JP2020076983A - Black resin composition for light blocking films, substrate with light blocking film obtained by curing composition, color filter having substrate with light blocking film, and touch panel - Google Patents

Abstract

To provide a black resin composition for light blocking films which is used to obtain a light blocking film that offers reduced reflectance, and to provide a substrate with the light blocking film formed thereon.SOLUTION: A black resin composition for light blocking films contains essential ingredients of (A) a light- or heat-curable resin and/or light- or heat-curable monomer, (B) a black light blocking particle-containing dispersion liquid comprising black light-blocking particles dispersed in a dispersion medium, and (C) a transparent particle-containing dispersion liquid comprising transparent particles dispersed in a dispersion medium. The black resin composition is characterized in that: a ratio D/Dof an average secondary particle diameter Dof the transparent particles in the ingredient (C) to an average secondary particle diameter Dof the black light-blocking particles in the ingredient (B) is in a range of 0.2 to 1.0; a ratio m/mof a mass mof the transparent particles in the ingredient (C) to a mass mof the black light-blocking particles in the ingredient (B) is in a range of 0.015 to 0.20; and the transparent particles have a refractive index that is no greater than that of a hardened product of the ingredient (A).SELECTED DRAWING: None

Description

  The present invention relates to a black resin composition for a light-shielding film, a substrate with a light-shielding film having a light-shielding film obtained by curing the composition on a transparent substrate such as glass, and an LCD having the substrate with the light-shielding film as a constituent element. The present invention relates to a color filter for a display and a touch panel for a display device. Specifically, a black resin composition that is cured by light or heat suitable for forming a fine light-shielding film on a transparent substrate, and a light-shielding film obtained by curing the black resin composition are selectively placed. The present invention relates to a formed substrate with a light-shielding film.

  A light-shielding film (bezel) is provided on the outer frame of the touch panel to shield light leakage from the periphery of the liquid crystal panel on the back surface, and the liquid crystal panel is provided with a black matrix for shielding the TFT elements in the color filter. With the recent development of mobile terminals, the number of display devices such as touch panels and liquid crystal panels that are used outdoors or in vehicles is increasing, and the light shielded from the outside of the panel is installed on the glass substrate or plastic film substrate. The reflected light from the film affects the appearance of the liquid crystal display device when it is not lit, so that the reflectance is the same as the reflected light from the surrounding colored film and the hue (reflected chromaticity) is controlled. This is a new technical issue.

  Such a light-shielding film is formed by printing a composition mainly composed of a curable resin and a light-shielding material on a transparent substrate (Patent Documents 1 and 2). As a light-shielding material, black pigments such as carbon black and black titanium oxide that absorb visible light are often used. If these black pigments are used to increase the black pigment concentration in the light-shielding film in order to improve the light-shielding property of the light-shielding film (to reduce the light-transmitting property of the light-shielding film), the black pigment becomes blacker than the transparent substrate or the curable resin. Since the pigment has a high refractive index, the reflectance of the transparent substrate when viewed from the surface opposite to the surface on which the light shielding film is formed becomes high. That is, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, compared to the reflection at the interface between the colored layer on the transparent substrate and the transparent substrate and the reflection at the interface between the colored bezel and the air. If it becomes large, there arises a problem that the black matrix boundary is conspicuous due to the reflection on the light-shielding film and the difference in reflectance from the color filter colored portion. For this reason, the higher the degree of light shielding, the more difficult it is to satisfy the required characteristics that the reflectance is equivalent to that of the colored layer or colored bezel other than the light shielding film.

  As a means for reducing the reflection that occurs at the interface between different materials, for example, a method of installing a low-refractive index film that reduces the reflection of external light on the substrate surface (eg, 1/4 wavelength circularly polarizing plate), an anti-glare method that roughens the substrate surface. In addition, it has been proposed to take additional means such as a means for forming a thin film having an intermediate refractive index between the substrate and the light shielding film. The film thickness of the thin film having an intermediate refractive index is a transparent film of 100 to 300 μm corresponding to a quarter wavelength of a visible light wavelength or a multilayer film of these (Non-Patent Document 1).

  In the black matrix on the color filter in the liquid crystal panel and the light-shielding film for the frame of the touch panel, it is necessary to pattern the light-shielding film only in a necessary portion, and when the additional means as described above is taken, the purpose is to reduce the reflection. The thin film (low-reflection film) is formed in advance between the transparent substrate and the light-shielding film, that is, by patterning the low-reflection film and the light-shielding film individually by, for example, a photolithography method, the low-reflection film and the light-shielding film are formed. It is necessary to form a layered structure. Alternatively, a method of forming a light-shielding film on a transparent thin film, subjecting the light-shielding film to pattern exposure / development by a photolithography method, and using this as a photomask to form a transparent thin film pattern is conceivable. In this method, it is necessary that the black resin composition for a light shielding film does not erode the transparent thin film formed in advance.

  A conventional black resin composition for a light-shielding film is mainly composed of a curable resin component and a light-shielding material component, and has a desired light-shielding degree (OD value) of 4 or more while lowering the concentration of the light-shielding material having a higher refractive index. It is possible to form a light-shielding film on a transparent substrate with a film thickness corresponding to, and reduce the reflectance at the interface between the formed light-shielding film and the transparent substrate. However, if an attempt is made to form a patterned light-shielding film with a film thickness of more than 1.5 μm by the photolithography method, there is a difference in the cross-linking density in the film thickness direction at the exposed portion during the thermal baking process after exposure / development. However, there is a problem that a difference occurs in heat-curing shrinkage between the surface of the coating film and the transparent substrate, the surface roughness of the coating film increases, the surface smoothness deteriorates, and wrinkles occur on the surface. On the other hand, in Patent Document 3, by coexisting silica particles having a predetermined average primary particle size range in the light-shielding film composition, the sharpness of the edge shape of the pattern is excellent even in the case of a thick film exceeding 1.5 μm. A technique is disclosed in which a pattern can be formed, and the coating film surface is smooth even in the subsequent heat-baking step so that deterioration of surface roughness due to heat-curing shrinkage does not occur. It was necessary to add a certain amount or more of silica to the light shielding material. Further, Patent Document 4 discloses a technique of a resin composition containing fine acrylic resin particles and carbon black. In this case as well, in order to stabilize the pattern shape in a thick film, acrylic particles are added to the light shielding material. Had to be added above a certain level.

  In recent years, a method of directly printing a curable resin composition on a transparent substrate by an inkjet method has been proposed (Patent Document 5). Since the ink jet printing method directly forms a printed pattern, it basically does not require an exposure / development step for pattern formation as in the photolithography method, and only needs to consider the composition of the cured product in consideration of reliability. Good. In the case of only heat curing, there is less concern that wrinkles will occur in the case of thick film compared to the case of using light curing together, but on the other hand, the reliability of the cured light shielding film (chemical resistance during pattern etching of transparent electrodes and wiring etc.) Property, it is necessary to coexist with a curing agent and / or a curing accelerator for thermosetting reaction, and coexistence of surface-active silica particles and the like may reduce the storage stability of the thermosetting resin composition. there were.

JP-A-4-177202 JP-A-8-278629 JP, 2008-304583, A JP, 2010-256589, A WO2011 / 155446

Optical Thin Films User's Handbook, by James D. Rancourt, translated by Shigetaro Ogura, pp. 10

  The present invention has been made in view of the drawbacks of the technique, and an object thereof is a black light-shielding film having a high light-shielding property and reflecting light to a color (coloring) part of a color filter. It is to provide a black resin composition for a light-shielding film that can form a light-shielding film that can be significantly reduced, and the light-shielding film. Furthermore, the black resin composition for forming the light-shielding film has excellent viscosity stability and excellent surface smoothness of the formed pattern light-shielding film.

  As a result of intensive studies to solve the above-mentioned problems of the prior art, the inventors of the present invention refracted light as compared with black light-shielding particles in a black resin composition for a light-shielding film and a resin cured by light or heat. It was found that this object can be achieved by adding transparent particles having a low rate.

That is, the gist of the present invention is as follows.
(1) (A) a light- or heat-curable resin, and / or a light- or heat-curable monomer, and (B) a black light-shielding particle-containing dispersion liquid in which black light-shielding particles are dispersed in a dispersion medium. , And (C) a transparent particle-containing dispersion obtained by dispersing transparent particles in a dispersion medium as an essential component, and the average secondary particle diameter D _B of the black light-shielding particles in the component (B) is 60 to 150 nm. The ratio D _C / D _{B of} this D _B to the average secondary particle diameter D _C of the transparent particles in the component (C) is in the range of 0.2 to 1.0, and the mass of the transparent particles in the component (C). and m _C, is in the range of the mass ratio m _{C /} m _B is from 0.015 to 0.20 of the mass m _B of the black light-shielding particles of the component (B), also, the refractive index of the transparent particles, the component (a) The black resin composition for a light-shielding film is characterized by having a refractive index not more than that of the cured product.

(2) The present invention also provides the black resin composition for a light shielding film as described in (1), wherein the transparent particles in the component (C) have an average secondary particle diameter D _C of 30 to 100 nm. is there.
(3) The present invention also provides the black resin composition for a light shielding film according to (1) or (2), wherein the transparent particles in the component (C) have a refractive index of 1.55 or less.
(4) In the present invention, the black light shielding particles in the component (B) are carbon black, and the transparent particles in the component (C) have a reactive (meth) acryloyl group in the molecule. The black resin composition for a light shielding film according to any one of (1) to (3), which is silica surface-treated with a coupling agent.
(5) In the present invention, the dispersion medium in the component (C) is a curable monomer having a (meth) acryloyl group, and the transparent particles have a (meth) acryloyl group in the molecule. The black resin composition for a light-shielding film according to any one of (1) to (4), which is silica surface-treated with a ring agent.

(6) The light-shielding film according to any one of (1) to (5), wherein the light-shielding film obtained by curing with light or heat has a light-shielding rate OD of 2.8 / μm or more. It is a black resin composition.
(7) The present invention also provides that the black resin composition for a light shielding film contains a solvent (D) as a dispersion medium in the components (B) and (C) and / or as an additional component, and The solvent (D) contains a solvent having a boiling point of 180 ° C. or higher as a main component and is used as a black resin composition for a light-shielding film for inkjet printing (1) to (6). Is a black resin composition for a light-shielding film.
(8) The present invention also provides a black resin composition for a light-shielding film, which comprises a photocurable alkali-soluble resin and / or (E) an alkali-soluble resin as the component (A), thereby providing a photolithography method. The black resin composition for a light-shielding film according to any one of (1) to (6), which is used as a black resin composition for a light-shielding film.

(9) The present invention also provides a substrate with a light-shielding film obtained by applying or printing the black resin composition for a light-shielding film according to any one of (1) to (8) on one surface of a transparent substrate and further curing the composition. The substrate with a light-shielding film is characterized in that the film thickness of the light-shielding film after curing is 1 to 3 μm.
(10) The present invention also provides a color filter having the substrate with a light-shielding film of (9).
(11) The present invention is also a touch panel having the substrate with a light-shielding film of (9).

  According to the black resin composition for a light-shielding film of the present invention, with respect to the average secondary particle diameter in the dispersion medium of the black light-shielding particles, transparent particles having a certain level of the average secondary particle diameter, black light-shielding particles On the other hand, by adding a relatively small amount, the reflectance of the light-shielding film can be reduced as compared with the case where transparent particles are not added. Here, as the transparent particles, it is effective to use particles having a refractive index smaller than that of the black light-shielding particles, and particularly when inorganic particles such as silica are used, by performing a specific surface treatment, It is effective to disperse so as to have a desired average secondary particle diameter in a solvent or a curable monomer that is cured by light or heat. By using such a black resin composition for a light-shielding film, it is possible to provide a light-shielding film having a high light-shielding rate and excellent design as a light-shielding film for a color filter or a touch panel.

The present invention will be described in detail below.
As the curable resin by light or heat and / or the curable monomer by light or heat, which is the component (A) in the black resin composition for a light shielding film of the present invention, a functional group that causes a curing reaction by light or heat, That is, a resin or monomer having at least one ethylenically unsaturated double bond such as a (meth) acryloyl group or vinyl group or a cyclic reactive group such as an epoxy group or an oxetane group in a molecule is preferably used.

  Examples of the light- or heat-curable resin include alkyl acrylates or alkyl methacrylates such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate (hereinafter, these are collectively referred to as “ Alkyl (meth) acrylate ", etc.), cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene and the like, and a molecular weight synthesized from about 3 to 5 kinds of monomers. It is preferable that the polymer (acrylic resin) having a molecular weight of about 5,000 to 100,000 has one or more functional groups that cause a curing reaction by the above-mentioned heat or light at the side chains and / or terminals. For example, as a resin obtained by adding an unsaturated double bond to a part of an acrylic resin, a resin obtained by copolymerizing a monomer having a carboxyl group in the above acrylic resin is added to an isocyanate group and at least one ethylenic resin. A photosensitive copolymer having an acid value of 50 to 150, which is obtained by reacting a compound such as isocyanate ethyl acrylate or methacryloyl isocyanate having an unsaturated double bond, can be preferably used in terms of heat resistance, developability and the like.

  Further, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polyglycidyl ester of polycarboxylic acid compound, polyglycidyl ether of polyol compound, aliphatic or alicyclic epoxy resin, glycidyl amine type epoxy resin, Ordinary photopolymerizable resin such as epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy resin such as triphenolmethane type epoxy resin or dihydroxybenzene type epoxy resin, and further epoxy (meth) acrylate It can be also suitably used as a resin composition capable of forming a development pattern by a photolithography method by reacting with an acid anhydride.

  Examples of the polymerizable monomer having an ethylenically unsaturated double bond include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. (Meth) acrylic acid esters having ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra ( (Meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa ( Examples thereof include (meth) acrylates such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate modified with caprolactone.

Specific examples of the compound having at least one cyclic reactive group such as an epoxy group and an oxetane group in the molecule include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, and phenol novolac type epoxy compounds. , Cresol novolac type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, 3,4-epoxycyclohexanecarboxylic acid (3 ', 4'- Alicyclic epoxy compounds represented by epoxycyclohexyl) methyl, polyfunctional epoxy compounds having a dicyclopentadiene skeleton (for example, HP7200 series manufactured by DIC), 1,2-bis (hydroxymethyl) -1-butanol 1,2. -Epoxy-4- (2-oxiranyl) cyclohexane adduct (for example, "EHPE3150" manufactured by Daicel), epoxidized polybutadiene (for example, "NISSO-PB.JP-100" manufactured by Nippon Soda Co., Ltd.), an epoxy compound having a silicone skeleton, and the like. Can be mentioned.
These resins and monomers that are cured by light or heat may be used alone, or by mixing a plurality of them, it becomes possible to impart characteristics such as reliability.

  Further, a compound which usually reacts with these by light or heat, for example, a compound having a carboxyl group, an amino group, a hydroxy group, a thiol group, and a photopolymerization initiator that generates radicals, cations, anions or the like by ultraviolet rays or heat, thermal polymerization It is preferable to use it together with an initiator and the like.

  Regarding the exemplified component (A), it is preferable to select a component whose cured product has a refractive index in the range of 1.48 to 1.6. For example, in the case of an acrylic resin-based cured product, the refractive index is 1.48 to 1.55, and the refractive index is adjusted by including an aromatic group in the chemical structure, for example, by copolymerization with a styrene monomer. The epoxy resin type is 1.50 to 1.60, and the refractive index becomes higher when using a bisphenol type epoxy resin or an aromatic acid anhydride curing agent, and an aliphatic epoxy resin, an alicyclic epoxy resin or an alicyclic acid anhydride curing agent is used. When used, the refractive index becomes relatively low.

  The black light-shielding particles in the component (B) have a refractive index of more than 1.6, and a black pigment that absorbs visible light has a high light-shielding rate in a target thin film and a storage stability of the composition for a light-shielding film. Mainly used from the viewpoint. Carbon black is preferable as the black pigment used in the present invention. As the carbon black, any of lamp black, acetylene black, thermal black, channel black, furnace black and the like may be used. In addition, one kind or a mixture of plural kinds may be used for the purpose of adjusting the light-shielding property of the black dye or the like, but the black light-shielding particles are preferably 60% by mass or more in the entire light-shielding material. For example, if many organic pigment-based / dye-based light-shielding materials are used, the light-shielding rate decreases.

These light-shielding materials are dispersed in a bead mill together with a dispersion medium such as a polymer dispersant or a solvent to prepare a dispersion liquid containing black light-shielding particles, which is mixed with the component (A) and the component (C) described later. Thus, the black resin composition for a light-shielding film for the purpose is prepared. The average secondary particle diameter D _B of the black light-shielding particles in the dispersion is preferably adjusted to 60 nm to 150 nm, more preferably 80 nm to 120 nm. In the present invention, the "average secondary particle diameter" means an average particle diameter value obtained by the cumulant method after being diluted with a dispersion solvent or a corresponding solvent, measured by a dynamic light scattering method. For example, for carbon black, it is a value measured at a particle concentration of 0.1% by mass in a PGMEA solvent. If the average secondary particle diameter D _B is less than 60 nm, the addition of a polymer dispersant necessary for increasing the concentration of black light-shielding particles in order to achieve a high light-shielding rate will increase or the viscosity will increase during storage. Is likely to occur. If the average secondary particle diameter D _B exceeds 150 nm, the surface smoothness of the formed light-shielding film is not preferable, and the linearity of the pattern edge when formed by the photolithography method is impaired.

  By the way, the light-shielding degree (OD = -log [transmittance]) of the light-shielding film for the touch panel and the black matrix for the color filter is required to be OD4 or more, while the film thickness is required to be 3 μm or less, preferably 2 μm or less. ing. The reason is that, in the touch panel, disconnection is prevented when connecting the metal wiring on the light-shielding film and the conductive film on the touch panel, and in the color filter, flatness is ensured after the RGB pixels are formed on the black matrix. For the purpose of obtaining a high light-shielding degree even with such a thin light-shielding film, carbon black is, for example, 35% by mass or more and 70% by mass or less based on the total solid content in the composition.

  On the other hand, when the concentration of black light-shielding particles in the total solid content of the composition (all components remaining on the substrate after curing) is increased, the reflection between the light-shielding film formed on the transparent substrate and the transparent substrate is reduced. However, there is a problem that the boundary is conspicuous due to the reflection on the light-shielding film and the difference in reflectance from the color filter colored portion. That is, in the case of only the cured resin component (A) and the light shielding material component (B) not including the component (C) described later, the reflectance between the light shielding film and the transparent substrate in the cured and formed light shielding film is ( Dependence solely on the mass ratio of the black light-shielding particles in the component (A) and the component (B), if the mass ratio was constant, the reflectance was not significantly reduced even if the film thickness of the light-shielding film was increased.

  In view of the above facts, the present inventors, in the cured product of the component (A), by coexisting transparent particles having a refractive index not higher than the refractive index of the cured product of the component (A), It has been found that the reflectance can be reduced while keeping the same concentration of black light-shielding particles in all solids (while maintaining the light-shielding degree). That is, in the present invention, transparent particles having a refractive index equal to or lower than the refractive index of the cured product of the component (A) are used as an essential component [(C) component used in a state of being dispersed in a dispersion medium], and transparent particles are known as Examples thereof include inorganic transparent fine particles such as metal oxides of silica and the like, and resin transparent fine particles such as acrylic resin, styrene-acrylic resin, silicone resin, epoxy resin and melamine resin. Since the resin-made transparent fine particles may be provided as a dispersion solution in which the composition of the present invention is dispersed in an organic solvent, it is preferably composed of a crosslinked resin insoluble in the organic solvent.

  The curable resin and / or curable monomer contained in the component (A) and used as a matrix for the black light-shielding particles in the component (B) and the transparent particles in the component (C) is cured by light or heat. The cured product of the component (A) has a refractive index depending on the chemical structure, and is preferably in the range of 1.48 to 1.6. Therefore, the refractive index of the component forming the transparent particles of the component (C) is not more than the refractive index of the cured product of the component (A), preferably in the range of 1.40 to 1.60, and more preferably 1.42 to 1.55. In the present invention, the “refractive index of the cured product of the component (A)” means the black light shielding particles in the component (B) and the transparency in the component (C) from the black resin composition for a light shielding film of the present invention. It is the refractive index of the cured product obtained by curing the coating film forming component of the light-shielding film, excluding the particles and the solvent that is removed during the curing process. The curing agent and the polymerization are used to cure the component (A) by light or heat. When an initiator and the like coexist, it is the refractive index of a cured product including them. When the refractive index of the transparent particles in the component (C) exceeds the "refractive index of the cured product of the component (A)", the effect of reducing the reflectance is lost. The refractive index of the component used as a known transparent particle is 1.44 to 1.50 for silica, 1.47 to 1.60 for acrylic resin or epoxy resin, and 1.40 to 1.45 for silicone resin. These may be used alone or in combination of two or more. The transparency of the transparent particles is 10% or more in terms of total light transmittance, and the light wavelength dependency of the transparency can be used even if it is colored as long as it contributes to achromaticity of the light shielding film.

Further, the transparent particles in the component (C) have an average secondary particle diameter D _C of 0.2 or a ratio D _C / D _B to the average secondary particle diameter D _B of the black light-shielding particles in the component (B) of 0.2. Is 1.0 to 1.0, and the ratio m _C / m _B between the mass m _C of the transparent particles in the component (C) and the mass m _B of the black light-shielding particles in the component (B) in the composition. Is 0.015 to 0.20, preferably 0.03 to 0.10, and more preferably 0.03 to 0.09. The average secondary particle diameter D _C is a value of an average particle diameter obtained by the cumulant method after being diluted with a dispersion solvent or a corresponding solvent and measured by a dynamic light scattering method. For example, for silica particles, it is a measured value at a particle concentration of 1 to 10 mass% in methanol. When the average secondary particle diameter ratio D _C / D _B exceeds 1.0, the smoothness of the surface of the formed light-shielding film is unfavorable and the light-shielding rate (OD / μm) decreases. Further, if D _C / D _B is less than 0.2, the effect of reducing the reflectance of the formed light shielding film is weakened. When the mass ratio m _C / m _B in the composition is less than 0.015, the effect of reducing the reflectance of the formed light-shielding film is not observed, and when it exceeds 0.20, the light-shielding ratio (OD / μm) of the light-shielding film is reduced. .. In particular, when a large amount of the component (B) is used to increase the light-shielding rate (OD / μm), the component ratio of the component (A) that is cured by light or heat is reduced, and the matrix Since problems such that the cured physical properties do not reach a desired level or the pattern formation by the photolithography method cannot be sufficiently performed, in the present invention, even if the addition amount of the transparent particles in the component (C) is small. It is very useful because it can reduce the reflectance.

  The following is presumed as a mechanism for exhibiting a reflection reducing effect in a substrate with a light-shielding film formed as a light-shielding film obtained by curing the present composition. That is, as the light-shielding film, a light-shielding resin composition containing a solvent is applied on one surface of a transparent substrate, dried and then cured to form a light-shielding film. When the coating film after drying has no unevenness and the surface is smooth, the component (A), which is a low-viscosity substance, becomes a matrix inside the coating film, and the black light shielding in the component (B), which is an elastic substance. The particles are dispersed therein. In the drying process, as the solvent evaporates in the coating film, the volume shrinks in the film thickness direction, but the solvent between dispersed particles is eliminated and the distance between particles shrinks. The same applies to the interface between the transparent substrate and the applied composition. At this time, the curable resin and the monomer component have a higher viscosity than the black light-shielding particles that are elastic bodies, so they are deformed and contracted between the dispersed particles, and finally they cure to produce a black light-shielding property. The position of the particles is fixed. In such a substrate with a light-shielding film, a part of the light incident from the transparent substrate side is exclusively black-shielding particles [the refractive index of carbon black is about 2 (A) component in the light-shielding film at the interface of the transparent substrate and in the vicinity thereof]. Which is sufficiently higher than the refractive index of the cured product] and is reflected and scattered to appear on the transparent substrate side. Therefore, as the concentration of the black light shielding particles in the composition is increased, the reflection / scattering by the black light shielding particles will increase. On the other hand, when the transparent particles are coexisted, the transparent particles having elasticity similar to that of the black light-shielding particles are not deformed as compared with the component (A) and between the black light-shielding particles and between the transparent substrate and the black light-shielding particles. To exist in. Therefore, the reflection / scattering by the transparent particles having a lower refractive index than the black light-shielding particles is reduced, and the light incident on the transparent particles existing on the transparent substrate interface is further absorbed by the surrounding black light-shielding particles. Therefore, it is assumed that this absorption is effective when the film thickness is large to some extent.

  In order to effectively exhibit the above-described mechanism for reducing the reflectance, it is necessary to stably disperse the transparent particles together with the black light-shielding particles in the composition and in the film coated on the transparent substrate without self-aggregation. Assumed to be. Therefore, it is considered that the means for improving the dispersion stability of the black light-shielding particles and the transparent particles is effective, and the viscosity stability of the composition is an index thereof. In the transparent particles in the component (C) used in the present invention, it is effective to suppress reaggregation by subjecting the particles to a surface treatment.

  For example, the silica used as transparent particles in the component (C) of the present invention is preferably silica surface-treated with a silane coupling agent having a reactive (meth) acryloyl group in the molecule, and colloidal silica. The surface-treated silica can be prepared by the known means described in JP-A-57-131214, JP-A-2000-289172 and the like. These surface-treated silicas can be relatively stably dispersed in a solvent such as a monoalkyl ether or a monoalkyl ether acetate in the presence of a polymer dispersant. It is suitably used for the black resin composition for a light shielding film. Further, since the surface-treated silica can be dispersed in the curable monomer such as the (meth) acrylate having an ethylenically unsaturated group in a relatively easy manner, it is not limited to the solvent and is not limited to the solvent. Alternatively, the component (C) may be a dispersion of transparent particles in a curable monomer that is cured by heat. It can also be used by dispersing it in a mixture of a solvent and a curable monomer, or in a solution in which a curable resin is dissolved. The silica particles used for the surface-treated silica are manufactured by a general manufacturing method such as a gas phase reaction or a liquid phase reaction, and are not limited to a shape (spherical or non-spherical), The primary particle size is 20-40 nm. These silica particles were surface-treated by a known method, and the surface-treated silica was dispersed in an organic solvent with a bead mill. A dispersion was diluted to 1 to 10 wt% in methanol, and a dynamic light scattering method was used. Those having an average secondary particle diameter of 30 to 100 nm, preferably 30 to 60 nm, which is determined by the cumulant method as measured by the above method can be relatively easily produced, and should be formulated as transparent particles in the component (C) of the present invention. You can

On the other hand, the average secondary particle diameter D _B of the carbon black, which is the black light-shielding particle, is 60 nm to 150 nm, preferably 80 to 120 nm, as described above, in order to effectively exhibit the light shielding property and ensure the dispersion stability. .. Therefore, the average secondary particle diameter of the surface-treated silica can be relatively easily prescribed below the average secondary particle diameter of carbon black.

  Further, acrylic resin particles are also suitable as the transparent particles in the component (C), and the acrylic resin particles are not limited by the manufacturing method and shape (spherical, non-spherical, mononuclear structure, core shell structure, etc.). However, crosslinked acrylic fine particle fine sphere series manufactured by Nippon Paint Co., Ltd., acrylic fine particles described in JP 2010-256589 A, etc. can be used as those having less cohesiveness and excellent dispersibility.

  One or more kinds of solvents may be contained for the purpose of dissolving or dispersing the essential components of the present invention and are not particularly limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone. , Toluene, xylene, aromatic hydrocarbons such as tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, glycol ethers such as diethylene glycol diethyl ether, ethyl acetate, butyl acetate, Acetic acid esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. can be mentioned. By dissolving and mixing these with several kinds, black light shielding particles and transparent It is possible to obtain a uniform composition in which particles and the like are stably dispersed.

  Further, in the black resin composition for a light shielding film of the present invention, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, etc., if necessary. Additives can be added. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like.Examples of the antioxidant include hindered phenol compounds, and the plasticizer includes: Examples thereof include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, and examples of the defoaming agent and leveling agent include silicone-based compounds, fluorine-based compounds, and acrylic compounds. Further, examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

  As a method for applying the black resin composition for a light-shielding film onto a transparent substrate, a known solution dipping method, a spray method, an inkjet machine, a roller coater machine, a land coater machine, a method using a slit coater machine, a spinner machine, or the like can be used. Either method can be adopted. A dry coating film is formed by adjusting the viscosity to the appropriate level to obtain a good coating film with a solvent, applying the desired thickness with these methods, and then removing the solvent under heating or reduced pressure (prebaking). To be done. Subsequently, the desired substrate with a light-shielding film is produced by curing with light and / or heat.

  The light-shielding film of the present invention obtained by curing the above-mentioned black resin composition for light-shielding film with light or heat preferably has a light-shielding rate OD of 2.8 / μm or more, and has such characteristics. A resin composition for a light shielding film is preferably used. The light-shielding film for a touch panel and the black matrix for a color filter are required to have a light-shielding degree (OD = −log [transmittance]) of OD4 or more, while the film thickness is preferably 3 μm or less, more preferably 2 μm or less. The reason for this is that in the touch panel, the disconnection is prevented when connecting the metal wiring on the touch panel light shielding film and the conductive film on the touch panel, and in the color filter, the flatness is ensured after the RGB pixels are formed on the black matrix. In order to obtain a high light-shielding degree even with such a thin light-shielding film, a light-shielding film having a light-shielding degree of 2.8 / μm or more can be prepared by, for example, setting carbon black to 35% by mass or more based on the total solid content in the composition. .. On the other hand, when the light-shielding film has an OD / μm of less than 2.8, the reflection L * between the transparent substrate and the light-shielding film is 5.5 or less, which is not a problem.

  As a method for forming a light-shielding film pattern on a transparent substrate, the black resin composition for a light-shielding film of the present invention is applied on a transparent substrate, the dried coating film is irradiated with ultraviolet rays through a photomask, and the unexposed portion is developed. There is a photolithography method in which a liquid is removed and heat treatment is further performed. In addition, there are methods such as screen printing, intaglio printing, and gravure printing that use a transfer plate for printing. In recent years, inkjet printing has been attracting attention as a digital printing method that does not require a mask or a printing plate. The black resin composition for a light-shielding film of the present invention can be applied to any of the light-shielding film pattern forming methods, and in order to obtain a resin composition having a viscosity and a surface tension suitable for each method, a curable resin / A curable monomer (monomer), a solvent and a surfactant / fat composition are selected. Further, a forming method, a printing machine and the like are selected depending on the accuracy and resolution of the light shielding film pattern. Particularly in the black resin composition for a light-shielding film of the present invention, black light-shielding particles and transparent particles are stably dispersed, coarse particles are not generated due to aggregation of dispersed particles, and the viscosity stability during storage is excellent. Therefore, it can be preferably used particularly for an inkjet printing method and a photolithography method.

  For example, when a light-shielding film is formed by an inkjet printing method using the black resin composition for a light-shielding film of the present invention, black light-shielding particles and transparent particles are less likely to re-aggregate, and thus the inkjet nozzle is blocked during intermittent ejection. Is small, and the viscosity is stable during storage, which contributes to the stability of the pattern film thickness during continuous printing. The inkjet device is not particularly limited as long as the discharge amount of the composition can be adjusted, but an ink composition that stably forms droplets in a commonly used piezoelectric element inkjet head. Although the physical properties vary depending on the configuration of the head, the viscosity at the temperature inside the head is preferably 3 mPa · sec to 150 mPa · sec, and more preferably 4 mPa · sec to 30 mPa · sec. When the viscosity value is larger than this, it becomes impossible to eject the liquid droplets. On the contrary, when the viscosity value is smaller than this, the liquid droplet ejection amount is not stable. Further, the temperature inside the head varies depending on the stability of the ink composition used, but it is desirable to use at a room temperature of 20 ° C to 45 ° C. Among them, in order to increase the solid content in the ink composition and improve the film thickness, a temperature of about 35 to 40 ° C. is generally adopted in order to obtain a viscosity capable of stable ejection.

  The characteristics of the black resin composition for a light-shielding film for the inkjet printing method as described above are mainly adjusted by the solvent and the surfactant constituting the black resin composition, and further the drying of the composition in the nozzle portion during continuous printing is performed. In order to suppress it, the solvent is mainly one having a boiling point of 180 ° C. or higher, and it is 60% or more, preferably 80% or more in all the solvent components, and one kind or a plurality of kinds can be used. Solvents having a boiling point of 180 ° C. or higher include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol mono-n-butyl ether acetate. Alkyl ether acetates; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether; and high boiling point solvents such as γ-butyrolactone it can.

  On the other hand, in the photolithography method, since the black resin composition for a light-shielding film of the present invention causes less coarse particles due to re-aggregation of black light-shielding particles and transparent particles, it is possible to improve the pattern edge linearity after development. it can. The suppression of the generation of coarse particles is also suitable for other pattern forming methods, for example, for transferring a printing ink placed on a printing plate onto a transparent substrate, and for reducing defects such as surface foreign matter and craters in the printing pattern. is there.

  In the black resin composition for a light-shielding film of the present invention used in the photolithography method, the component (A) is a photocurable resin and / or a photocurable monomer, and an alkali-soluble resin for further dissolving in an alkali developing solution. To mix. Examples of the alkali-soluble resin include alkyl acrylates or alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate, cyclohexyl acrylate or cyclohexyl methacrylate having a cyclic functional group, and hydroxyethyl acrylate having a hydroxyl group. Alternatively, a molecular weight of 5,000 to 100,000 was synthesized using 2 to 5 kinds of monomers selected from monomers such as hydroxyethyl methacrylate and styrene, and a monomer (monomer) having a carboxyl group such as acrylic acid and methacrylic acid. (E) alkali-soluble resin having no photocurable functional group.

  Further, as a preferable example of the alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin having a polymerizable unsaturated group and an acidic group such as a carboxyl group in the molecule can be mentioned, which is one of the components (A). It is also preferably used when the photocurable resin itself is the polymerizable unsaturated group-containing alkali-soluble resin. At this time, it is also possible to use together (E) the alkali-soluble resin having no photocurable functional group. Examples of the polymerizable unsaturated group-containing alkali-soluble resin, for example, (meth) acrylic acid and (meth) a part of the carboxyl group of the resin obtained by radical copolymerization of an acrylic acid ester compound, (meth) acrylic acid A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a compound having a polymerizable unsaturated group such as glycidyl and an epoxy group in one molecule, or an epoxy resin obtained by reacting (meth) acrylic acid A wide variety of resins can be used, including a polymerizable unsaturated group-containing alkali-soluble resin obtained by adding an acid anhydride to an epoxy (meth) acrylate resin.

  The method for curing the light-shielding film printed on the transparent substrate and the curable resin component (A) are selected so as to meet the heat resistance of the transparent substrate, the environment in which it is used, the required dimensional accuracy, and reliability.

  Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

Various evaluations in the following examples were performed as follows unless otherwise specified.
[Solid content concentration]
A glass filter [mass: W ₀ (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example described below, weighed [W ₁ (g)], and the mass [W ₁ ] after heating at 160 ° C. for 2 hours. ₂ (g)] from the following formula.
Solid content concentration (mass%) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ ).

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.].

[Molecular weight]
Gel permeation chromatography (GPC) {HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) [manufactured by Tosoh Corporation], temperature: 40 ° C., speed: 0.6 ml / min}, and measured as standard polystyrene [PS-Oligomer Kit manufactured by Tosoh Corporation] weight average molecular weight (Mw) Is the value obtained.

[Primary particle size measurement]
A sample for measurement prepared by diluting a particle-containing solution with a solvent to a particle concentration of about 0.1 wt% and dropping the obtained dispersion on a metal mesh with a carbon support film is a transmission electron microscope (TEM; JEOL). The particle size obtained by observing with JEM-2000EX) manufactured by the company was defined as the primary particle size.

[Measurement of average secondary particle size]
For the obtained black light-shielding particle-containing dispersion or transparent particle-containing dispersion, a dynamic light scattering particle size distribution meter (manufactured by Otsuka Electronics Co., Ltd., particle size analyzer FPAR-1000) is used to determine an average of 2 by the cumulant method. Each secondary particle size was measured. The black light-shielding particle-containing dispersion liquid was diluted with propylene glycol monomethyl ether acetate (PGMEA) so that the concentration of the dispersed particles was 0.1 to 0.5% by mass to prepare a measurement sample. In addition, the dispersion liquid containing transparent particles was diluted with methanol to a particle concentration of 1 to 10 w% so as to obtain a measurable scattering intensity, which was used as a measurement sample.

[Viscosity measurement]
The viscosity of the black resin composition for a light shielding film was measured at 23 ° C. with an E-type viscometer (RE80L manufactured by Toki Sangyo Co., Ltd.). The measurement is carried out immediately after the preparation of the composition, then transferred to a container that can be sealed, after storage for 1 month refrigerated at 5 ° C and after accelerated aging for 1 week at 40 ° C, the viscosity is measured under the same conditions, and the initial viscosity is The increase in viscosity was determined.

[Shading degree (OD value) measurement]
Using a glass substrate with a light-shielding film after post-baking, measurement was carried out with an OD meter manufactured by Otsuka Electronics.

[Film thickness measurement]
The glass substrate with the light-shielding film after post-baking was measured using a stylus type film thickness meter [manufactured by Tencor Co., Ltd.].

[Measurement of refractive index]
It was measured using an Abbe refractometer.

[Measurement of reflective optical characteristics]
Using a glass substrate with a light-shielding film after post-baking, using a Konica Minolta colorimeter CM2600d from the surface opposite to the surface on which the light-shielding film is formed, measurement is performed with a D65 light source, 10 ° field of view. It was
Further, the reflectance was calculated by the following calculation formula from the measured value of L * obtained by the measurement of the reflective optical characteristic.
Reflectance (%) = {(L * + 16) / 116} ³ x 100

[Inkjet ejection stability test]
A black resin composition for a light-shielding film was charged into a Konica Minolta IJ piezo element drive type inkjet head (14pL / drop; KM512M), and after purging and cleaning of the inkjet head ejection surface, the ejection state of the composition was continuously maintained for 30 minutes The result was confirmed with a flight observation camera, and when there were no significant problems such as no liquid droplets being ejected and the flight trajectory being not apparently vertical, it was rated as O. Furthermore, in the intermittent ejection test (counting the number of non-ejection nozzles when re-ejection after leaving still for 30 minutes after cleaning the ejection surface of the inkjet head), if the number of non-ejection nozzles is less than 10 out of 512 nozzles, ○, 30 Less than 30 pieces was marked with Δ, and 30 or more pieces were marked with x.

[Development characteristics evaluation]
The black resin composition for a light-shielding film was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 1.2 μm, and prebaked at 80 ° C. for 1 minute. Then, on the dried coating to adjust the exposure gap in 80 [mu] m, covered with a negative type photomask having a line / space = 20 [mu] m / 20 [mu] m, an ultrahigh-pressure mercury lamp of I-line irradiance 30 mW / cm ² for 100 mJ / cm ² UV The light-curing reaction of the exposed portion was carried out. Next, this exposed coated plate was subjected to 1 kgf / cm ² pressure shower development in a 0.05% aqueous solution of potassium hydroxide at 23 ° C., and the time when the pattern was observed was defined as the development omission time (BT second). After the development, spray washing with 5 kgf / cm ² pressure is performed to remove the unexposed area of the coating film to form a pixel pattern on the glass substrate, and then at 230 ° C for 30 minutes using a hot air dryer. Heat post-baked. The evaluation items and methods of the obtained light-shielding film in each Example and Comparative Example are as follows.
Pattern linearity and smoothness of coating film surface: The 20 μm line after post-baking was observed with a microscope and SEM. When jaggedness was observed, x was given; Further, when the line film thickness varied due to coarse particles, the smoothness was judged to be ×.

Next, synthetic examples of the resins used in the examples will be shown. First, the following synthetic examples and abbreviations used in the examples will be shown.
BPFE: A reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane.
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate
BDGAC: Diethylene glycol monobutyl ether acetate
DPHA: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [DPHA manufactured by Nippon Kayaku Co., Ltd.]
HDDA: 1,6-hexanediol diacrylate
TMPTA: trimethylolpropane triacrylate

[Synthesis example 1]
In a 500 ml four-necked flask equipped with a reflux condenser, BPFE 78.63g (0.17mol), acrylic acid 24.50g (0.34mol), TPP 0.45g, and PGMEA 114g were charged and stirred for 12 hours under heating at 100 to 105 ° C. And a reaction product was obtained.
Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were charged to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 120 to 125 ° C. to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution ( A) -1 was obtained. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (solid content conversion) was 103 mgKOH / g, and the Mw by GPC analysis was 2,600.

[Preparation of resin solution: component A solution]
Resin solutions A1 to A3 containing the following (A) components were prepared. The refractive index of each of the cured products obtained by drying and curing the resin solutions A1 to A3 was 1.50 to 1.55.

(1) Resin solution A1 (for inkjet printing-1): photocurable resin composition
BDGAC 86.9 parts by mass, urethane acrylate [Kyoeisha Chemical Co., Ltd., trade name UA-306H] 10.0 parts by mass, photoinitiator OXE-02 (BASF) 0.75 parts by mass, BYK Chemie Japan Co., Ltd. trade name BYK (registered) Trademark) -333 10% BDGAC diluted solution 1.23 parts by mass, 3-ureidopropyltriethoxysilane [trade name KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.] 1.14 parts by mass, and pressure filtered with a 1 μm depth filter. Then, a resin solution A1 was prepared.

(2) Resin solution A2 (for inkjet printing-2): Thermosetting resin composition
BDGAC 82.9 parts by mass, polymerizable unsaturated group-containing alkali-soluble resin solution (A) -1 obtained in Synthesis Example 1 6.3 parts by mass, phenol novolac type epoxy resin [trade name JER154 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 178] 3.2 parts by mass, DPHA 4.0 parts by mass, 1.24 parts by mass of 10% BDGAC diluted solution of BYK (registered trademark) -333 manufactured by BYK Japan KK 2.95 parts by mass of ureidopropyltriethoxysilane (trade name KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed to prepare a resin solution A2.

(3) Resin solution A3 (for photolithography): Photocurable resin composition
PGMEA 78.7 parts by mass, polymerizable unsaturated group-containing alkali-soluble resin solution (A) -1 obtained in Synthesis Example 1 12.3 parts by mass, DPHA 2.41 parts by mass, photopolymerization initiator OXE-02 (manufactured by BASF) 0.81 parts by mass 1.24 parts by mass of a 10% BDGAC diluted solution of BYK (registered trademark) -333 manufactured by BYK Chemie Japan Co., Ltd., 3-ureidopropyltriethoxysilane [trade name KBE-585] manufactured by Shin-Etsu Chemical Co., Ltd. 2.95 Parts by mass were mixed to prepare a resin solution A3.

[Preparation of dispersion liquid containing black light-shielding particles: component B]
(1) Carbon black dispersion B1 (for inkjet printing): carbon black concentration of 25% by mass in BDGAC, dispersion resin [resin component in resin solution (A) -1] 8% by mass, polymer dispersant 2% by mass Dispersion was carried out in a bead mill so that the proportion became%, to obtain carbon black dispersion B1. The average secondary particle diameter of carbon black in the obtained dispersion was 106 nm.
(2) Carbon black dispersion B2 (for photolithography): carbon black concentration in PGMEA 25% by mass, dispersion resin [resin component in resin solution (A) -1] 8% by mass, polymer dispersant 2% by mass. The dispersion was carried out in a bead mill as described above to obtain a carbon black dispersion B2. The average secondary particle diameter of carbon black in the obtained dispersion was 98 nm.

[Preparation of transparent particle-containing dispersion: component C]
The refractive index of silica was 1.45 (reference value), and the refractive index of alumina was 1.74 (reference value). The characteristics of the prepared dispersion liquid are shown in Table 1.
(1) Silica dispersion C1: colloidal silica manufactured by Nissan Chemical Industries, Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, and the surface-treated silica is polymer-dispersed to a concentration of 50% by mass. A silica dispersion liquid C1 was obtained by dispersing in a bead mill in HDDA together with 5% by mass of the agent.
(2) Silica dispersion C2: Colloidal silica manufactured by Nissan Chemical Industries, Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, and polymer is dispersed so that the surface-treated silica has a concentration of 30% by mass. A silica dispersion C2 was prepared by dispersing in a bead mill in DPHA together with 3% by mass of the agent.
(3) Silica dispersion C3: 3% by mass of a polymer dispersant so that the concentration of silica obtained by surface-treating colloidal silica manufactured by Nissan Chemical Industries, Ltd. with γ-methacryloxypropyltrimethoxysilane is 30% by mass. At the same time, dispersion was carried out in TMPTA using a bead mill to obtain silica dispersion C3.
(4) Silica Dispersion C4: Granular silica (Aerosil manufactured by Nippon Aerosil Co., Ltd.) was dispersed in a PGMEA with a bead mill together with 10% by mass of a polymer dispersant so as to have a concentration of 20% by mass. did.
(5) Alumina dispersion C5: Nissan Chemical Industries Co., Ltd. colloidal alumina was surface-treated with γ-methacryloxypropyltrimethoxysilane, so that the concentration of the surface-treated colloidal alumina was 30% by mass. A bead mill was used to disperse the mixture in an HDDA together with 3% by mass of a molecular dispersant to obtain an alumina dispersion C5.

[Preparation and evaluation of black resin composition for light-shielding film and its light-shielding film]
[Example 1]
14.5 parts by mass of resin solution A2, 15 parts by mass of carbon black dispersion B1 and 0.5 parts by mass of silica dispersion C1 (total 30 parts by mass) were subjected to pressure filtration with a 1 μm depth filter, and black for light-shielding film. A resin composition was prepared. The initial viscosity (room temperature) of the prepared composition was 10.3 mPa · sec. This black resin composition for a light-shielding film is applied onto non-alkali glass by spin coating while changing the rotation speed, and these are dried at 90 ° C for 5 minutes, and further post-baked at 230 ° C for 30 minutes to provide a light-shielding film. A glass substrate was created.

[Examples 2 to 3, Comparative Examples 1 to 3]
The resin solution A2 and the carbon black dispersion B1 and the transparent particle-containing dispersion were mixed at the parts by mass shown in Tables 2 to 3 to prepare a black resin composition for light-shielding film, and the viscosity was changed in the same manner as in Example 1. The measurement was performed. Further, this black resin composition for a light-shielding film was applied on non-alkali glass, dried at 90 ° C. for 5 minutes, and further post-baked at 230 ° C. for 30 minutes to prepare a glass substrate with a light-shielding film. The results are shown in Tables 2-3.
The glass substrate with a light-shielding film in Examples 1 to 3 was able to reduce the reflectance as compared with the glass substrate with a light-shielding film in Comparative Example 1 containing no transparent particles despite the same carbon black concentration. On the other hand, in the glass substrate with a light-shielding film of Comparative Example 2 containing alumina particles (refractive index literature value: 1.74), no reduction in reflectance was observed. Further, in Comparative Example 3 using silica particles having an average secondary particle diameter larger than that of carbon black particles, the reflectance of the glass substrate with a light-shielding film was reduced, but the cured film surface was observed by SEM to aggregate. The protrusions on the surface of the cured film due to the particles were observed, which was not preferable and the film thickness was uneven. Further, in the black resin composition for a light-shielding film, the viscosity at the time of storage at 40 ° C. was remarkably increased as compared with the initial value, and further, the nozzle clogging occurred in the inkjet discharge test.

[Example 4]
14.5 parts by mass of the resin solution A1, 15 parts by mass of the carbon black dispersion B1 and 0.5 parts by mass of the silica dispersion C1 (30 parts by mass in total) were subjected to pressure filtration with a 1 μm depth filter to obtain a black film for a light shielding film. A resin composition was prepared. The initial viscosity (room temperature) of the prepared composition was 10.0 mPa · sec. This black resin composition for light-shielding film is applied on non-alkali glass by spin coating while changing the rotation speed, dried at 90 ° C for 5 minutes, and further exposed to ultraviolet light of 1000 mJ (365 nm standard), 120 ° C for 30 minutes. A glass substrate with a light-shielding film was prepared by baking.

[Examples 5 to 6, Comparative Examples 4 to 6]
The resin solution A1 and the carbon black dispersion B1 and the transparent particle-containing dispersion described above were mixed in a mass part shown in Tables 2 to 3 to prepare a black resin composition for a light-shielding film, and the same procedure as in Example 1 was performed. And the viscosity was measured. Further, this black resin composition for light-shielding film was applied on alkali-free glass by spin coating while changing the rotation speed, dried at 90 ° C for 5 minutes, further exposed to ultraviolet rays of 1000 mJ (365 nm standard), 120 ° C for 30 minutes. Post-baking was performed to prepare a glass substrate with a light shielding film.
The glass substrates with a light-shielding film in Examples 4 to 6 had a lower reflectance than Comparative Example 4 containing no transparent particles despite the same carbon black concentration. On the other hand, in the glass substrate with the light-shielding film of Comparative Example 5 containing alumina particles (refractive index literature value: 1.74), no reduction in reflectance was observed. Further, in Comparative Example 6 using silica particles having an average secondary particle size larger than that of carbon black particles, the reflectance of the glass substrate with a light-shielding film was reduced, but the smoothness of the cured film surface was not preferable. ..

[Example 7, Comparative Examples 7 to 8]
Carbon black concentration relative to the total solid content concentration is changed to 40% by weight, to prepare a black resin composition for a light-shielding film similar to Example 1 and Comparative Example 3 and Comparative Example 1, its viscosity and the glass substrate with a light-shielding film. The optical properties were evaluated. The results are shown in Tables 2-3.
With the light-shielding film-coated glass substrate of Example 7, the reflectance could be reduced compared to Comparative Example 8 containing no transparent particles, despite the same carbon black concentration. On the other hand, in Comparative Example 7 using silica particles having an average secondary particle size larger than that of carbon black particles, although the reflectance of the glass substrate with a light-shielding film is reduced, when the cured film surface was observed by SEM aggregation The protrusions on the surface of the cured film due to the particles were observed, which was not preferable, and the film thickness varied. Further, in the black resin composition for a light-shielding film, the viscosity at the time of storage at 40 ° C. was remarkably increased as compared with the initial value, and further, the nozzle clogging occurred in the inkjet discharge test.

[Example 8 and Comparative Examples 9 to 10]
A black resin composition for a light shielding film for photolithography was prepared as the resin solution A3 and the carbon black dispersion B2, and the viscosity was similarly measured. This black resin composition for a light-shielding film was applied onto non-alkali glass by spin coating, dried at 80 ° C for 5 minutes, exposed to ultraviolet light through a quartz mask at 100 mJ (365 nm standard), and then in 0.05% KOH aqueous solution at 23 ° C. For 40 seconds, and further post-baked at 230 ° C. for 30 minutes to prepare a glass substrate with a light-shielding film. The results are shown in Table 4.
The substrate with a light-shielding film in Example 8 had a lower reflectance than Comparative Example 9 containing no transparent particles, despite the same carbon black concentration. On the other hand, in Comparative Example 10 using silica particles having an average secondary particle size larger than that of carbon black particles, although the reflectance of the substrate with a light-shielding film is reduced, the cured film surface was observed by SEM aggregate particles As a result, protrusions on the surface of the cured film were observed, and the film thickness was undesirably varied. Furthermore, in the edge shape of the 20 μm line, jaggedness not observed in Example 8 and Comparative Example 9 was found. Further, in the black resin composition for a light shielding film, the viscosity at the time of storage at 40 ° C showed an increase in viscosity as compared with the initial value.

[Examples 9 to 10]
The resin solution is A2 and carbon black dispersion B1, and a black resin composition for a light-shielding film is prepared by changing the silica concentration (C1) with respect to the total solid content concentration, and the optical characteristics of the glass substrate with a light-shielding film are prepared in the same manner as in Example 1. Was evaluated. The results are shown in Table 5. It was found that the reflectance was lowered by adding the silica dispersion in both cases.

[Examples 11 to 12]
The resin solution was A3 and carbon black dispersion B2, and the black resin composition for a light-shielding film was prepared by changing the silica concentration (C1) with respect to the total solid content concentration. The characteristics were evaluated. The results are shown in Table 5. It was found that the reflectance was lowered by adding the silica dispersion in both cases.

Claims (11)

(A) a light- or heat-curable resin, and / or a light- or heat-curable monomer, (B) a black light-shielding particle-containing dispersion liquid in which black light-shielding particles are dispersed in a dispersion medium, and ( C) A transparent particle-containing dispersion obtained by dispersing transparent particles in a dispersion medium is an essential component, and the average secondary particle diameter D _B of the black light-shielding particles in the component (B) is 60 to 150 nm. and _B, and (C) the ratio D _{C /} D range of _B is 0.2 to 1.0 and the average secondary particle diameter D _C of the transparent particles in the component, and (C) the mass m _C of the transparent particles in component , The mass ratio m _C / m _B to the mass m _B of the black light-shielding particles of the component (B) is in the range of 0.015 to 0.20, and the refractive index of the transparent particles is a cured product of the component (A). The black resin composition for a light-shielding film, which has a refractive index not more than The black resin composition for a light-shielding film according to claim 1, wherein the average secondary particle diameter D _C of the transparent particles in the component (C) is 30 to 100 nm.   The black resin composition for a light-shielding film according to claim 1 or 2, wherein the transparent particles in the component (C) have a refractive index of 1.55 or less.   The black light-shielding particles in the component (B) are carbon black, and the transparent particles in the component (C) are surface-treated with a silane coupling agent having a reactive (meth) acryloyl group in the molecule. The black resin composition for a light-shielding film according to claim 1, wherein the black resin composition is silica.   Silica in which the dispersion medium in the component (C) is a curable monomer having a (meth) acryloyl group, and the transparent particles are surface-treated with a silane coupling agent having a (meth) acryloyl group in the molecule. The black resin composition for a light shielding film according to any one of claims 1 to 4, wherein   The resin composition for a light-shielding film according to claim 1, wherein the light-shielding film obtained by curing with light or heat has a light-shielding rate OD of 2.8 / μm or more.   The black resin composition for a light shielding film contains a solvent (D) as a dispersion medium in the components (B) and (C) and / or as an additional component, and the solvent (D) has a boiling point of 180. The black resin for a light-shielding film according to any one of claims 1 to 6, which is used as a black resin composition for a light-shielding film for inkjet printing by containing a solvent having a temperature of ℃ or more as a main component. Resin composition.   The black resin composition for a light-shielding film contains a photocurable alkali-soluble resin and / or (E) an alkali-soluble resin as the component (A), and thus as a black resin composition for a light-shielding film for a photolithography method. It is used, The black resin composition for light-shielding films in any one of Claims 1-6 characterized by the above-mentioned.   It is a substrate with a light-shielding film obtained by applying or printing the black resin composition for a light-shielding film according to any one of claims 1 to 8 on one surface of a transparent substrate and further curing the film, which is a film of the light-shielding film after curing. A substrate with a light-shielding film, which has a thickness of 1 to 3 μm.   A color filter comprising the substrate with a light-shielding film according to claim 9. A touch panel comprising the substrate with a light-shielding film according to claim 9.