material in the substrate with light-shielding material according to the first embodiment.

As a photopolymerizable compound used by this invention, the compound (henceforth an "ethylenic monomer") which has at least 1 ethylenic unsaturated group in a molecule|numerator is mentioned. Specific examples thereof include (meth)acrylic acid, alkyl (meth)acrylate, acrylonitrile, styrene, and monoesters of carboxylic acids having one ethylenically unsaturated bond and polyhydric alcohols or monohydric alcohols.

In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.

Examples of such polyfunctional ethylenic monomers include: esters of aliphatic polyols and unsaturated carboxylic acids; esters of aromatic polyols and unsaturated carboxylic acids; esters of aliphatic polyols , esters obtained by esterification of polyhydroxy compounds such as aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids, etc.

Examples of esters of the aforementioned aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate and other aliphatic polyol acrylates, will Methacrylate obtained by replacing the acrylate of these exemplary compounds with methacrylate, similarly, itaconate obtained by replacing the acrylate of the above-mentioned exemplary compounds with itaconate, and crotonate obtained by replacing Crotonate, or a maleic acid ester substituted with a maleic acid ester, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate Acrylate and methacrylate of aromatic polyhydroxy compounds such as acrylate and pyrogallol triacrylate.

As esters obtained by esterification of polyvalent carboxylic acids and unsaturated carboxylic acids and polyhydroxy compounds, they do not necessarily have to be a single substance, and typical examples thereof include acrylic acid, phthalic acid, and ethylene glycol. Condensates, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, etc.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate are reacted, or a polyisocyanate compound is reacted with a polyol and a hydroxyl group-containing (meth)acrylate. Urethane (meth)acrylates; epoxy acrylates such as addition reactants of polyvalent epoxy compounds with hydroxyl (meth)acrylates or (meth)acrylic acid; ethylene bisacrylamide Acrylamides such as acrylamides; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.

These may be used alone or in combination of two or more.

<Dispersant>

In the light-shielding material in the substrate with light-shielding material according to the first embodiment and the colored resin composition used for forming the light-shielding material, finely dispersing the (A) color material and stabilizing the dispersed state are crucial to ensuring Since the stability of quality is important, it is preferable to contain a dispersant.

As a dispersant, a polymer dispersant with a functional group is preferred, and further, from the perspective of dispersion stability, it is preferred to have a carboxyl group; a phosphoric acid group; a sulfonic acid group; or their bases; a primary amino group, a secondary amino group or a tertiary amino group; group; a polymer dispersant derived from functional groups such as pyridine, pyrimidine, pyrazine and other nitrogen-containing heterocyclic groups. Among them, polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are particularly preferred.

In addition, examples of polymer dispersants include polyurethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, monomers having amino groups, and macromolecular monomers. dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic ester dispersant, aliphatic Modified polyester dispersant, etc.

Specific examples of such dispersants include trade names EFKA (manufactured by EFKA-Chemicals BV), Disperbyk (manufactured by BYK-Chemie, registered trademark), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd., registered trademark), SOLSPERSE (Lubrizol Co., Ltd., registered trademark), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), Ajisper (Ajinomoto Co., Ltd., registered trademark), etc.

These polymer dispersants may be used alone or in combination of two or more.

The weight-average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among these, it is particularly preferable that the dispersant contains a functional group-containing polyurethane polymer dispersant and/or an acrylic polymer dispersant from the viewpoint of adhesiveness and linearity.

Examples of polyurethane-based polymer dispersants include Disperbyk (registered trademark) 160-167, 182 series (manufactured by BYK-Chemie), EFKA4046, and EFKA4047 (manufactured by BASF). Examples of the agent include Disperbyk (registered trademark) 2000 and 2001 (the above are manufactured by BYK-Chemie).

Examples of specific preferred chemical structures of polyurethane polymer dispersants include polyisocyanate compounds, compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and polyisocyanate compounds in the same molecule. A dispersion resin with a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having active hydrogen and a tertiary amino group.

Examples of the above-mentioned polyisocyanate compounds include p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1 , 5-diisocyanate, aromatic diisocyanate such as benzylidine diisocyanate, hexamethylene diisocyanate, lysine methyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer Aliphatic diisocyanates such as acid diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate, dimethylcyclohexane and other aliphatic diisocyanates , xylylene diisocyanate, α,α,α′,α′-tetramethylxylylene diisocyanate and other aliphatic diisocyanates with aromatic rings, lysine ester triisocyanate, undecane-1 ,6,11-triisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, hexamethylene-1,3,6-triisocyanate, dicycloheptane triisocyanate, triphenylmethane triisocyanate , Triisocyanates such as phosphorothioate triphenyl triisocyanate, and their trimers, water adducts, and their polyol adducts. As the polyisocyanate, preferred are trimers of organic diisocyanates, most preferred are trimers of toluene diisocyanate and trimers of isophorone diisocyanate. These may be used alone or in combination of two or more.

As a method for producing a trimer of isocyanate, the following method can be mentioned: using an appropriate trimerization catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Partial trimerization of isocyanate groups is carried out, the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin film distillation, thereby obtaining the target polyisocyanate containing trimeric isocyanate groups.

Examples of compounds having 1 or 2 hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, etc. , and those obtained by alkoxylation of one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and a mixture of two or more thereof.

As polyether diol, polyether diol, polyether ester diol, and the mixture of these 2 or more types are mentioned. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexamethylene glycol, Polyoxyoctylene glycol and mixtures of two or more thereof.

Examples of polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other diols with dicarboxylic acids or their anhydrides, or by reacting alkylene oxide with polyester diols, For example, poly(polyoxytetramethylene) adipate and the like. As the polyether diol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound obtained by alkoxylation of one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms is most preferable. .

Examples of polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) Diol, Diethylene Glycol, Triethylene Glycol, Propylene Glycol, Dipropylene Glycol, Tripropylene Glycol, 1,2-Butanediol, 1,3-Butanediol, 1,4-Butanediol, 2,3-Butanediol Diol, 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-tris Methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2- Aliphatic diols such as methyl-1,8-octanediol and 1,9-nonanediol, aliphatic diols such as bis(hydroxymethyl)cyclohexane, benzenedimethanol, bis(hydroxyethoxy ) Aromatic diols such as benzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate , poly-1,6-hexanediol adipate, polyethylene glycol propylene adipate, etc., or polylactones obtained by using the above-mentioned diols or monohydric alcohols with 1 to 25 carbon atoms as initiators Diols or polylactone monoalcohols, such as polycaprolactone diol, polymethylvalerolactone, and mixtures of two or more thereof. As the polyester diol, polycaprolactone diol or polycaprolactone obtained by using an alcohol having 1 to 25 carbon atoms as an initiator is most preferable.

Examples of the polycarbonate diol include: poly(1,6-hexanediol) carbonate diol, poly(3-methyl-1,5-pentanediol) carbonate diol, etc. Examples of the alcohol include polybutadiene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and the like.

These may be used alone or in combination of two or more.

The number average molecular weight of the compound which has 1 or 2 hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as hydroxyl, amino, and mercapto groups, among which hydrogen atoms of amino groups, especially primary amino groups, are preferred.

The tertiary amino group is not particularly limited, and may be, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.

Examples of such compounds having active hydrogen and tertiary amino groups in the same molecule include: N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propane Diamine, 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-butylenediamine, N,N-di Ethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

In addition, examples of the nitrogen-containing heterocycle when the tertiary amino group has a nitrogen-containing heterocycle structure include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, and indazole ring. , benzimidazole ring, benzotriazole ring, benzo Nitrogen-containing 5-membered heterocycles such as azole ring, benzothiazole ring, benzothiadiazole ring, etc.; pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Nitrogen 6-membered heterocycle. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

Specific examples of these compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole, and the like. In addition, specific examples of compounds having these triazole rings and amino groups 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-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. Among them, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, 1-(3-aminopropyl)imidazole, 3-amino- 1,2,4-triazole.

These may be used alone or in combination of two or more.

The preferred compounding ratio of raw materials for the production of polyurethane-based polymer dispersants is as follows: 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule per 100 parts by mass of polyisocyanate compound parts, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and compounds having active hydrogen and tertiary amino groups in the same molecule are 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

The production of the polyurethane polymer dispersant is carried out in accordance with known methods for producing polyurethane resins. As solvents during production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate are generally used ; Benzene, toluene, xylene, hexane and other hydrocarbons; diacetone alcohol, isopropanol, sec-butanol, tert-butanol and other alcohols; dichloromethane, chloroform and other chlorinated substances; tetrahydrofuran, ether and other ethers; Polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more.

In the above-mentioned production, a urethanization reaction catalyst is generally used. Examples of the catalyst include tins such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dicaprylate, and tin octoate, irons such as iron acetylacetonate and iron chloride, triethylamine, One or two or more of tertiary amines such as triethylenediamine.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably such that the amine value after the reaction is controlled within the range of 1 to 100 mgKOH/g, more preferably within the range of 5 to 95 mgKOH/g. The amine value is a value corresponding to the acid value expressed in mg of KOH by neutralizing the basic amino group with an acid. When the amine value is less than the above range, the dispersibility tends to decrease, and when it exceeds the above range, developability tends to decrease.

In the above reaction, when isocyanate groups remain in the polymer dispersant, it is preferable to further destroy the isocyanate groups with an alcohol or an amino compound because the stability of the product over time will increase.

The weight average molecular weight (Mw) of a polyurethane type polymer dispersant is 1,000-200,000 normally, Preferably it is 2,000-100,000, More preferably, it is the range of 3,000-50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and when it exceeds 200,000, the solubility decreases, the dispersibility is poor, and the control of the reaction becomes difficult.

As the acrylic polymer dispersant, it is preferable to use a monomer having a functional group (the functional group mentioned here is a functional group described above as a functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group but containing Random copolymers, graft copolymers, and block copolymers formed from monomers with unsaturated groups. These copolymers can be produced by known methods.

Specific examples of monomers having functional groups and unsaturated groups include: (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxy Ethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, unsaturated monomers with carboxyl groups such as acrylic acid dimer, dimethylaminoethyl (meth)acrylate, Unsaturated monomers with tertiary amino groups and quaternary ammonium bases, such as diethylaminoethyl (meth)acrylate and their quaternary compounds. These monomers may be used alone or in combination of two or more.

Examples of monomers that do not have a functional group but contain an unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid Tricyclodecanyl ester, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide N-substituted maleimides such as imide, N-benzylmaleimide, acrylonitrile, vinyl acetate and poly(meth)acrylate macromers, polystyrene macromers Macromers such as poly(2-hydroxyethyl meth)acrylate macromers, polyethylene glycol macromers, polypropylene glycol macromers, polycaprolactone macromers, etc. These monomers may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer composed of an A block with a functional group and a B block without a functional group. In addition to the group monomers, the above-mentioned monomers containing no functional groups but containing unsaturated groups may be included, and these structures may be contained in any form of random copolymerization or block copolymerization in the A block. In addition, the content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less.

The B block is formed by the above-mentioned monomers that do not contain functional groups but contain unsaturated groups. One B block can contain more than two types of monomers. These monomers can be randomly copolymerized or block in the B block. Arbitrary form in block copolymerization contains.

The A-B or B-A-B block copolymer can be prepared, for example, by living polymerization.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a free radical living polymerization method, wherein the polymerization active species of the anionic living polymerization method is an anion. The active species of polymerization in the free radical living polymerization method is a free radical.

When synthesizing the acrylic polymer dispersant, it can be used in Japanese Patent Application No. 9-62002, P.Lutz, P.Masson et al, Polym.Bull.12, 79 (1984), B.C.Anderson, G.D.Andrews et al , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right, Koichi Hatada, Polymer Processing, 36, 366 (1987 ), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Known methods described in Synthetic Organic Chemistry, 43, 300 (1985), D.Y. Sogoh, W.R. Hertler et al, Macromolecules, 20, 1473 (1987) and the like.

Whether the acrylic polymer dispersant used in the present invention is an A-B block copolymer or a B-A-B block copolymer, the ratio of the A block/B block constituting the copolymer is preferably 1/99 to 80/20, especially It is preferably 5/95 to 60/40 (mass ratio), and when it is out of this range, good heat resistance and dispersibility may not be compatible.

In addition, the amount of the quaternary ammonium salt group in 1 g of the A-B block copolymer and B-A-B block copolymer of the present invention is usually preferably 0.1 to 10 mmol, and outside this range, good heat resistance and dispersibility may not be compatible.

In addition, although such a block copolymer usually contains the amino group which arises in the manufacturing process, its amine value is about 1-100 mgKOH/g.

Here, the amine value of these dispersants such as block copolymers is represented by the mass of KOH per 1 g of solid content of the dispersant sample, and is measured by the following method. Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker, and dissolve it with 50 mL of acetic acid. Using an automatic titration device equipped with a pH electrode, the solution was neutralized and titrated with 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve was regarded as the titration end point, and the amine value was obtained by the following formula.

Amine value [mgKOH/g]=(561×V)/(W×S)

[Wherein, W: represents the weighed amount of the dispersant sample [g], V: represents the titration amount [mL] at the end of the titration, and S: represents the solid content concentration [mass %] of the dispersant sample. ]

In addition, the acid value of the block copolymer depends on the presence or absence and the type of the acidic group as the basis of the acid value. Generally, the acid value is lower, usually below 10 mgKOH/g, and its weight average molecular weight (Mw) Preferably, it is the range of 1000-100,000. When the weight-average molecular weight of the block copolymer is less than 1,000, dispersion stability tends to decrease, and when it exceeds 100,000, developability and resolution tend to decrease.

<Pigment Derivatives>

From the viewpoint of improving dispersion stability, the above-mentioned dispersant may be used in combination with the following pigment derivatives.

Examples of pigment derivatives include azos, phthalocyanines, quinacridones, benzimidazolones, quinophthalones, isoindolinones, Azines, anthraquinones, indanthrene, perylenes, pyrenes, diketopyrrolopyrroles, diketopyrrolopyrroles, Derivatives such as oxazines, among which phthalocyanines and quinophthalones are preferable.

As the substituent of pigment derivatives, sulfonic acid group, sulfonamide group and its quaternary salt, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amido group, etc. can be listed, and they can be directly Or it is bonded to the pigment skeleton via an alkyl group, an aryl group, a heterocyclic group, etc. Among the substituents of the above-mentioned pigment derivatives, a sulfonic acid group is preferred. In addition, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole derivatives. Sulfonic acid derivatives, two Sulfonic acid derivatives of oxazine, etc. These pigment derivatives may be used alone or in combination of two or more.

<Other Compounding Components of Colored Resin Composition>

In the colored resin composition for forming the light-shielding material in the substrate with light-shielding material according to the first embodiment, phosphoric acid-based additives, silane coupling agents, surfactants, mercaptans, and Additives, UV absorbers, antioxidants, etc.

(1) Phosphoric acid additives

As the phosphoric acid additive, (meth)acryloyloxy group-containing phosphoric acid esters are preferable, and those represented by the following general formula (5a), (5b) or (5c) are preferable.

[chemical formula 21]

[In the above general formulas (5a), (5b) and (5c), R ⁵¹ represents a hydrogen atom or a methyl group, p and p' are integers from 1 to 10, and q is 1, 2 or 3. ]

These phosphoric acid additives may be used alone or in combination of two or more.

(2) Silane coupling agent

In order to improve the adhesiveness with a transparent substrate, you may add a silane coupling agent.

As the kind of the silane coupling agent, one type of various silane coupling agents such as epoxy type, (meth)acryl type, and amino type can be used alone or in combination of two or more types.

Examples of preferred silane coupling agents include (meth)acrylic acid such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Acyloxysilanes, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Epoxysilanes such as oxysilane, 3-glycidoxypropyltriethoxysilane, etc., ureidosilanes such as 3-ureapropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane As isocyanate silanes such as silanes, epoxysilane-based silane coupling agents are particularly preferable.

These silane coupling agents may be used alone or in combination of two or more.

(3) Surfactant

As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, nonionic surfactants are preferably used from the viewpoint of low possibility of adversely affecting various properties, and among them, fluorine-based surfactants and silicon-based surfactants are effective in terms of coatability. of.

Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicones), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Toray Silicone Co., Ltd.), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Japan Unica Co., Ltd.), FC4430 (manufactured by Sumitomo 3M Co., Ltd.), etc.

These surfactants may be used alone or in combination of two or more of them in arbitrary combinations and ratios.

(4) Mercaptan additives

Thiols may also be added in order to achieve high sensitivity and improve adhesion to transparent substrates. Examples of mercaptans include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butylenediol dimercaptoacetate, and dimercaptoacetic acid. Ethylene glycol esters, trimethylolpropane trimercaptoacetate, butylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercapto Propionate, Pentaerythritol Tetramercaptoacetate, Trihydroxyethyl Trimercaptopropionate, Ethylene Glycol Bis(3-Mercaptobutyrate), Butylene Glycol Bis(3-Mercaptobutyrate), Trimethylol Propane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol Bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, etc. These thiol additives may be used alone or in combination of two or more.

<Amounts of Components Blended in the Colored Resin Composition>

In the colored resin composition used to form the light-shielding material in the substrate with light-shielding material according to the first embodiment, the content of the (A) color material can usually be 1 to Choose within the range of 70% by mass.

In this range, it is more preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass. When there is too little content of (A) color material, the light-shielding property as a light-shielding material will fall, and when there is too much content, sufficient image formability may not be acquired.

In addition, in the colored resin composition forming the light-shielding material on the transparent substrate side or the first layer of the light-shielding material, the content of the (A) coloring material is more preferably 1 with respect to the total solid content in the colored resin composition. -30% by mass, particularly preferably 1-20% by mass. When there is too much content of (A) color material, since the reflectance of the interface of a transparent substrate and a light-shielding material will become high, it is unpreferable.

In addition, in the colored resin composition that forms the second and subsequent layers of the light-shielding material on the side opposite to the transparent substrate, the content of the (A) coloring material is more preferably 20 to 70% by mass, particularly preferably 30 to 60% by mass. When there is too little content of (A) color material, sufficient light-shielding property may not be acquired.

When a dispersant is used, its content is usually 50% by mass or less, preferably 30% by mass or less, and usually 1% by mass or more, preferably 3% by mass or more in the solid content of the colored resin composition. Moreover, content of a dispersing agent is 5 mass % or more normally with respect to (A) color material, Especially preferably 10 mass % or more, Usually 200 mass % or less, Especially preferably, 80 mass % or less. If the content of the dispersant is too small, sufficient light-shielding properties may not be obtained, and if it is too large, the ratio of other components will decrease relatively, and the color density, sensitivity, film-forming property, etc. will tend to decrease.

In particular, as a dispersant, it is preferable to use a combination of a polymer dispersant and a pigment derivative. In this case, the compounding ratio of the pigment derivative is usually 1% by mass or more with respect to the total solid content of the colored resin composition of the present invention, Usually, it is 10 mass % or less, Preferably it is 5 mass % or less.

The content of the (B) organic binder is usually at least 5% by mass, preferably at least 10% by mass, and usually at most 85% by mass, preferably at most 80% by mass, based on the total solid content of the colored resin composition of the present invention.

(B) When the organic binder is an alkali-soluble resin, if the content thereof is remarkably small, the solubility of the unexposed portion in the developing solution is lowered, and poor development is likely to occur. Conversely, when there is too much content of (B) organic binder, the penetrability of a developing solution to an exposure part will become high, and there exists a possibility that resolution and adhesiveness of a pixel may fall.

Moreover, the quantity of (B) organic binder with respect to (A) color material is 10-500 mass % normally, Preferably it is 30-300 mass %, More preferably, it is the range of 50-200 mass %. If the content of (B) organic binding material relative to (A) color material is too low, the solubility of the unexposed part in the developer solution will decrease, which will easily cause poor development. If it is significantly higher, it will be difficult to obtain the desired pixel film. thick.

In addition, in the light-shielding material on the transparent substrate side formed therein, and in the colored resin composition of the first layer in the light-shielding material, the content of the (B) organic binder is expressed relative to the total of the (A) color material and (C) fine particles. The amount of content is preferably 10 to 300% by mass, particularly preferably 20 to 200% by mass.

The content of (C) fine particles in the colored resin composition for forming the light-shielding material on the transparent substrate side or the first layer of the light-shielding material is usually 10 to 40% by mass relative to the total solid content of the colored resin composition of the present invention. % range, preferably 15 to 35% by mass. If the content of (C) fine particles is too small, when forming the light-shielding material on the side opposite to the transparent substrate, or the second and subsequent layers of the light-shielding material, when the colored resin composition is applied, there will be a phenomenon that causes the transparent substrate side The light-shielding material and the coating film of the first layer in the light-shielding material may be dissolved. On the contrary, if the content of (C) particles is too large, the solubility of the unexposed part in the developer will decrease, which will easily cause poor development. In addition, it is preferable that the colored resin composition used for forming the layer after the 2nd layer in a light-shielding material on the side opposite to a transparent substrate does not contain (C) microparticles|fine-particles.

The content of the photopolymerization initiator (E) is usually at least 0.1% by mass, preferably at least 0.5% by mass, more preferably at least 0.7% by mass, and usually 30% by mass based on the total solid content of the colored resin composition of the present invention or less, preferably 20% by mass or less. If the content of the (E) photopolymerization initiator is too small, the sensitivity may be lowered. Conversely, if the content of the (E) photopolymerization initiator is too large, the solubility of the unexposed part in the developing solution will decrease, which will easily cause Poor development.

When an accelerator is used together with the (E) photopolymerization initiator, the content of the accelerator is usually 0% by mass or more, preferably 0.02% by mass or more, based on the total solid content of the colored resin composition of the present invention, usually It is 10 mass % or less, Preferably it is 5 mass % or less, It is preferable to use an accelerator in the ratio of 0.1-50 mass % with respect to (E) photoinitiator, especially 0.1-10 mass %. If the compounding ratio of the photopolymerization initiator components composed of (E) photopolymerization initiator and accelerator etc. is significantly low, it may cause a decrease in sensitivity to exposure light. When the compounding ratio of the photopolymerization initiator component composed of a photopolymerization initiator, an accelerator, etc. is significantly high, the solubility of the unexposed portion in the developing solution is lowered, and poor development may be caused.

In addition, the blending ratio of the sensitizing dye in the colored resin composition of the present invention is usually 0 to 20% by mass, preferably 0 to 15% by mass, and more preferably 0% by mass based on the total solid content of the colored resin composition. ~10% by mass.

When using a photopolymerizable compound, the content is usually 90 mass % or less with respect to the total solid content of the colored resin composition of this invention, Preferably it is 80 mass % or less. When there is too much content of a photopolymerizable compound, the penetrability of a developing solution to an exposure part will become high, and it may become difficult to obtain a favorable image. In addition, the lower limit of content of a photopolymerizable compound is 1 mass % or more normally, Preferably it is 5 mass % or more.

In addition, when using a silane coupling agent and/or a phosphoric acid additive, their content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass. If the content of the silane coupling agent and/or phosphoric acid additive is less than the above range, the effect of improving the adhesion cannot be obtained sufficiently, and if the content of the silane coupling agent and/or phosphoric acid additive is large, the sensitivity may decrease , or residues remain after development and become defects.

When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03% by mass relative to the total solid content of the colored resin composition. ~0.3% by mass. When the content of the surfactant is less than the above range, there is a possibility that the smoothness and uniformity of the coating film cannot be exhibited. If the content of the surfactant is large, the smoothness and uniformity of the coating film cannot be exhibited. It may cause deterioration of other characteristics.

When using a mercaptan additive, its content is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and usually 10% by mass relative to the total solid content of the colored resin composition of the present invention. % or less, preferably 5% by mass or less. When the content of the mercaptan additive is too small, the sensitivity may be lowered, and on the contrary, if the content is too large, the storage stability may be deteriorated.

In addition, the colored resin composition of this invention can be liquid-prepared so that solid content concentration may be 5-50 mass % normally, and preferably 10-30 mass % using the above-mentioned (D) organic solvent.

<Manufacturing method of colored resin composition>

The colored resin composition (hereinafter also referred to as "resist") for forming the light-shielding material in the substrate with light-shielding material according to the first embodiment can be produced by a conventional method.

Usually, for the (A) color material, it is preferable to perform dispersion treatment in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (A) color material is atomized by the dispersion treatment, the coating properties of the resist are improved. Moreover, when using a black color material as (A) color material, it contributes to improvement of light-shielding ability.

Dispersion treatment is usually preferably carried out in a system that uses (A) a color material, (D) an organic solvent, and if necessary a dispersant, and (B) an organic binder and/or other binder resin in combination. (Hereafter, the mixture used for the dispersion treatment and the composition obtained by the treatment are also referred to as "ink"). In particular, when a polymer dispersant is used as a dispersant, it is preferable because it can suppress the thickening of the obtained ink and resist over time (that is, it is excellent in dispersion stability).

In addition, when performing dispersion treatment on a liquid containing all components to be blended into the colored resin composition, highly reactive components may be modified due to heat generation during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment with a system containing the aforementioned components.

When dispersing the (A) color material with a sand mill, it is preferable to use glass beads or zirconia beads with a diameter of approximately 0.1 to 8 mm. Dispersion treatment conditions are usually in the range of 0°C to 100°C, preferably room temperature to 80°C. Depending on the composition of the liquid and the size of the dispersion treatment device, etc., the appropriate time for the dispersion time is different, so it should be adjusted appropriately. The approximate standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741-1997) of the resist falls within the range of 100 to 200. When the gloss of the resist is low, the dispersion treatment is insufficient, and rough pigment (color material) particles may remain in many cases, which may result in insufficient developability, adhesion, resolution, etc. . In addition, if the dispersion treatment is carried out until the gloss value exceeds the above-mentioned range, the pigment will be crushed to generate a large number of ultrafine particles, and thus the dispersion stability tends to be impaired instead.

Next, the ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the resist to prepare a uniform solution. In the resist manufacturing process, since fine dust is often mixed into the liquid, it is preferable to filter the obtained resist with a filter or the like.

[Formation method of light-shielding material]

Hereinafter, a method of forming the light-shielding material of the present invention on a transparent substrate using the colored resin composition of the present invention described above will be described.

In addition, as a transparent substrate, the transparent substrate exemplified in the description of the color filter mentioned later can be used, for example.

Examples of the method for forming the light-shielding material of the present invention include a method of etching a coating film of a colored resin composition with a positive resist or the like, a method of using a photosensitive colored composition, and the like.

As a method of etching, it is possible to form a coating film of a colored resin composition on a transparent substrate, then form a desired pattern with a coating film of a positive photoresist, then perform etching using an etching solution, and finally peel off with a stripping agent. positive photoresist to form a light-shielding material.

In the case of using a photosensitive coloring composition, the photosensitive coloring resin composition is coated on a transparent substrate and dried, and then a photomask is laminated on the formed coating film, and through the photomask, the The image is exposed, developed, and if necessary, thermally or photocured to form a pixel image, thereby forming a light-shielding material.

The light-shielding material of the present invention is a material in which two or more light-shielding layers are laminated and formed on a transparent substrate. Therefore, in the method for producing the light-shielding material described above, for each layer of each light-shielding layer, based on the coloring resin composition or photosensitivity Formation of a coating film by applying and drying the colored resin composition, and after forming a multilayer laminated coating film, in the case of positive etching, post-etching to form a positive photoresist coating film , in the case of using a photosensitive colored resin composition, image exposure is performed.

Hereinafter, the case of forming a light-shielding material laminated with two light-shielding layers using a photosensitive colored resin composition will be described with reference to FIGS. 2(a) to 2(c). The limitations of the method. Moreover, when forming the light-shielding material which has 3 or more layers of light-shielding layers, it can perform similarly to the method demonstrated below except having performed the formation of the coating film for 2nd light-shielding layers several times in the same way.

As shown in FIG. 2( a), a first light-shielding layer coating film 12A is formed by coating a photosensitive colored resin composition for forming a first light-shielding layer on a transparent substrate 11 and drying it. 2. The photosensitive colored resin composition for light-shielding layer formation is dried, and 13 A of 2nd coating films for light-shielding layers are formed. Then, as shown in FIG. 2( b ), by laminating a photomask 15 on the laminated coating film, exposing through the photomask 15, developing, and performing thermal curing or photocuring as necessary, thereby By forming a pixel image, a light-shielding material having a laminated structure formed of the first light-shielding layer 12 and the second light-shielding layer 13 as shown in FIG. 2( c ) is formed.

(1) Coating of photosensitive colored resin composition

Coating of the photosensitive colored resin composition can be performed by a spin coating method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among them, the use of die coating can significantly reduce the amount of coating liquid used, and there is no influence of fogging and the like attached during spin coating, and the generation of foreign matter can be suppressed, so it is preferable from a comprehensive point of view.

If the thickness of the coating film is too thick, pattern development becomes difficult, and for example, in the use of color filters for liquid crystal display devices, gap adjustment in the process of forming liquid crystal cells may become difficult. If the thickness of the coating film is too thin, In this case, it is difficult to increase the pigment concentration, and desired light-shielding properties may not be achieved. The thickness of the coating film can be set to a thickness capable of forming a layer having an appropriate film thickness of the aforementioned light-shielding material, first light-shielding layer, and second light-shielding layer.

(2) Drying of the coating film

It is preferable to perform drying of the coating film after apply|coating a photosensitive colored resin composition on a transparent substrate by the drying method using a hot plate, IR oven, and a convection oven. Drying conditions can be appropriately selected according to the type of the above-mentioned solvent component, the performance of the drier to be used, and the like. The drying time can be selected in the range of 15 seconds to 10 minutes at a temperature of 40 to 200° C., preferably in the range of 30 seconds to 10 minutes at a temperature of 50 to 150° C. Choose from a range of 5 minutes.

Among them, the drying conditions of the coating film for the first light-shielding layer are particularly preferably selected within the range of 60 seconds to 5 minutes at a temperature of 100 to 150°C.

If the drying is too weak, the coating film for the first light-shielding layer may dissolve when the photosensitive colored resin composition for forming the second light-shielding layer is applied, and if it is too strong, poor development may occur.

In addition, the drying process of this coating film can also perform the reduced pressure drying method which does not raise a temperature, but performs drying in a reduced pressure chamber.

Coating and drying of the above-mentioned photosensitive colored resin composition are carried out for each light-shielding layer to be formed, and subsequent exposure is carried out after forming a coating film of the required number of laminated layers.

(3) Exposure

Image exposure is performed by superimposing a negative mask pattern on the laminated coating film of the photosensitive colored resin composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen. The light source used for the above-mentioned image exposure is not particularly limited. Examples of light sources include lamps such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; Molecular laser, nitrogen laser, helium cadmium laser, semiconductor laser and other laser light sources, etc. When irradiating and using light of a specific wavelength, an optical filter can also be used.

(4) Development

An image can be formed on the substrate by development using an organic solvent or an aqueous solution containing a surfactant and a basic compound after image-wise exposure of the coating film formed of the photosensitive colored resin composition with the light source described above. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Examples of basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds, or monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or Trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or tri Organic basic compounds such as isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. These basic compounds may be a mixture of two or more.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates, etc. Agents; amphoteric surfactants such as alkyl betaines and amino acids.

As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. are mentioned, for example. An organic solvent may be used alone or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited, and usually the development temperature can be in the range of 10°C to 50°C, preferably at 15°C to 45°C, particularly preferably at 20°C to 40°C, by dipping, spraying, or brush development. It is carried out by any method among the developing methods such as the ultrasonic developing method and the ultrasonic developing method.

(5) Thermal curing treatment

After development, thermal curing treatment may also be performed. The thermal curing treatment conditions at this time can be selected within the range of temperature 100-280° C., preferably 150-250° C., and the time can be selected within the range of 5-60 minutes.

It should be noted that the light-shielding material of the present invention is mainly used as a black matrix of a color filter, but is not limited to a black matrix at all.

[Ingredient compounding amount in the light-shielding material]

In the light-shielding material of the substrate with light-shielding material according to the first embodiment, since the coloring material in the colored resin composition remains in the light-shielding material, the content of the (A) coloring material relative to the total mass of the light-shielding material is generally It is in the range of 1 to 70% by mass, preferably 10 to 60% by mass.

In addition, among these, in the region on the transparent substrate side, the content of the (A) coloring material is more preferably 1 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total mass of the light-shielding material.

In addition, in the region opposite to the transparent substrate, the content of the (A) coloring material is more preferably 20 to 70% by mass, particularly preferably 30 to 60% by mass, based on the total mass of the light-shielding material.

Since polymerization, decomposition, etc. will occur due to the exposure, development treatment, and thermal curing treatment described above, the light-shielding material does not necessarily have the same composition as that added as the colored resin composition other than the (A) color material. The state is formed, and its composition is roughly as follows.

When using a dispersant, it is usually 50 mass % or less, Preferably it is 30 mass % or less, Usually 1 mass % or more, Preferably it is 3 mass % or more with respect to the total mass of a light-shielding material.

(B) The organic binder is usually at least 5% by mass, preferably at least 10% by mass, and usually at most 85% by mass, preferably at most 80% by mass, based on the total mass of the light-shielding material.

(E) The photoinitiator is 0.01 mass or more normally with respect to the total mass of a light-shielding material, and 30 mass % or less normally.

When using a photopolymerizable compound, it is 90 mass % or less normally with respect to the gross mass of a light-shielding material, and normally 0.01 mass % or more.

It should be noted that most of the (D) organic solvent contained in the light-shielding material of the present invention will be lost due to evaporation and the like during the exposure, development treatment, and thermal curing treatment described above. Generally, only 0 to 1% by mass tends to remain in the total mass.

<Substrate with light-shielding material according to the second embodiment>

A substrate with a light-shielding material according to a second embodiment of the present invention has a light-shielding material on a transparent substrate, wherein the light-shielding material includes (A) a color material and (B) an organic binder, and satisfies the following (3) ~(5).

(3) The transparent substrate side of the said light-shielding material contains a black pigment as (A) color material.

(4) The side opposite to the transparent substrate of the light-shielding material contains a pigment as the (A) color material.

(5) The OD value per 1 μm of the light-shielding material is different in the thickness direction, and the OD value per 1 μm is higher on the side opposite to the transparent substrate than on the transparent substrate side.

In this way, by making the transparent substrate side of the light-shielding material contain a black pigment as the (A) color material, it is possible to efficiently absorb light incident from the transparent substrate side regardless of the wavelength, thereby reducing the wavelength dependence of reflectance. tendency. Moreover, there exists a tendency for the reflection of the light which may generate|occur|produce on the side opposite to a transparent substrate to be suppressed by making the side opposite to a transparent substrate contain a pigment as (A) color material. Furthermore, by making the OD value per 1 μm of the light-shielding material different in the thickness direction and making the side opposite to the transparent substrate higher than the transparent substrate side, there is a tendency that both high light-shielding and low reflectivity can be easily achieved.

As an example of the substrate with a light-shielding material according to the second embodiment of the present invention, the OD value per 1 μm of the light-shielding material gradually changes in the thickness direction, and the side opposite to the transparent substrate is mentioned. A substrate with a light-shielding material that has a higher OD value per 1 μm on the side. In order to obtain such a board|substrate with a light-shielding material, the method of applying the coloring resin composition with which the density|concentration of (A) coloring material differs multiple times so that the density|concentration of (A) coloring material may increase gradually is mentioned. In this case, by constituting the (B) organic binders in various colored resin compositions using the same or similar materials, there is a tendency that the formation of the interface due to multiple coatings can be suppressed.

In addition, a substrate with a light-shielding material in which the light-shielding material is composed of two or more layers, and the OD value per 1 μm of the layer on the side opposite to the transparent substrate is higher than that of the layer on the transparent substrate side can be mentioned. For example, in order to obtain such a board|substrate with a light-shielding material, the method of applying the colored resin composition of (A) coloring material density|concentration several times so that the density|concentration of (A) coloring material may increase gradually is mentioned. In this case, by constituting (B) the organic binder in various colored resin compositions with different types of materials, there is a tendency that an interface can be formed at the time of multiple application. The laminated structure is not particularly limited, and for example, two or more light-shielding layers may be laminated parallel to the contact surface with the transparent substrate. In addition, there is no particular limitation on the number of lamination layers, but when the number of lamination layers is large, the number of coating steps of the colored resin composition at the time of forming the light-shielding material increases and the production efficiency deteriorates, so it is preferably 2 to 4 layers, more preferably 2 to 4 layers. 2 to 3 layers, more preferably 2 layers.

The unit OD value of the transparent substrate side of the light-shielding material, the unit OD value of the side opposite to the transparent substrate, the unit OD value of the light-shielding material as a whole, and the film thickness are preferably the values described in the first embodiment.

In addition, it is preferable to set the difference between the relative reflectance at a wavelength of 550 nm and the upper limit and lower limit of the relative reflectance at a wavelength of 450 to 650 nm to be the value described in the first embodiment.

In addition, like 1st Embodiment, (C) microparticles|fine-particles may also be contained. As for the specific configuration, the configuration described in the first embodiment can be preferably adopted.

As the black pigment contained on the transparent substrate side of the light-shielding material according to the second embodiment, for example, the black pigments exemplified in the aforementioned <(A) color material> can be used. From the viewpoint of color tone, aniline black, Perylene black, cyanine black and other organic black pigments, carbon black. In addition, a combination of pigments in which a difference in reflectance due to a difference in wavelength is reduced by mixing a red pigment, a yellow pigment, an orange pigment, etc. with a black pigment may also be used. Among them, carbon black is more preferable from the viewpoint of color tone and light-shielding properties.

In addition, as the pigment contained on the side opposite to the transparent substrate of the light-shielding material, for example, the pigments exemplified in the aforementioned <(A) color material> can be used, and aniline black and perylene black are preferable from the viewpoint of light-shielding properties. , Cyan black and other organic black pigments, carbon black, titanium black. In addition, blue pigments, red pigments, yellow pigments, orange pigments, etc. may be used in combination. Among these, carbon black and titanium black are more preferable from the viewpoint of light-shielding properties.

In addition to this, the configuration exemplified as the substrate with a light-shielding material according to the first embodiment may also be adopted.

In addition, examples of the (B) organic binder include those obtained by curing the aforementioned (B') organic binder. When the (B') organic binder containing the aforementioned (E) photopolymerization initiator and other components is used, the light-shielding material may also contain the (E) photopolymerization initiator and other components. As a transparent substrate, those described in description of the color filter of this invention mentioned later can be used normally.

The light-shielding material in the substrate with light-shielding material according to the second embodiment can be formed using the colored resin composition described in the first embodiment.

<Colored resin composition according to the third embodiment>

The colored resin composition according to the third embodiment of the present invention is a photosensitive colored resin composition characterized by comprising (A) a color material, (B') an organic binder, and (C) a refractive index of not less than 1.2 and not more than 1.8 and (D) organic solvent, and the content of (C) fine particles is 15% by mass or more.

In this way, by including a specific amount or more of (C) microparticles having a refractive index within a specific range, when the colored resin composition is coated on a substrate, and another colored resin composition is further coated thereon, Dissolution of the colored resin composition can also be suppressed, and there is a tendency that a substrate with a light-shielding material capable of achieving excellent low reflectivity can be formed with high productivity.

As (C) fine particles, those exemplified in the first embodiment can be preferably used.

(C) The content of fine particles is 15% by mass or more, preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less. It exists in the tendency for the dissolution of the colored resin composition after coating completion to be suppressed by being more than the said lower limit, and it exists in the tendency for suitable developability to be imparted by being below the said upper limit.

As the (A) color material, those described in the aforementioned <(A) color material> can be preferably used, and as the (B') organic binding material, it can be preferably used in the aforementioned <(B') organic binding material. > Those described in, and as the (D) organic solvent, those described in the aforementioned <(D) Organic Solvent> can be preferably employed. Furthermore, the aforementioned (E) photopolymerization initiators, photopolymerizable compounds, adhesion improving agents such as silane coupling agents, applicability improving agents, development improving agents, ultraviolet absorbers, and antioxidants may also be included as needed. , surfactant, pigment derivative and other compounding components, each compounding component is usually used in the state of being dissolved or dispersed in (D) organic solvent.

In addition to this, the configuration exemplified as the colored resin composition for the light-shielding material used to form the light-shielding material-attached substrate according to the first embodiment may also be employed.

[Anti-reflection film]

When the light-shielding material of the present invention is provided as a light-shielding layer such as a black matrix of a color filter for a liquid crystal display device, in order to reduce the reflection of the display device, it may be placed on the surface of the transparent substrate opposite to the side on which the light-shielding material is formed. Provide anti-reflection film. As an antireflection film, an antireflection film obtained by laminating multiple types of films having different refractive indices, an antireflection film obtained by introducing air into a material by some method, and the like are effective. The anti-reflection film may also be an anti-reflection layer formed integrally with the transparent substrate.

As one of them, for example, a method of forming a fine uneven structure on the surface of a transparent film is widely known. According to this method, since the refractive index of the entire layer on the surface on which the fine uneven structure is formed depends on the volume ratio of air to the material forming the fine uneven structure, the refractive index can be greatly reduced, and the reflectance can be improved even if the number of laminated layers is small. reduce.

In addition, an antireflection film in which pyramid-shaped protrusions are continuously formed on the entire film as described in Japanese Re-Exposition No. 2008-096872, for example, can also be used. Since the cross-sectional area of the anti-reflection film formed with pyramid-shaped protrusions (fine concave-convex structure) changes continuously when it is cut along the film surface direction, its refractive index will gradually increase from the air to the substrate, so it can be an effective way of anti-reflection. In addition, the antireflection film exhibits excellent optical properties that cannot be replaced by other methods.

The height of the protrusions is preferably 100 nm or more, more preferably 150 nm or more. When the height is less than 100 nm, the minimum reflectance increases or the reflectance of a specific wavelength increases, resulting in insufficient antireflection properties.

In addition, the aspect ratio (height of the above-mentioned convex portion/interval between adjacent convex portions) is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and most preferably 1.5 to 3.0. If the aspect ratio is less than 1.0, the minimum reflectance or the reflectance of a specific wavelength will increase, and the anti-reflection property will become insufficient. If the aspect ratio is greater than 5, the convex portion will easily bend during friction. May result in reduced scratch resistance, or may not exhibit anti-reflection performance.

The method for forming the micro-concave-convex structure on the surface of the transparent film is not particularly limited, and examples thereof include: a method in which a transparent film is injection-molded or press-molded to form a micro-concave-convex structure using a press mold formed with a micro-concave-convex structure; The active energy ray-curable composition is filled between the stamper of the structure and the transparent film, and the active energy ray-curable composition is cured by irradiation of active energy rays to transfer the concave-convex shape of the stamper, and then the mold is released, thereby relatively A method of laminating a surface layer with a fine concave-convex structure on a transparent film; filling an active energy ray-curable composition between a stamper formed with a fine concave-convex structure and a transparent substrate, and transferring the concave-convex shape of the stamper to the active energy A method in which the ray-curable composition is released from the mold and then irradiated with active energy rays to cure the active energy ray-curable composition, thereby laminating a surface layer with a fine uneven structure on a transparent film.

In the examples described later, an antireflection film formed separately using a stamper formed with a fine concavo-convex structure was simply bonded to a transparent film and used.

[color filter]

Hereinafter, the color filter having the light-shielding material of the present invention will be described according to its manufacturing method.

(1) Transparent substrate

The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has moderate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone. sheet, thermosetting resin sheet such as epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, or various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance.

The transparent substrate may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, or various resin thin film forming treatments such as polyurethane resin to improve surface properties such as adhesiveness as necessary.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably in the range of 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resins, the film thickness is normally 0.01-10 micrometers, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix (shading material)

A color filter can be manufactured by disposing a black matrix on a transparent substrate and generally forming red, green, and blue pixel images.

As mentioned above, the light-shielding material of the present invention can be mainly used for black matrix applications, but is not limited thereto.

When forming the black matrix of a color filter using the light-shielding material of this invention, the black matrix is formed according to the formation method of the light-shielding material mentioned above.

When using the light-shielding material of the present invention for, for example, the frame of a display panel other than the black matrix of the color filter, and using a material other than the light-shielding material of the present invention as the black matrix, the black matrix can be formed by a conventional method. .

(3) Formation of pixels

(3-1) Coating of photosensitive colored resin composition

After coating and drying a photosensitive colored resin composition containing one color of red, green, and blue on a transparent substrate provided with a black matrix, a photomask is laminated on the coating film, and the process is carried out through the photomask. The image is exposed, developed, and if necessary, heat-cured or photo-cured to form a pixel image, thereby producing a colored layer. Color filter images can be formed by performing this operation on each of the photosensitive colored resin compositions of three colors of red, green, and blue.

The coating method of the colored resin composition for color filters can employ|adopt the method similar to the coating method of the photosensitive colored resin composition in the formation method of the light-shielding material of this invention mentioned above.

If the thickness of the coating film is too thick, it will be difficult to develop the pattern, and sometimes it will become difficult to adjust the gap in the process of forming a liquid crystal unit. If the thickness of the coating film is too thin, it will be difficult to increase the pigment concentration, and sometimes the desired of shading. The thickness of the coating film is usually preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.8 to 5 μm in terms of the film thickness after drying.

(3-2) Drying of the coating film

The coating film after coating the photosensitive colored resin composition on the substrate can be dried using the same method and conditions as the drying method and conditions of the coating film in the above-mentioned method of forming the light-shielding material of the present invention.

(3-3) Exposure

For image exposure, the same operation method as the exposure method in the above-mentioned method of forming the light-shielding material of the present invention can be employed.

(3-4) Development

The color filter according to the present invention can be produced by image-exposing the coating film formed of the photosensitive colored resin composition using the above-mentioned light source, followed by the developing method in the above-mentioned method of forming the light-shielding material of the present invention. Likewise, an image is formed on a substrate by development using an organic solvent, or an aqueous solution containing a surfactant and a basic compound. About the aqueous solution used for image development, it may be the same as the developing solution in formation of the light-shielding material of this invention mentioned above.

(3-5) Thermal curing treatment

Thermal curing treatment is performed on the color filter substrate after development. The thermal curing conditions at this time can be selected within the range of temperature 100-280°C, preferably within the range of 150-250°C, and the time can be selected within the range of 5-60 minutes. Through the above-mentioned series of steps, the patterned image of one color is formed. This step is repeated sequentially to pattern black, red, green, and blue, thereby forming a color filter. In addition, the order of patterning of 4 colors is not limited to the said order.

(4) Formation of transparent electrodes

The color filter can form a transparent electrode such as ITO on the image in its original state, and it can be used as a part of a color display, a liquid crystal display device, etc. A top coat of polyamide, polyimide, etc. is placed on the image. In addition, in applications such as a partial planar alignment driving method (IPS mode), transparent electrodes may not be formed.

[Liquid crystal display device]

The liquid crystal display device of the present invention is a liquid crystal display device produced using the above-mentioned color filter of the present invention.

A liquid crystal display device is generally manufactured by forming an alignment film on a color filter, spreading a spacer on the alignment film, bonding it to a counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and The opposite electrodes are connected to complete the liquid crystal display device. As the alignment film, a resin film such as polyimide is preferable. In order to form an alignment film, a gravure printing method and/or a flexographic printing method can generally be used, and the thickness of an alignment film can be several 10 nm. After the alignment film is cured by thermal firing, surface treatment is performed by irradiation of ultraviolet rays or by treatment with a rubbing cloth to obtain a surface state in which the deflection of the liquid crystal can be adjusted.

As the spacer, a spacer suitable for the size of the gap (slit) between the counter substrate and the opposing substrate can be used, and usually, a spacer of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film may be formed on the color filter substrate by photolithography, and the photo spacer (PS) may be effectively used instead of the spacer. As the opposing substrate, an array substrate is generally used, and a TFT (Thin Film Transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected within the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.

For liquid crystal cells whose periphery is sealed, after cutting into panel units, depressurize in a vacuum chamber, immerse the liquid crystal injection port in liquid crystal, and release the pressure in the vacuum chamber to inject liquid crystal into the liquid crystal cell. The degree of reduced pressure in the liquid crystal cell is usually 1×10 ^-2 to 1×10 ^-7 Pa, preferably 1×10 ^-3 to 1×10 ^-6 Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The heating and holding at the time of depressurization are normally made into the range of 10 to 60 minutes, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by curing a UV curable resin in a liquid crystal cell into which a liquid crystal is injected and sealing a liquid crystal injection port.

The types of liquid crystals are not particularly limited, and may be currently known liquid crystals such as aromatics, aliphatics, and polycyclic compounds, and may be any type of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them may be used.

In addition, the color filter of this invention is not limited to a liquid crystal display device, It can also be used suitably for other liquid crystal display devices, such as an organic electroluminescent display device.

Example

Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples, but the present invention is not limited to the following examples within the scope not exceeding the gist of the present invention.

<Manufacture Example 1: Manufacture of coated carbon black>

Carbon black was produced by the usual oil furnace method. Among them, ethylene tar with low Na, Ca, and S contents was used as a raw material oil, and gaseous fuel was used for combustion. In addition, production was performed using pure water treated with an ion exchange resin as reaction-terminated water. 540 g of the obtained carbon black was stirred together with 14500 g of pure water for 30 minutes at 5,000 to 6,000 rpm using a homogenizer to obtain a slurry. This slurry was transferred to a container with a screw type mixer, and while mixing at about 1,000 rpm, 600 g of toluene in which 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in small portions. After about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, forming particles of about 1 mm.

Next, after dehydrating with a 60-mesh metal mesh, it put into a vacuum drier, dried at 70 degreeC for 7 hours, and toluene and water were completely removed, and coated carbon black was obtained.

<Production Example 2: Production of Ink (a1)>

With respect to 20 parts by mass of the coated carbon black prepared in Production Example 1, 4.4 parts by mass of Disperbyk-167 (manufactured by BYK-Chemie) as a dispersant and 1 part by mass of S12000 (manufactured by Lubrizol) as a pigment derivative were added , and propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content concentration became 35% by mass.

This was fully stirred with a stirrer and premixed. Next, dispersion treatment was carried out in the range of 25 to 45° C. for 6 hours using a paint shaker, 0.5 mmφ zirconia beads were used as beads, and 60 g of the dispersion liquid and 180 g of beads were added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to produce an ink (a1).

<Production Example 3: Synthesis of Organic Binder (b'1)>

[chemical formula 22]

Add 50g of the epoxy compound (epoxy equivalent weight 264) of the above structure, 13.65g of acrylic acid, 60.5g of methoxybutyl acetate, 0.936g of triphenylphosphine and 0.032g of p-methoxyphenol into a mixer equipped with a thermometer and agitator. and a condenser tube, the reaction was carried out at 90° C. while stirring until the acid value became 5 mgKOH/g or less. The reaction took 12 hours and an epoxy acrylate solution was obtained.

25 parts by mass of the above epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) It was added to the flask equipped with the thermometer, the stirrer, and the condenser, and it heated up gradually to 105 degreeC, stirring, and it reacted.

When the resin solution became transparent, it was diluted with methoxybutyl acetate and adjusted to a solid content of 50% by mass to obtain an acid value of 131 mgKOH/g, which was measured by GPC and converted to a weight average molecular weight (Mw) of polystyrene. ) is 2600 organic binding material (b'1).

<Manufacturing Example 4: Preparation of Dispersion Resin>

145 parts by mass of propylene glycol monomethyl ether acetate were stirred while substituting the inside of the reaction container with nitrogen, and the temperature was raised to 120°C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monoacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd. "FA-513M") were added dropwise thereto, and further heated at 120° C. Stirring was continued for 2 hours.

Next, the inside of the reaction container was replaced with air, 27.0 parts by mass of acrylic acid, 0.7 parts by mass of tris(dimethylaminomethyl)phenol, and 0.12 parts by mass of hydroquinone were charged, and the reaction was continued at 120° C. for 6 hours. Then, 52.0 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a dispersed resin solution. The weight average molecular weight (Mw) of the obtained dispersion resin was about 15000, and the acid value was 100 mgKOH/g.

<Manufacture Example 5: Synthesis of Photopolymerization Initiator (e1)>

<Diketone Body>

Ethylcarbazole (5g, 25.61mmol) and o-naphthoyl chloride (5.13g, 26.89mmol) were dissolved in 30ml of dichloromethane, cooled to 2°C in an ice-water bath and stirred, and AlCl ₃ (3.41g , 25.61 mmol). After further stirring at room temperature for 3 hours, a solution of crotonyl chloride (2.81 g, 26.89 mmol) in 15 ml of dichloromethane was added to the reaction solution, and AlCl ₃ (4.1 g, 30.73 mmol) was added, and stirring was continued for 1 hour and 30 minutes. The reaction liquid was added to 200 ml of ice water, and 200 ml of methylene chloride was added to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a white solid (10 g).

<Oxime body>

Diketone (3.00 g, 7.19 mmol), NH ₂ OH·HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed in 30 ml of isopropanol, and refluxed for 3 hours.

After completion of the reaction, the reaction solution was concentrated, and 30 ml of ethyl acetate was added to the obtained residue, followed by washing with 30 ml of saturated aqueous sodium bicarbonate solution and 30 ml of saturated brine, and drying over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 3.01 g of a solid. This solid was purified by column chromatography to obtain 2.22 g of a pale yellow solid.

<Oxime ester>

Oxime (2.22g, 4.77mmol) and acetyl chloride (1.34g, 17.0mmol) were added to 20ml of dichloromethane and cooled in an ice bath, triethylamine (1.77g, 17.5mmol) was added dropwise and kept in this state The reaction was carried out for 1 hour. After confirming the disappearance of the raw material by thin layer chromatography, water was added to terminate the reaction. The reaction liquid was washed twice with 5 ml of saturated aqueous sodium bicarbonate solution, twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate/hexane=volume ratio 2/1) to obtain 0.79 g of the photopolymerization initiator (e1 ) (hereinafter referred to as "initiator (e1)").

The ¹ H-NMR measured value and structural formula of the obtained initiator (e1) are shown below.

¹ H-NMR (CDCl ₃ ): σ1.17(d,3H),1.48(t,3H),1.53(s,3H),1.81(s,3H),2.16(s,3H),2.30(s, 3H),3.17-3.32(m,2H),4.42(q,2H),4.78-4.94(br,1H),7.45-7.59(m,5H),7.65(dd,1H),7.95(m,2H) ,8.04(m,2H),8.14(dd,1H),8.42(d,1H),8.64(d,1H)

[chemical formula 23]

<Manufacturing Example 6: Preparation of Resist>

Each component was added so that the ratio of the resist to the solid content became the ratio shown in Table 1 below, and propylene glycol was added as an organic solvent (d1) so that the resist solid content concentration became 20% by mass. Monomethyl ether acetate was stirred and dissolved with a stirring bar, and black resists (1) to (16) were prepared.

Among them, the following components were used as the inks (a2) and (a3), the fine particles (c1) to (c6), the photopolymerizable compound, and the surfactant. In addition, below, "%" which shows the content ratio of a component composition is all "mass %".

Ink (a2): titanium black ink

(titanium black pigment 15%, polyurethane basic dispersant 3.5%, additive 1%, propylene glycol monomethyl ether acetate 80.5%)

Ink (a3): organic pigment mixed color ink

Solid content ratio B15:6/R254/V23/Y139=50%/19%/6%/25%, polyethyleneimine dispersant 17%, resin (b2) 32% solid content concentration 30% propylene glycol monomethyl ether ethyl Ester solution

Microparticles (c1): ORGANOSILICA SOL PMA-ST manufactured by Nissan Chemical Co., Ltd.

(Silicon dioxide content 30.7% propylene glycol monomethyl ether acetate dispersion solution, average particle diameter (BET method) 10nm, refractive index 1.7)

Microparticles (c2): ORGANOSILICA SOL MEK-ST manufactured by Nissan Chemical Co., Ltd.

(Silicon dioxide content 30.4% methyl ethyl ketone dispersion solution, average particle diameter (BET method) 40nm, refractive index 1.7)

Microparticles (c3): ORGANOSILICA SOL MEK-ST manufactured by Nissan Chemical Co., Ltd.

(Silicon dioxide content 30.6% methyl ethyl ketone dispersion solution, average particle diameter (BET method) 70nm, refractive index 1.7)

Particles (c4): Catalyzed into industrial zirconia dispersion

(20% methanol solution, average particle size 46nm coated zirconia refractive index 1.7)

Microparticles (c5): Catalyzed into industrial zirconia dispersion

(20% isopropanol solution, average particle size 14nm coated zirconia refractive index 1.7)

Fine particles (c6): Alumina dispersion made by Harima Chemicals Group

(20% propylene glycol monomethyl ether acetate solution, average particle size 54nm alumina refractive index 1.45)

Photopolymerizable compound: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

Surfactant: Fluorosurfactant F475 manufactured by DIC Corporation

<Manufacturing example 6: Production of anti-reflection film>

1.5 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals) was dissolved in 20 parts by mass of dipentaerythritol hexaacrylate, 70 parts by mass of ARONIX M-260 (manufactured by Toagosei Co., Ltd.), and 10 parts by mass of hydroxyethyl acrylate to obtain active Energy ray curable composition. A few drops of this curable composition was dropped on a stamper made of porous alumina obtained by anodic oxidation, and covered with an acrylic resin film while spreading it, and then from the film side at 400mJ/cm ² The energy is irradiated with ultraviolet rays to photocure the active energy ray-curable composition. The film was separated from the stamper to obtain an antireflection film having a fine concavo-convex structure (aspect ratio 1.0) with a distance between adjacent convex portions of 200 nm and a height of the convex portions of 200 nm.

[Examples 1-15, Comparative Examples 1-4]

{Evaluation experiment 1}

<Production of substrate with light-shielding material>

In order to form the coating film for 1st light-shielding layers, the resist (1) was apply|coated by the spin coater on the glass substrate so that the film thickness after firing might become 0.6 micrometers. Then, drying was performed for 60 seconds in a vacuum drier, and then drying was performed on a hot plate at 140° C. for 5 minutes. Next, in order to form the second coating film for light-shielding layer, a resist (6) was applied with a spinner on the first coating film for light-shielding layer under the condition that the total film thickness after firing would be 1.6 μm. Then, it was dried for 60 seconds with a vacuum drier. Next, drying was performed on a hot plate at 110° C. for 2 minutes. This substrate was baked in an oven at 230° C. for 25 minutes to obtain the substrate with a light-shielding material of Example 1.

Similarly, resist type, film thickness, etc. were carried out in the same manner as described in Tables 2, 4, 5, and 6, and the substrates with light-shielding materials of Examples 2-15 and Comparative Examples 1-4 were obtained.

Among them, when the cross-sections of the substrates with light-shielding materials in Examples 2 and 4 were subjected to elemental analysis based on SEM-EDS by the method described above, the following results were confirmed: in the light-shielding materials, the transparent substrate side and the opposite side of the transparent substrate The concentration of (C) fine particles on the side differs in the thickness direction, and in particular, the concentration on the opposite side is lower than that on the transparent substrate side.

<Measurement of unit OD value>

The film thickness of the first light-shielding layer and the film thickness of the second light-shielding layer after application of the obtained substrate with light-shielding material were measured using a non-contact surface/layer cross-sectional topography measurement system ("Vert Scan" manufactured by Ryoka Systems Co., Ltd.).

On the other hand, the OD value of the first light-shielding layer and the OD value of the second light-shielding layer after coating were measured using a spectroscopic characteristic detection device "LCF" manufactured by Otsuka Electronics Co., Ltd., and the unit OD value (/μm ). The results are shown in Tables 2, 4, 5 and 6.

Unit OD value = measured OD value / film thickness

<Measurement of reflectance>

Fig. 3(a) and Fig. 3(b) show the measuring method of the reflectance. In FIG. 3( a ) and FIG. 3( b ), reference numeral 16 denotes a measurement incident light path, and reference numeral 17 denotes a measurement reflection light path.

A spectrophotometer ("UV-3100" manufactured by Shimadzu Corporation) was provided with a tool for specular reflection measurement. Next, the antireflection film 14 produced in Production Example 6 was provided on the glass substrate surface on the side where the light-shielding material was not formed, which is the back surface of the sample substrate. In this state, with the mirror plate as a reference plate, the relative reflectance when the incident angle was 5 degrees was measured as shown in FIG. ).

On the other hand, the reflectance of the substrate provided with the antireflection film produced in Production Example 3 was measured in the same manner on both sides of the glass substrate without the light-shielding material. As a result, the reflectance at a wavelength of 550 nm was 0.337%.

The reflectance R (%) between the transparent substrate and the light-shielding material was calculated by the following formula, and the results are shown in Tables 2, 4, 5 and 6.

R(%)=R1(%)-(0.337/2)

Next, for each substrate with a light-shielding material, the relative reflectance measured with the antireflection film 14 provided as shown in FIG. The reflectance (%) is R2 (%), and the relative reflectance (%) at 550nm measured without anti-reflection film 14 as shown in FIG. 3(a) is R3 (%). The reflectance (%) at the wavelength of the light source is described in Table 3 as R4 (%). In addition, the relative reflectance (%) at 550 nm of the substrate which provided the antireflection film on both surfaces of the glass substrate which did not provide the light-shielding material was 0.338%.

As can be seen from Table 3, in the absence of an anti-reflection film, the absolute value of the reflectance becomes high due to the reflection between the air and the glass, but the light-shielding material of the embodiment of the present invention can achieve a lower value than that of the comparative example. Reflectivity.

The graph of the reflectance distribution with respect to the wavelength when the reflectance R1 was measured in Example 2 with the antireflection film is shown in FIG. 4( a ). In Example 2, when the reflectance R3 was measured without providing an antireflection film, the graph of the reflectance distribution with respect to the wavelength is shown in FIG. 4( b ). It can be seen from FIG. 4( a ) and FIG. 4( b ) that the light-shielding material according to the embodiment of the present invention has little change in the relative reflectance in the entire visible light region, regardless of the wavelength. In addition, the table|surface in FIG. 4(a) and FIG. 4(b) shows the reflectance value every 50 nm wavelength in the graph of a reflectance distribution.

<Appearance evaluation of light-shielding material>

White light was irradiated from the side of the glass substrate surface on which the light-shielding material was not formed, and the reflection was visually evaluated for appearance. The case where reflection was low was evaluated as "◯", the case where reflection was slightly high was evaluated as "△", and the case where reflection was high was evaluated as "×". The results are shown in Table 2.

{Evaluation experiment 2}

In order to form the coating film for 1st light-shielding layers, the resist (1) was apply|coated by the spin coater on the glass substrate so that the film thickness after firing might become 0.6 micrometers. Thereafter, it was dried in a vacuum drier for 60 seconds, and then dried on a hot plate at 140° C. for 5 minutes. Next, in order to form the second coating film for light-shielding layer, a resist (6) was applied with a spinner on the first coating film for light-shielding layer under the condition that the total film thickness after firing would be 1.6 μm. Then, it was dried for 60 seconds with a vacuum drier. Next, drying was performed on a hot plate at 110° C. for 2 minutes to obtain a substrate before exposure of Example 1.

This sample was exposed through a linear photomask with an opening of 10 μm (the distance between the photomask and the sample was 200 μm) using a high-pressure mercury lamp at 50 mJ/cm ² . Then, spray image development was performed using the KOH aqueous solution of density|concentration 0.05 mass % at the temperature of 25 degreeC, and the patterning property was evaluated according to the following reference|standard.

Patternability: After development, whether or not the lines of the 10 μm opening of the photomask were reproduced was confirmed with an optical microscope, and the case of reproduction was evaluated as "◯" and the case of not reproduced was evaluated as "×".

Similarly, the resist type, film thickness, etc. were carried out in the same manner as described in Tables 2 and 4, and the patternability of Examples 2-10 and Comparative Examples 1-4 were evaluated. The results are shown in Tables 2 and 4.

table 3

In Example 12, as a result of observing the film surface with an optical microscope, unevenness occurred. This is because the average particle diameter of the fine particles is too large.

As can be seen from Table 2, although the OD value per 1 μm of the light-shielding materials of Examples 1 to 48 is 2.5 or more, it becomes glossy by making the relative reflectance between the substrate and the light-shielding material 1.0% or less. A material with excellent suppression, low reflection, and light-shielding properties. Moreover, both developability and patternability were also favorable. In particular, it can be seen from Examples 1 to 3 that it does not depend on the content ratio of (C) fine particles in the first layer. In addition, it can be seen from Examples 4 and 5 that it does not depend on the total film thickness. In addition, from Examples 6 to 5 8, it can be seen that a light-shielding material with low reflection and excellent light-shielding properties was obtained regardless of the concentration of the color material in the first layer. Moreover, from Example 9, even when the density|concentration of the color material of a 2nd layer is low, low reflection can be achieved. On the other hand, for the light-shielding materials of Comparative Examples 1 to 3, although the OD value per 1 μm was 2.5 or more, the relative reflectance between the substrate and the light-shielding material exceeded 1.0%, so although the light-shielding properties were excellent, Insufficient reflexes.

As can be seen from Table 4, for the light-shielding materials of Examples 5 and 10, by forming the first layer using a resist having a content ratio of (C) particles of 15% by mass or more, high A substrate with a light-shielding material having a relative reflectance between the substrate and the light-shielding material of 1.0% or less can be productively formed. On the other hand, for the light-shielding material of Comparative Example 4, the first layer was formed using a resist containing less than 15% by mass of (C) fine particles, and the relative reflection between the substrate and the light-shielding material rate exceeded 1.0%. This is because, when the second layer was applied, the first layer was dissolved and the desired layer structure could not be formed.

As can be seen from Table 5, for the light-shielding materials of Examples 11 and 12, although the average particle diameter of the (C) particles was changed in the range of 40 to 100 nm, in any of the examples, the substrate and the light-shielding material could be separated. The relative reflectance among the materials is 1.0% or less, and a material with suppressed gloss, low reflection, and excellent light-shielding properties was obtained.

As can be seen from Table 6, for the light-shielding materials of Examples 13, 14, and 15, although particles other than silicon dioxide are used as (C) particles, by selecting and using particles with a refractive index in the range of 1.2 to 1.8, it is possible to Obtains the same effect as silica.

From the above result, according to this invention, it turns out that the black matrix with low reflectivity and high light-shielding property can be formed using the colored resin composition which can pattern by exposure and image development.

Claims (18)

1. A substrate with a light-shielding material, which has a light-shielding material on a transparent substrate, Wherein, the light-shielding material includes (A) color material and (B) organic binding material, and satisfies the following (1) and (2), (1) The light-shielding material contains (C) fine particles with a refractive index of 1.2 or more and 1.8 or less; (2) The concentration of the particles in the light-shielding material is different in the thickness direction, and the concentration of the particles on the side opposite to the transparent substrate is lower than the concentration of the particles on the side of the transparent substrate. 2. The substrate with a light-shielding material according to claim 1, wherein the OD value per 1 μm of the light-shielding material is different in the thickness direction, and the OD value per 1 μm on the side opposite to the transparent substrate is higher than that of the transparent substrate. OD value per 1 μm on the transparent substrate side. 3. The substrate with a light-shielding material according to claim 1 or 2, wherein the (C) fine particles are inorganic fine particles. 4. The substrate with a light-shielding material according to claim 3, wherein the inorganic fine particles are silica particles. 5 . The substrate with a light-shielding material according to claim 1 , wherein the (A) color material contains one or more selected from carbon black, titanium black, and organic coloring pigments. 6. A substrate with a light-shielding material, which has a light-shielding material on a transparent substrate, Wherein, the light-shielding material includes (A) color material and (B) organic binding material, and satisfies the following (3)-(5), (3) The transparent substrate side of the light-shielding material contains black pigment as (A) color material; (4) The side opposite to the transparent substrate of the light-shielding material contains a pigment as (A) color material; (5) The OD value per 1 μm of the light-shielding material is different in the thickness direction, and the OD value per 1 μm on the side opposite to the transparent substrate is higher than the OD value per 1 μm on the side of the transparent substrate. 7 . The substrate with a light-shielding material according to claim 1 , wherein the OD value per 1 μm of the light-shielding material is 2.5 or more. 8 . The substrate with a light-shielding material according to claim 1 , wherein (B) the organic binder is a cured product of an alkali-soluble resin. 9 . The substrate with a light-shielding material according to claim 1 , wherein the light-shielding material further contains (E) a photopolymerization initiator. 10. The substrate with a light-shielding material according to any one of claims 1 to 9, which has a relative reflectance of 1.0% or less at a wavelength of 550 nm, Here, the relative reflectance is a value measured by incident light from the side of the transparent substrate at an incident angle of 5 degrees and using a mirror plate as a reference. 11. The substrate with a light-shielding material according to claim 10, wherein the difference between the upper limit and the lower limit of the relative reflectance at a wavelength of 450 to 650 nm is 0.5% or less. 12. The substrate with a light-shielding material according to any one of claims 1 to 11, wherein the light-shielding material is composed of two or more layers. The color filter which has the board|substrate with a light-shielding material as described in any one of Claims 1-12. 14. A liquid crystal display device comprising the color filter according to claim 13. 15. A colored resin composition comprising: (A) a coloring material, (B') an organic binder, (C) particles having a refractive index of 1.2 or more and 1.8 or less, and (D) an organic solvent, However, the content of (C) fine particles is 15% by mass or more. 16. The colored resin composition according to claim 15, wherein the (C) fine particles are inorganic fine particles. 17. The colored resin composition according to claim 16, wherein the inorganic fine particles are silica particles. 18. The colored resin composition according to any one of claims 15 to 17, wherein the (A) color material contains one or more selected from carbon black, titanium black, and organic coloring pigments.