JPWO2017150069A1 - Resin composition, resin film, color filter, light shielding film, solid-state imaging device, and image display device - Google Patents

Abstract

Resin composition capable of forming a resin film excellent in low reflectivity and moisture resistance, and a resin film, color filter, light-shielding film, solid-state imaging excellent in low reflectivity and moisture resistance An element and an image display device are provided. The resin composition is at least any selected from titanium nitride-containing particles containing at least one metal atom other than titanium atoms, a binder resin, a filler, and a compound containing at least one of a fluorine atom and a silicon atom. Contains heels.

Description

  The present invention relates to a resin composition, a resin film, a color filter, a light-shielding film, a solid-state imaging device, and an image display device.

A solid-state imaging device includes a photographing lens, a solid-state imaging device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographing lens, and a circuit on which the solid-state imaging device is mounted. A substrate. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smartphone, and the like.
In a solid-state imaging device, noise due to reflection of visible light may occur. Therefore, in Patent Document 1, the generation of noise is suppressed by providing a predetermined light shielding film in the solid-state imaging device. As the composition for forming the light shielding film, a light shielding composition containing a black pigment such as titanium black is used.

JP 2007-115921 A

On the other hand, in recent years, various characteristics are required for the light shielding film.
For example, as the solid-state imaging device is reduced in size, thickness, and sensitivity is increased, further reduction in reflection of the light shielding film is required.
In addition, the present inventors have found that the spectral performance of the light-shielding film containing titanium black is lowered (that is, inferior to “humidity resistance”) when exposed to high temperature and high humidity. Since the desired light-shielding ability may not be exhibited when the spectral performance of the light-shielding film deteriorates, improvement is desired.

In view of the above circumstances, an object of the present invention is to provide a resin composition capable of forming a resin film having excellent low reflectivity and excellent moisture resistance.
Another object of the present invention is to provide a resin film excellent in low reflectivity and excellent in moisture resistance, a color filter including the resin film, a light shielding film, a solid-state imaging device, and an image display device.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have at least selected from compounds containing predetermined titanium nitride-containing particles, a binder resin, a filler, and at least one of a fluorine atom and a silicon atom. The present inventors have found that the above problems can be solved by using a resin composition in combination with any of the above, and thus completed the present invention.
That is, it has been found that the above object can be achieved by the following configuration.

(1) a titanium nitride-containing particle containing at least one metal atom other than a titanium atom;
A binder resin,
A resin composition comprising a filler and at least one selected from a compound containing at least one of a fluorine atom and a silicon atom.
(2) When the X-ray diffraction spectrum of the titanium nitride-containing particles is measured using CuKα rays as an X-ray source, the peak diffraction angle 2θ derived from the TiN (200) plane of the titanium nitride-containing particles is 42. The resin composition as described in (1) which exists in the range of 5 degrees or more and 43.5 degrees or less.
(3) The resin composition according to (1) or (2), wherein the filler is at least one of silica particles and acrylic particles.
(4) The resin composition according to (3), wherein the filler is hollow silica.
(5) The resin composition according to any one of (1) to (4), wherein the maximum value in the particle size distribution of the filler is 50 to 500 nm.
(6) A compound containing at least one of the fluorine atom and silicon atom is contained, and the content of the compound containing at least one of the fluorine atom and silicon atom is based on the total solid content in the resin composition. The resin composition according to any one of (1) to (5), which is 1 to 15% by mass.
(7) The compound containing at least one of the fluorine atom and the silicon atom is a polymer compound containing a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group. The resin composition according to any one of (1) to (6).
(8) The resin composition according to any one of (1) to (6), wherein the compound containing at least one of the fluorine atom and the silicon atom is a reactive silicone.
(9) The resin composition according to any one of (1) to (8), further containing a dispersion resin.
(10) The resin composition according to any one of (1) to (9), further comprising a polymerization initiator.
(11) The resin composition according to (10), wherein the polymerization initiator is an oxime compound.
(12) Furthermore, the resin composition in any one of (1)-(11) containing the silane coupling agent which has an epoxy group.
(13) The resin composition according to any one of (1) to (12), further comprising a polymerizable compound having a cardo skeleton.
(14) The resin composition according to (13), wherein the polymerizable compound having a cardo skeleton is a polymerizable compound having a 9,9-bisarylfluorene skeleton.
(15) The resin composition according to any one of (1) to (14), wherein the content of the titanium nitride-containing particles is 30 to 60% by mass with respect to the total solid content in the resin composition. object.
(16) titanium nitride-containing particles containing at least one metal atom other than titanium atoms;
A resin film containing a binder resin,
The resin film whose surface roughness Ra of the outermost surface of the said resin film is 100-2000 mm.
(17) The resin film according to (16), further comprising a filler.
(18) The resin film according to (17), wherein the maximum value in the particle size distribution of the filler is 50 to 500 nm.
(19) The resin film according to any one of (16) to (18), further including a resin having a polysiloxane structure.
(20) The resin film is a resin film in which the pigment layer X1 and the pigment layer X2 each containing the titanium nitride-containing particles are laminated adjacently,
The concentration of the titanium nitride-containing particles contained in the pigment layer X2 is smaller than the concentration of the titanium nitride-containing particles contained in the pigment layer X1,
The resin film according to any one of (16) to (19), wherein the surface roughness Ra of the surface of the resin film on the pigment layer X2 side is 100 to 2000 mm.
(21) a pigment layer containing titanium nitride-containing particles containing at least one metal atom other than titanium atoms;
And a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom, which is disposed adjacent to the pigment layer.
(22) The resin film according to (21), wherein the compound containing at least one of a fluorine atom and a silicon atom contains a resin containing at least one of a fluorine atom and a silicon atom.
(23) The resin containing at least one of the fluorine atom and the silicon atom includes a repeating unit containing at least one of a fluorine atom and a silicon atom, and a repeating unit having a polymerizable group. Resin film.
(24) A resin film in which a pigment layer Y1 and a pigment layer Y2 each containing titanium nitride-containing particles containing at least one metal atom other than a titanium atom are laminated adjacently,
Resin films having different concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2.
(25) A color provided with any one selected from the resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24) filter.
(26) Light shielding provided with any one selected from the resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24) film.
(27) A solid provided with any of the resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24) Image sensor.
(28) An image including any one selected from the resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24). Display device.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the resin film excellent in low reflectivity and excellent in moisture resistance can be provided.
According to the present invention, it is also possible to provide a resin film excellent in low reflectivity and excellent in moisture resistance, a color filter including the resin film, a light shielding film, a solid-state imaging device, and an image display device.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
The “pigment” in the present invention means, for example, an insoluble coloring compound that does not dissolve in a solvent. Here, examples of the “solvent” include the solvents exemplified in the solvent column described later. Therefore, the coloring compound which does not melt | dissolve in these solvents corresponds to the pigment in this invention.
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. . In the present invention, “light” means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not limited to exposure with a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
Further, in the present invention, “1 同” is synonymous with “0.1 nanometer (nm)”.

[First embodiment: resin film with Ra of 100 to 2000 mm]
The resin film in the first embodiment includes titanium nitride-containing particles containing at least one metal atom other than titanium atoms and a binder resin, and the surface roughness Ra of the outermost surface is 100 to 2000 mm. It is characterized by.
Now, the present inventors have obtained a film obtained by setting the surface roughness of the outermost surface of a resin film containing titanium nitride-containing particles containing at least one metal atom other than titanium atoms within the above numerical range. Has been found to be excellent in low reflectivity and moisture resistance. In particular, it is obtained when a method of roughening the film surface by containing a filler (preferably silica particles) or a resin having a polysiloxane structure in the resin film (Embodiments 1A and 1B, respectively) is obtained. In addition to further improving the low reflection performance of the film, it has been confirmed that the moisture resistance is remarkably excellent.

The surface roughness (arithmetic mean roughness Ra) of the resin film is preferably such that the surface roughness Ra is from 300 to 2,000 (angstroms), more preferably from 300 to 1,500 で in that the effect of the present invention is more excellent.
The surface roughness Ra is calculated by measuring the distance of 1 mm of the resin film with a resolution of 1 μm / point using DektakXT manufactured by BRUKER.

  The thickness of the resin film is not particularly limited, and is preferably 0.2 to 10 μm, more preferably 0.5 to 3 μm, from the viewpoint that the effect of the present invention is more excellent. The above thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the resin film and arithmetically averaging them.

Hereinafter, various materials and manufacturing methods for constituting the resin film of the first embodiment will be described.
Below, the aspect which makes a resin film contain a filler first is demonstrated as a method of roughening the film | membrane surface first.

[Embodiment 1A]
Examples of the material constituting the resin film include titanium nitride-containing particles containing at least one metal atom other than titanium atoms, a binder resin, and a filler. The resin film can be formed by applying a resin composition containing the above-described constituent materials or precursor materials thereof onto a substrate.
Moreover, the said resin composition can also be used as the photosensitive resin composition which has exposure and developability. In this case, a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition. Furthermore, a binder resin, a polymerizable compound, a dispersion resin described later, and the like may be used as the alkali-soluble material.
Hereinafter, various materials contained in the above-described resin composition (hereinafter referred to as “resin composition A”) will be described in detail.

[Resin composition A]
<Titanium nitride-containing particles containing at least one metal atom other than titanium atoms>
Resin composition A contains, as a black pigment, titanium nitride-containing particles (hereinafter also referred to as “titanium nitride-containing particles”) containing at least one metal atom other than titanium atoms. Titanium nitride-containing particles contain titanium atoms and at least one metal atom other than titanium atoms. In the following description, “metal atom” means “metal atom other than titanium atom”.

The titanium nitride-containing particles described above are composite fine particles composed of titanium nitride particles and metal fine particles. “Composite fine particles” refers to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that the particles are composed of both titanium nitride and metal components, and “highly dispersed” means that the titanium nitride particles and metal particles are It means that the particles exist individually and the small amount of particles are not aggregated and are uniformly and uniformly dispersed.
Further, the “titanium nitride particles” include titanium nitride as a main component, and are usually low-order titanium oxides represented by titanium oxide TiO ₂ and Ti _n O _2n-1 (1 ≦ n ≦ 20) as subcomponents. And TiN _y O _z (y and z are each greater than 0 and less than 2).

The content of metal atoms and the content of titanium atoms are analyzed by ICP (high frequency inductively coupled plasma) emission spectroscopy, and the content of nitrogen atoms is analyzed by inert gas melting-thermal conductivity method, and the content of oxygen atoms The amount can be analyzed by an inert gas melting-thermal conductivity method. Based on these analysis results, the amount of elements contained in the particles is calculated. However, depending on the method of producing the fine particles, atoms other than the titanium atom, nitrogen atom, oxygen atom, and metal atom may be contained as impurities. However, if the amount of impurities is small and difficult to specify, the impurities are considered. Calculation without
From the viewpoint of dispersion stability and light-shielding property, the specific surface area is preferably ^{5 m} 2 / g or more 100 m ² / g or less of titanium nitride-containing particles, ^{10 m} 2 / g or more ^{60 m} 2 / g or less is more preferable. The specific surface area can be determined by the BET method.

The metal atom (metal fine particle) is not particularly limited. For example, copper, silver, gold, vanadium, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium , Tantalum, calcium, titanium, bismuth, antimony and lead, and alloys thereof. Among these, at least one selected from copper, silver, gold, iron, platinum, palladium, nickel, vanadium, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, copper, silver, gold, nickel, More preferably, it is at least one selected from vanadium, platinum, tin and iron, and alloys thereof. From the viewpoint of better moisture resistance, at least one selected from silver and iron is more preferable, and silver is particularly preferable.
In the titanium nitride-containing particles, the content of metal atoms (metal fine particles) is preferably more than 0.001% by mass and less than 50% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01% by mass. % To 30% by mass, more preferably 0.2% to 30% by mass. In addition, when multiple types of metal atoms (metal fine particles) are included, the total content is included in the above numerical range.
When the content of the metal atom is more than 0.001% by mass, the patterning property of the cured film is excellent. When the metal atom content is less than 50% by mass, the moisture resistance and rubbing resistance are excellent. The corrosion resistance of the electrode by the cured film is excellent. That is, it can suppress that a cured film corrodes an electrode.
The metal atom contained in the titanium nitride-containing particle has excellent adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particle was attached to the electrode and the substrate via the metal atom. Conceivable. For this reason, it is considered that metal atoms remain on the electrode and the substrate after the patterning of the cured film such as development processing, and the titanium nitride is easily removed. Therefore, it is presumed that the patterning property of the cured film is improved by setting the content of metal atoms in the titanium nitride-containing particles to a predetermined amount or more.

  In addition, when storing at high temperature and high humidity, the content of metal atoms is preferably 0.001% by mass or more and less than 0.4% by mass. It is presumed that the anticorrosion property of the electrode became excellent by setting the content of metal atoms in the titanium nitride-containing particles to less than 0.4% by mass. When obtaining this effect, it is more preferably 0.01 to 0.2% by mass, and further preferably 0.02 to 0.1% by mass.

The metal fine particles in the titanium nitride-containing particles exist in a stable state as fine particles without performing surface coating or the like.
In order to obtain higher light-shielding properties as metal fine particles, it is preferable that the fine particles be appropriately formed. The crystallite size determined from the half-width of the strongest main peak in the X-ray diffraction spectrum of the metal fine particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less. The crystallite size can be calculated from the full width at half maximum of the X-ray diffraction peak using Scherrer's equation.
For example, in the case of an X-ray diffraction spectrum of silver, when CuKα ray is used as an X-ray source, a peak derived from the (111) plane is seen in the vicinity of 2θ = 38.1 ° as the strongest peak. The crystallite size obtained from the half width of the (111) plane is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less.

The titanium nitride particles preferably have the following characteristics in order to improve light shielding properties.
In the X-ray diffraction spectrum of titanium nitride, when CuKα ray is used as an X-ray source, TiN has a peak with the strongest intensity, and a peak derived from the (200) plane is observed in the vicinity of 2θ = 42.5 °. ) A peak derived from the surface is seen in the vicinity of 2θ = 43.4 °. On the other hand, most if not strength strong peaks, anatase TiO ₂ is observed in peak 2 [Theta] = 48.1 ° near derived from (200) plane, rutile TiO ₂ has a peak derived from the (200) plane It is observed in the vicinity of 2θ = 39.2 °. Therefore, a titanium compound having a crystal structure having nitrogen atoms and oxygen atoms has the strongest peak in the diffraction angle 2θ range of 42.5 ° to 43.4 °, and is in a crystalline state containing a large amount of oxygen atoms. The more the peak position is shifted to the higher angle side with respect to 42.5 °.

From the viewpoint of light shielding properties, the titanium nitride particles preferably contain TiN as a main component, and the peak diffraction angle 2θ derived from the (200) plane is preferably 42.5 ° or more and 43.5 ° or less, 42 The angle is more preferably from 5 ° to 42.8 °, still more preferably from 42.5 ° to less than 42.7 °. Titanium nitride particles are usually partially in the form of oxynitrides containing oxygen atoms due to oxidation of the particle surface. Usually, the mixing of oxygen during the synthesis of titanium nitride particles becomes particularly noticeable when the particle size is small. A smaller amount of oxygen is preferable because higher light shielding properties can be obtained, and it is particularly preferable not to contain TiO ₂ as a subcomponent. The oxygen atom content is preferably 10% by mass or less, and more preferably 6.0% by mass or less, based on the mass of the titanium nitride particles.

  From the viewpoint of light shielding properties, the crystallite size of the titanium nitride particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less. When the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the particle volume becomes small and a good balance is obtained. As a result, titanium nitride-containing particles that are remarkably excellent in heat resistance or durability can be obtained.

The diffraction angle 2θ of the peak derived from the TIN (200) plane of the titanium nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less from the viewpoint of light shielding properties, in order to improve the light shielding properties. Is more preferably 42.5 ° or more and 42.8 ° or less, and further preferably 42.5 ° or more and less than 42.7 °. When titanium oxide TiO ₂ is contained as a subcomponent, a peak derived from anatase TiO ₂ (101) is seen as the strongest peak in the vicinity of 2θ = 25.3 °, and rutile TiO ₂ (110). The peak derived from is seen in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes light-shielding properties to decrease, it is preferably reduced to such an extent that it is not observed as a peak.

  The titanium nitride-containing particles are preferably produced through a process of mixing and condensing Ti and a metal element in a gas phase, and produced by a thermal plasma method using a nitrogen-containing gas as a plasma gas. It is more preferable that

As the titanium nitride-containing particles, those described in International Publication No. 2010/147098, Japanese Patent Application Laid-Open No. 2007-153662, and the like can be further referred to.
The content of titanium nitride-containing particles is preferably 30 to 60% by mass, more preferably 35 to 60% by mass, and 40 to 55% by mass with respect to the total solid content in the resin composition. More preferably.

As a method for producing titanium nitride-containing particles, the ones described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to.
Further, the titanium nitride-containing particles are produced for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours) in a closed container in which the oxygen concentration is controlled without immediately exposing the titanium nitride-containing particles to the atmosphere. And more preferably 12 to 24 hours). At that time, it is more preferable that the water content is controlled. Thereby, the surface and crystal grain boundary of the titanium nitride-containing particles are stabilized, and it is estimated that the performance of the composition is improved. Specifically, the generation of pinholes in a cured film obtained using the composition of the present invention can be suppressed.
The oxygen (O ₂ ) concentration and the moisture content in the closed container in which the oxygen concentration is controlled are each preferably 100 mass ppm or less, more preferably 10 mass ppm or less, and more preferably 1 mass ppm or less. More preferably. Nitrogen above oxygen (O ₂₎ concentration, and the adjustment of the water content, the above oxygen (O ₂₎ concentration, and oxygen (O ₂₎ in the above range of the content of _water, and a water-containing It is preferable to use an inert gas such as gas or argon gas, and among these, it is more preferable to use nitrogen gas. Thereby, the surface and crystal grain boundary of the titanium nitride-containing particles are stabilized, and it is estimated that the performance of the composition is improved. Specifically, titanium nitride-containing particles having a high optical density can be obtained, and generation of pinholes in a cured film obtained using the composition of the present invention can be suppressed. Further, the temperature for standing for a predetermined time is preferably 300 ° C. or less, more preferably 200 ° C. or less, and particularly preferably 100 ° C. or less. Within this range, titanium nitride-containing particles having a higher optical density can be obtained.

  It is preferable that the titanium powder material used for manufacturing the titanium nitride-containing particles is of high purity. The titanium powder material is not particularly limited, and a titanium element having a purity of 99.99% by mass or more is preferable, and a material having 99.999% by mass or more is more preferably used.

Further, the content of silicon atoms in the titanium powder material is preferably less than 0.3% by mass, more preferably less than 0.1% by mass, substantially including the total amount of the titanium powder material. It is particularly preferred not to.
In addition, the water content in the titanium powder material is preferably less than 1% by mass, more preferably less than 0.1% by mass with respect to the total amount of the titanium powder material, and substantially no inclusion. Particularly preferred. A desired effect can be acquired more notably that it is said range.

Examples of the process for dispersing the titanium nitride-containing particles include a process using compression, squeezing, impact, shearing, cavitation or the like as a mechanical force used for dispersion. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, ultrasonic dispersion, and a microfluidizer. Also, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” or “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and disperser described in “Issuance, October 10, 1978” can be preferably used. You may perform the refinement | miniaturization process of the pigment by a salt milling process. As materials, equipment, processing conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.
Among these, a sand mill (bead mill) is preferable. In the grinding of pigments in a sand mill (bead mill), it is preferable to use beads having a small diameter or to process under conditions where the grinding efficiency has been increased by increasing the filling rate of beads. It is preferable to remove the elementary particles by centrifugation or the like.

  Said titanium nitride containing particle | grains are used suitably also for the process of disperse | distributing the pigment mentioned later.

<Binder resin>
Resin composition A contains a binder resin.
The binder resin preferably contains neither fluorine atoms nor silicon atoms. Here, “containing neither fluorine atom nor silicon atom” means that fluorine atom and silicon atom are not substantially contained in the resin, and each content is 3 with respect to the total mass of the resin. It is preferable that it is mass% or less, and it is more preferable that it is 0.1 mass% or less.

It does not specifically limit as binder resin, It is preferable to use a linear organic polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily.
The molecular weight of the binder resin is not particularly defined, and it is preferable that the weight average molecular weight (Mw) is 5000 to 100,000 as a polystyrene converted value by GPC (gel permeation chromatography) method. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The GPC method uses HLC-8020 GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

  As described above, the resin composition A can have exposure / developability. Therefore, when the resin composition A is a photosensitive resin composition, the binder resin is preferably a resin that can be developed with water or weakly alkaline water, and is soluble or swellable in water or weakly alkaline water. More preferably, it is a linear organic polymer. Among these, as the binder resin, an alkali-soluble resin (a resin having a group that promotes alkali-solubility) is particularly preferable.

The molecular weight of the alkali-soluble resin is not particularly defined, and the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000. A weight average molecular weight and a number average molecular weight can be measured by the above-mentioned method.
The alkali-soluble resin may be a linear organic polymer, and promotes at least one alkali-solubility in the molecule (preferably a molecule having an acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. An acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are more preferable.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are soluble in an organic solvent and developed with a weakly alkaline aqueous solution. What is possible is preferred. Only one type of acid group may be used, or two or more types may be used.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable with (meth) acrylic acid is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and N-substituted maleimide monomers. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene monomer Romonoma, polymethyl methacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, N- phenylmaleimide, mention may be made of N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

In order to improve the crosslinking efficiency of the resin composition A, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in the side chain is useful.
Examples of the alkali-soluble resin having a polymerizable group include NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing, polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist). 106 (both manufactured by Osaka Organic Chemical Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD -F8 (manufactured by Nippon Shokubai Co., Ltd.).

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.
Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.

  The alkali-soluble resin includes a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing monomer components.

In General Formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

  In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, linear or branched alkyl groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, tert-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; phenyl group An alicyclic group such as cyclohexyl group, tert-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group; Alkyl groups substituted by alkoxy such as methoxyethyl group and 1-ethoxyethyl group; alkyl groups substituted by aryl group such as benzyl group; and the like It is. Among these, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, is particularly preferable in terms of heat resistance.

  As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used. The compound represented by the general formula (ED1) and / or the structure derived from the compound represented by the general formula (ED2) may be copolymerized with other monomers.

  The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

In Formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the formula (X), the number of carbon atoms of the alkylene group _{R 2} is preferably 2-3. The number of carbon atoms in the alkyl group of _{R 3} is from 1 to 20, more preferably 1 to 10, alkyl group of _{R 3} may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

  Specific examples of the alkali-soluble resin include the following. “Me” means a methyl group.

For the alkali-soluble resin, paragraphs 0558 to 0571 in JP 2012-208494 A (corresponding to <0685> to <0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and these can be referred to. The contents are incorporated herein.
Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in Examples, paragraphs 0088 to 0098 of JP2012-208474A The binder resin described and the binder resin used in the examples, the binder resin described in paragraph Nos. 0022 to 0032 of JP 2012-137531 A and the binder resin used in the examples, JP 2013-024934 A The binder resin described in paragraph Nos. 0132 to 0143 of the gazette and the binder resin used in the examples, the binder numbers used in the paragraphs 0092 to 0098 and the examples of JP 2011-242752 A, and JP 2012 Paragraph Nos. 0030 to 0072 of JP-032770 It is also possible to use a binder resin according. These contents are incorporated herein.

  The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

  Further, as other resins, polyimide resins described in International Publication No. 2008/123097 are also useful.

  As for content of the binder resin in the resin composition A, 0.01-40 mass% is preferable with respect to the total solid of a composition. The lower limit is more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and most preferably 1.5% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. In the resin composition A, only one type of binder resin may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<Filler>
Resin composition A contains a filler. Here, the “filler” is a particle provided for the purpose of roughening the surface. The above-mentioned titanium nitride-containing particles are not included in the filler. Moreover, the particle | grains used for coloring property provision, such as another pigment, are not contained in a filler, and a non-coloring thing is preferable as a filler.
The composition of the filler is not particularly limited, and either inorganic particles or organic particles may be used.
The inorganic particles are not particularly limited, and examples thereof include oxides such as silicon, titanium, aluminum, tin, zinc, and antimony. The inorganic particles may have a porous or hollow (hollow) structure inside.
The organic particles are not particularly limited, and examples thereof include cellulose derivatives, acrylic resins, polyolefins, polyamides, polycarbonates, polystyrene, vinyl acetate, vinyl alcohol, vinyl chloride or vinyl butyral homopolymer or copolymer. Resins such as vinyl polymers such as coalescence, diene homopolymers and copolymers, and the like.
Among these, silica particles and acrylic particles are preferable from the viewpoint of low reflectivity, and hollow silica having a hollow structure (hollow silica particles) is more preferable.

The maximum value in the particle size distribution of the filler is preferably 50 to 1000 nm, and more preferably 50 to 500 nm from the viewpoint of more excellent moisture resistance and scratch resistance.
The maximum value in the particle size distribution of the filler can be measured by Nanotrac UPA-EX manufactured by Microtrac Bell.

When the resin composition A contains a filler, the content thereof is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on the total solid content in the composition, More preferably, it is 3-15 mass%.
In the resin composition A, only one type of filler may be included, or two or more types of fillers may be included. When two or more types are included, the total amount is preferably within the above range.

<Dispersed resin>
The resin composition A may contain a dispersion resin. The dispersion resin contributes to the improvement of the dispersibility of the above-described titanium nitride-containing particles (hereinafter, also referred to as “black pigment” as appropriate) and other pigments such as other pigments used in combination as desired.
Examples of the dispersion resin include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene. Examples include sulfonic acid formalin condensate.
Dispersion resins (hereinafter also referred to as “polymer compounds”) can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers, based on their structures.

The polymer compound is adsorbed on the surface of a dispersion such as a black pigment and, if desired, a pigment used together, and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorptivity of the polymer compound to these can be promoted.

The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of a colored pigment such as a black pigment and dispersion stability after a lapse of time because it has an affinity for a solvent by the graft chain. It is. In addition, since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to a colored pigment such as a black pigment is lowered and the dispersibility tends to be lowered. For this reason, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is 60 to 500.
Here, the “graft chain” means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain. .

The graft chain preferably has a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility, the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. The graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.

  The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be preferably used.

  Corresponding to the structural unit having a graft chain of the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Gosei Co., Ltd.), AA-10 ( Product name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product) Name, manufactured by Toa Gosei Co., Ltd.), Aronix M-110 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-530 (Trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-5400 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-5700 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (product) Name, manufactured by NOF Corporation), BLEMMER PP-500 (trade name, manufactured by NOF Corporation), BLEMMER PP-800 (trade name, manufactured by NOF Corporation), BLEMMER PP-1000 (trade name, NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation), BLEMMER PSE-400 (trade name, NOF Corporation), BLEMMER PSE-1300 (trade name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) and the like are used. Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-110 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-5300 (Trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) and the like are used.

  The polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain. The following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).

In formulas (1) to ^{(4), W 1, W} 2, W 3, and ^{W 4} represents an oxygen atom or NH independently. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. . In the structure shown below, A and B each represent a binding site with the left terminal group and the right terminal group in Formulas (1) to (4). Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In Formula (1)-Formula (4), n, m, p, and q are the integers of 1 to 500 each independently.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

In Formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is more preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

In addition, the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be included, and in the formulas (1) to (4), n, m , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R ³ , R ⁴ and X ⁵ present in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoints of dispersion stability and developability.
Further, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  Moreover, as a structural unit represented by Formula (3), it is more preferable that it is a structural unit represented by following formula (3A) or Formula (3B) from a viewpoint of dispersion stability and developability.

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and p are as defined ^{X 3,} Y 3, ^{Z 3} and p in formula (3), and preferred ranges are also the same.

  The polymer compound preferably has a structural unit represented by the formula (1A) as a structural unit having a graft chain.

  In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a range of 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersibility of a colored pigment such as a black pigment is high, and the developability when forming a colored layer is good.

  The polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

  The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.

ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

  It is preferable that a high molecular compound has 1 or more types of structural units selected from the structural unit derived from the monomer represented by the following general formula (i)-(iii) as a hydrophobic structural unit.

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom number 1-6 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, etc.) are represented.
R ¹ , R ² , and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (for example, an arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), or a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, wherein R ³¹ is an aliphatic group, an aromatic group. Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

  6-20 are preferable, as for the carbon atom number of an aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In said formula (iii), R < ⁴ >, R < ⁵ > and R < ⁶ > are respectively independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a C1-C6 alkyl. Represents a group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred. Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.

Examples of typical compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of typical compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.

  In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90% and more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.

The polymer compound can introduce a functional group capable of forming an interaction with a colored pigment such as a black pigment. Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment.
Examples of the functional group capable of forming an interaction with the colored pigment such as the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. Or a structural unit having a functional group having reactivity.
In particular, when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, in the resin composition A, the polymer compound as a dispersion resin that contributes to the dispersion of a colored pigment such as a black pigment has alkali solubility. A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
This is because the acid group in the structural unit having an acid group easily interacts with a color pigment such as a black pigment, and the polymer compound stably disperses the color pigment such as a black pigment, This is presumably because the viscosity of the polymer compound to be dispersed is low and the polymer compound itself is easily dispersed stably.

  However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. The structural unit possessed is a structural unit different from the hydrophobic structural unit described above. That is, it does not correspond to the hydrophobic structural unit described above.

Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and particularly preferred is a carboxylic acid group that has good adsorptive power to colored pigments such as black pigments and has high dispersibility. .
That is, the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, and when it is contained, the content of the structural unit having an acid group is, in terms of mass, with respect to the total mass of the polymer compound, Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.

Examples of the basic group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom, There are amide groups and the like, and particularly preferred is a tertiary amino group which has a good adsorptive power to colored pigments such as black pigments and has high dispersibility. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group. When it is contained, the content of the structural unit having a basic group is based on the total mass of the polymer compound in terms of mass. The content is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing the development inhibition.

As a coordinating group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, Examples include acid chlorides. Particularly preferred is an acetylacetoxy group which has a good adsorptive power to colored pigments such as black pigments and high dispersibility. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, and if included, the content of these structural units is In terms of conversion, it is preferably 10% or more and 80% or less with respect to the total mass of the polymer compound, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developability inhibition.

  When the polymer compound in the present invention has a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, it forms an interaction with various colored pigments such as the black pigment as described above. It is only necessary to contain functional groups that can be used, and how these functional groups are introduced is not particularly limited, and the polymer compound is represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from monomers.

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom. An alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
In general formula (iv) to general formula (vi), R ¹¹ , R ¹² and R ¹³ are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Are each independently a hydrogen atom or a methyl group. In general formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.

Moreover, L < ₁ > in general formula (iv)-general formula (v) represents a single bond or a bivalent coupling group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a colored pigment such as a black pigment in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable that it is a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, propyl group, etc.), - represents a _{Z 1,} or _-L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or an oxyalkylene structure. A compound in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, and L ₁ is a single bond or an alkylene group, A compound in which Z is a carboxylic acid group is preferred.

Below, the typical example of the monomer (compound) represented by general formula (iv)-general formula (vi) is shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenol Such as Le methacrylamide.

  The content of the structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment is from the viewpoint of interaction with a colored pigment such as a black pigment, dispersion stability, and permeability to a developer. 0.05-90 mass% is preferable with respect to the total mass of a high molecular compound, 1.0-80 mass% is more preferable, and 10-70 mass% is still more preferable.

Furthermore, for the purpose of improving various performances such as image strength, the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and a colored pigment such as a black pigment, as long as the effects of the present invention are not impaired. Other structural units having various functions different from structural units having a functional group capable of forming an interaction (for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion) Furthermore, you may have.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g. The range is as follows.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming the resin layer is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Further, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored pigments such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.

  In the present invention, the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a resin film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
The GPC method uses HLC-8020 GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

  The polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (acid group). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA 4047, 4050 to 4010 to 4165 (polyurethane) ", EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA Amide), 5765 (high molecular weight polycarboxylate), 622 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester)” manufactured by Enomoto Kasei Co., Ltd. , DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) manufactured by Kao Corporation ) "," Homogenol L-18 (polymeric polycarboxylic acid) ", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)" manufactured by Nippon Lubrizol Co., Ltd. 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (Nikkor Chemicals) ” Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosi Xan polymer KP341, “W001: cationic surfactant” manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA manufactured by Morishita Sangyo Co., Ltd.” -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6, D Polymer dispersing agents such as “Sparse Aid 8, Disperse Aid 15, Disperse Aid 9100”, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 manufactured by ADEKA Corporation , F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Moreover, as a commercial product of amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, Ajisper PB822, Ajisper PB881 and the like.
These polymer compounds may be used alone or in combination of two or more.

  As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

Further, as the dispersion resin, in addition to the above-described polymer compound, graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding paragraphs 0075 to 0133 of US2011 / 0124824) can be used. The contents can be incorporated and incorporated herein.
In addition to the above, a structure having a side chain structure in which acidic groups of paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

  0.1-50 mass% is preferable with respect to the total solid of a composition, as for content of the dispersion resin in the resin composition A, 1-40 mass% is more preferable, and 1-30 mass% is still more preferable.

Examples of the process for dispersing the pigment include a process using compression, squeezing, impact, shearing, cavitation or the like as the mechanical force used for dispersion. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, ultrasonic dispersion, or a microfluidizer. Also, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” or “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and disperser described in “Issuance, October 10, 1978” can be preferably used. You may perform the refinement | miniaturization process of the pigment by a salt milling process. As materials, equipment, processing conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.
Among these, a sand mill (bead mill) is preferable. In the grinding of pigments in sand mills (bead mills), it is preferable to use beads with small diameters and to treat them under conditions that increase the grinding efficiency by increasing the filling rate of beads. It is preferable to remove the elementary particles by separation or the like.

<Polymerization initiator>
The resin composition A may contain a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. And the compounds described in the specification.

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Preferred are compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. .

  More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of a compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

In particular, when the resin film of the present invention is used for the production of a light-shielding film for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is preferred that From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

  The resin composition A preferably contains an oxime compound represented by the following formula (I) as a polymerization initiator.

In formula (I), R ^a represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, R ^b represents an alkyl group, an aryl group or a heterocyclic group, and a plurality of R ^c are each independently , A hydrogen atom, an alkyl group, or a group represented by -OR ^h . R ^h represents an electron withdrawing group or an alkyl ether group. However, at least one of the plurality of R ^c represents a group represented by —OR ^h .

In formula (I), R ^a represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, preferably an aryl group or a heterocyclic group, and more preferably a heterocyclic group.
1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, 1-10 are still more preferable, and 1-4 are especially preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-20 are preferable and, as for carbon number of an acyl group, 2-15 are more preferable. Examples of the acyl group include an acetyl group and a benzoyl group.
6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are still more preferable. The aryl group may be a single ring or a condensed ring.
The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4. 3-40 are preferable, as for the number of the carbon atoms which comprise a heterocyclic group, 3-30 are more preferable, and 3-20 are more preferable. As for the number of the hetero atoms which comprise a heterocyclic group, 1-3 are preferable. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

The above-described group represented by R ^a may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , —NHCOR ^X1 , —CONR ^X1 R ^X2 , —NHCONR ^X1 R ^X2 , —NHCOOR ^X1 , —SO ₂ R ^X1 , —SO ₂ OR ^X1 , —NHSO ₂ R ^{X1 and the} like can be mentioned. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As for carbon number of the alkyl group as a substituent and the alkyl group which R ^<X1> and R ^<X2> represent, 1-20 are preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. In the alkyl group, part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom). In the alkyl group, part or all of the hydrogen atoms may be substituted with the above substituents.
6-20 are preferable, as for carbon number of the aryl group which R ^{< X1>} and R ^<X2> represent as a substituent and R ^{< X1>} and R ^<X2 >, 6-10 are still more preferable. The aryl group may be a single ring or a condensed ring. In the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents.
The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably 5-membered rings or 6-membered rings. The heterocyclic group may be a single ring or a condensed ring. 3-30 are preferable, as for the number of the carbon atoms which comprise a heterocyclic group, 3-18 are more preferable, and 3-12 are more preferable. As for the number of the hetero atoms which comprise a heterocyclic group, 1-3 are preferable. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the hetero group, part or all of the hydrogen atoms may be substituted with the above substituents.

The heterocyclic group represented by R ^a is preferably a group represented by the following formula (II).

In the formula (II), Ar ¹ and Ar ² each independently represents an aromatic hydrocarbon ring which may have a substituent, R ³ represents an alkyl group or an aryl group, and * represents a bonding position. Represents.
In formula (II), Ar ¹ and Ar ² each independently represents an aromatic hydrocarbon ring which may have a substituent.
The aromatic hydrocarbon ring may be a single ring or a condensed ring. 6-20 are preferable, as for the carbon atom number which comprises the ring of an aromatic hydrocarbon ring, 6-15 are more preferable, and 6-10 are especially preferable. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring. Of these, at least one of Ar ¹ and Ar ² is preferably a benzene ring, and Ar ¹ is more preferably a benzene ring. Ar ² is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.
Examples of the substituent that Ar ¹ and Ar ² may have include the substituent described in ^Ra .
Ar ¹ is preferably unsubstituted. Ar ² may be unsubstituted or may have a substituent. As the substituent, —COR ^X1 is preferable. R ^X1 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
In formula (II), R ³ represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the above-mentioned R ^a.
1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-10 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are still more preferable. The aryl group may be a single ring or a condensed ring.

In formula (I), ^Rb represents an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group, and more preferably an alkyl group. An alkyl group, an aryl group, and a heterocyclic group are synonymous with the group demonstrated by ^Ra . These groups may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for ^Ra .

In formula (I), a plurality of R ^{c s} each independently represent a hydrogen atom, an alkyl group, or a group represented by —OR ^h . R ^h represents an electron withdrawing group or an alkyl ether group. However, at least one of the plurality of R ^c represents a group represented by —OR ^h .

Number of carbon atoms of the alkyl group R ^c represents preferably 1 to 20, more preferably from 1 to 15, more preferably 1 to 10, 1 to 4 are particularly preferred. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.

As the electron withdrawing group represented by R ^h in -OR ^h, for example, a nitro group, a cyano group, a fluorine atom, at least one hydrogen atom and an alkyl group having 1 to 20 carbon atoms which is substituted with a fluorine atom Can be mentioned.
Of these, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom is preferable. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 4 carbon atoms, and may be linear, branched or cyclic, and is preferably linear or branched.

Alkyl ether group represented by R ^h in -OR ^h refers to an alkyl group substituted with an alkoxy group. The alkyl group in the alkyl ether group and the alkyl group in the alkoxy group in the alkyl ether group preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and 1 to 4 carbon atoms. Is particularly preferred. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-8 are preferable, as for the total number of carbon number of an alkyl ether group, 2-6 are more preferable, and 2-4 are more preferable.

Of the plurality of R ^c , one or two are preferably groups represented by —OR ^h . In this case, when R ^h in -OR ^h is an electron withdrawing group (e.g., at least one alkyl group of 1 to 20 carbon atoms in which a hydrogen atom has been substituted with a fluorine atom), and the remaining R ^c, A hydrogen atom is preferred. On the other hand, when R ^h in -OR ^h is an alkyl ether group, the remaining R ^c, it is preferred that one is an other is hydrogen atom in an alkyl group.
Further, in the benzene ring to which R ^c is attached, relative to 1 carbons R ^c is not bound, the alkyl group represented by R ^c, or group represented by -OR ^h, the ortho or It is preferably located in the para position.

  Specific examples of the photopolymerization initiator represented by formula (I) or formula (II) include the following compounds.

  It is also preferable that the resin composition A contains an oxime compound represented by the following formula (III) as a polymerization initiator.

In Formula (III), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or carbonyl Indicates a group.

In the formula (III), R ⁵ represents —R ⁶ , —OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , ^{-OCSR 6, -COSR 6, -CSOR 6} , -CN, a halogen atom or a hydroxyl group, ^{R 6} is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 7 to 30 carbon atoms An arylalkyl group or a C4-C20 heterocyclic group is represented, and a represents an integer of 0-5.

In the above formula (III), R ¹ and R ² are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compound represented by the formula (III) include compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

  Specific examples of the oxime compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.

  Moreover, it does not specifically limit as a polymerization initiator marketed, IRSFACURE OXE 01 (1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl oxime)] by BASF Japan ), IRGACURE OXE 02 (ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) Examples include thioxanthen-9-one, O-acyloxime compounds (for example, Adekaoptomer N-1919, Adeka Arcles NCI-831, manufactured by ADEKA), Adeka Arcles NCI-930, and the like. Incorporated in the description.

As for content of a polymerization initiator, 0.1-30 mass% is preferable with respect to the total solid of a composition, More preferably, it is 0.5-20 mass%, More preferably, it is 1-10 mass%, Especially preferably, it is 1-7 mass%.
Resin composition A may contain only one type of polymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Silane coupling agent>
Resin composition A may contain a silane coupling agent.
The “silane coupling agent” is a compound having a hydrolyzable group and other functional group in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The “hydrolyzable group” refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the cured film, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded). Includes silicon atoms (excluding silicon atoms bonded with hydrolyzable groups), alkylene groups substituted with silicon atoms, straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Preferably not.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si- (R _Z1 ) ₃
In the formula (Z), R _Z1 represents a hydrolyzable group, and the definition thereof is as described above.

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group. Among these, an epoxy group is preferable from the viewpoints of improving adhesion, developing resistance, and solvent resistance.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.

  The molecular weight of the silane coupling agent is not particularly limited, and is preferably 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 in terms of more excellent effects of the present invention.

One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula _{(W) R Z2 -Lz-Si-} (R Z1) 3
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR _{^{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Especially, at least 1 sort (s) selected from the group which consists of the alkylene group which the C2-C10 halogen atom may substitute, and the arylene group which the C6-C12 halogen atom may substitute, or , At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group consisting of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.

  As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy Silane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503), 3-glycidoxypropylmethyldimethoxysilane (trade name KB manufactured by Shin-Etsu Chemical Co., Ltd.) -402), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. trade name LS-2940), glycidoxypropyltrimethoxysilane octyltrimethoxysilane (Shin-Etsu Chemical Co., trade name KBM-4803), and the like.

As another preferred embodiment of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided. Can be mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents further include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group, an amino group, a halogen atom, and a sulfonamide group. , An alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof may be substituted.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the above formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxyl group, or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to have two or more curable functional groups from the viewpoint of sensitivity and stability. Preferably has 2-20 curable functional groups, more preferably 4-15, and still more preferably 6-10 curable functional groups in the molecule.

  The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and include the above-described ranges (preferably 270 or more).

The content of the silane coupling agent in the resin composition A is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, with respect to the total solid content in the composition. -6 mass% is still more preferable.
The resin composition A may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

<Polymerizable compound>
The resin composition A may contain a polymerizable compound.
The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, further preferably 3 or more, and particularly preferably 5 or more. The upper limit is 15 or less, for example. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
100-3000 are preferable and, as for the molecular weight of a polymeric compound, 250-1500 are more preferable.
The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, or the above unsaturated carboxylic acid. A dehydration condensation reaction product of an acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

  In the present invention, the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. As examples thereof, for example, compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.

The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454, SR499, commercially available from Sartomer) preferable. These oligomer types can also be used. Moreover, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
Preferred embodiments of the polymerizable compound are shown below.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound having a caprolactone structure.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, Mention may be made of ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone. Especially, the compound which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2,
“*” Indicates a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

The polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

  As the polymerizable compound, a compound represented by the following general formula (Z-4) or (Z-5) can also be used.

In general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). -, Y represents each independently an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. .
In general formula (Z-5), the total of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. .

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is still more preferable.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the total of each n is more preferable, the integer of 3-24 is more preferable, and the integer of 6-12 is still more preferable.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen A form in which the end on the atom side is bonded to X is preferred.

  The compound represented by general formula (Z-4) or general formula (Z-5) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (Z-5), a form in which all six X are acryloyl groups, in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), among which exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, it is possible to obtain a resin composition A having an excellent photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

The polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 .

Moreover, it is also preferable that the resin composition A has a polymerizable compound having a cardo skeleton from the viewpoint of improving development resistance.
As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

General formula (Q3)

In the general formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represents an aryl group containing a benzene ring surrounded by a broken line.
a and b each independently represent an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4. R ^{1 to} R ⁴ each independently represent a substituent, e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are Ar ^{11 to} Ar ^14, respectively. This is a value obtained by subtracting a, b, c or d from the number of substituents which can be possessed. However, when Ar ^{11 to} Ar ¹⁴ are each a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are respectively It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.

In the general formula (Q3), the aryl group including a benzene ring surrounded by a broken line represented by Ar ^{11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms. (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.

In the general formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X ^{1 to} X ⁴ is not particularly limited, and is preferably an aliphatic group having a polymerizable group.
The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is not particularly limited, and is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and an alkylene group having 2 to 10 carbon atoms. It is more preferably a group, and further preferably an alkylene group having 2 to 5 carbon atoms.
In the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ , when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom. The non-adjacent —CH ₂ — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH ₂ — in the aliphatic group is More preferably, it is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted with 1 to 2 sites by hetero atoms, more preferably 1 site with hetero atoms, Ar ^{11 to} Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line ¹⁴ is substituted with a heteroatom.
As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively). Is preferred.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one. Specifically, Examples thereof include a vinyl group and a (meth) acryloyloxy group. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Examples include groups. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
The polymerizable group contained in the substituent contained in Ar ^{1 to} Ar ⁴ is preferably a radical polymerizable group.
Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable ^group, preferably contains a substituent with 2-4 polymerizable group of Ar 1 ~Ar ^4, Ar 1 ~Ar more preferably comprising a substituent group having 2 or 3 polymerizable groups of ^four, and more preferably comprising a substituent group having two polymerizable groups of Ar ¹ to Ar ^4.
When Ar ^{11 to} Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are each independently benzene surrounded by a broken line. Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.

In the general formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
In the general formula (Q3), c and d each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably c and d are both 0.

In the general formula (Q3), R ^{1 to} R ⁴ each independently represents a substituent. R ¹ to R ⁴ is not particularly limited as substituents represented by, for example, a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an aryl group, a heteroaryl Group, alicyclic group and the like. The substituent represented by R ^{1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. And more preferably a methyl group, a methoxy group or a phenyl group.
In the general formula (Q3), when Ar ^{11 to} Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ^{1 to} R ⁴ are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.

In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar ^{11 to} Ar ¹⁴ can have. The value obtained by subtracting a, b, c, or d from the number of.
e, f, g and h are each independently preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.
When Ar ^{11 to} Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.

  Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound having a 9,9-bisarylfluorene skeleton, compounds described in JP2010-254732A can also be suitably used.

  Examples of the commercially available polymerizable compound having a cardo skeleton include, but are not limited to, ONCOAT EX series (manufactured by Nagase Sangyo Co., Ltd.), Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.), and the like.

In the resin composition A, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and further preferably 2% by mass or more. For example, the upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less.
One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

  In the resin composition A, the mass ratio (M / B) of the total content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin described above is 0.3-2. 0 is preferable, and 0.45 to 1.5 is more preferable from the viewpoint of better abrasion resistance.

<Organic solvent>
The resin composition A may contain an organic solvent.
The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the resin composition A. In consideration of the solubility, coating property, and safety of the polymerizable compound, the binder resin, and the like. It is preferable to be selected.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) )), 2-oxypropionic acid alkyl esters (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionic acid) Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example 2 -Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2 -Ethyl oxobutanoate and the like, and As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like, and Suitable examples of aromatic hydrocarbons include toluene and xylene.

It is also preferable to mix two or more kinds of these organic solvents from the viewpoints of solubility of the polymerizable compound, the binder resin and the like, and improvement of the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the organic solvent in the resin composition A is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. -50 mass% is still more preferable.
The resin composition A may contain only one type of organic solvent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Other additives>
In the resin composition A, various additives such as a filler, an adhesion promoter, an antioxidant, a polymerization inhibitor, an anti-aggregation agent, a surfactant, an infrared absorber, an ultraviolet absorber and the like are added as necessary. Can be contained. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The resin composition A can contain, for example, a sensitizer or light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same publication, and the like.
Moreover, pigments or dyes other than the titanium nitride-containing particles can also be blended. Examples of other pigments include the following.

<Other pigments>
Examples of the pigment include conventionally known various inorganic pigments or organic pigments.
Examples of inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and tungsten, and composite oxides of the above metals.
The following can be mentioned as an organic pigment. However, the present invention is not limited to these.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
Carbon black, lignin black, acetylene black, aniline black, C.I. I. Pigment Black 27

<Dye>
Examples of the dye include various conventionally known dyes.

  Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-51115. The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structures, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds and pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

  These organic pigments or dyes can be used alone or in various combinations in order to increase color purity. Two or more kinds may be used in combination.

  For example, it is preferable to use a red pigment and the titanium nitride-containing particles in combination from the viewpoint of adjusting the color, and the red pigment is preferably Pigment Red 254, although not particularly limited. Moreover, it is preferable to use a yellow pigment and the said titanium nitride containing particle together from a viewpoint of improving light-shielding property, Although it does not specifically limit, It is preferable that it is pigment yellow 150 as a yellow pigment.

<Surfactant>
The composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  By including a fluorosurfactant in the composition of the present invention, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a to-be-coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
A compound containing at least one of a fluorine atom and a silicon atom is not included in the fluorine-based surfactant described here.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-1002.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

  Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like. Note that a resin having a polysiloxane structure, which will be described later, and reactive silicone are not included in the silicone-based surfactant described here.

  Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, more preferably 0.005 to the total solid content of the composition of the present invention. 0.98% by mass is most preferred.

[Embodiment 1B]
Next, as a method for roughening the film surface, an embodiment in which a resin having a polysiloxane structure is contained in the resin film will be described.
Examples of the material constituting the resin film include at least the titanium nitride-containing particles described above, a binder resin, and a resin having a polysiloxane structure. The resin film can be formed by forming a resin composition containing the above-described constituent materials or precursor materials thereof and applying the resin composition onto a substrate.
Moreover, the said resin composition can also be used as the photosensitive resin composition which has exposure and developability. In this case, a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition. Furthermore, a binder resin, a polymerizable compound, a dispersion resin described later, and the like may be used as the alkali-soluble material.
Below, the various materials contained in the resin composition mentioned above (henceforth "resin composition B") are explained in full detail.
The material in the resin composition B is the same except that the filler in the resin composition A is a reactive silicone, and the same applies to preferred embodiments.

[Resin composition B]
<Resin having a polysiloxane structure, reactive silicone>
In the present invention, as another means for roughening the surface of the resin film, a resin having a polysiloxane structure can be contained in the resin film.
Here, the resin having a polysiloxane structure is preferably a resin formed from reactive silicone described later. Reactive silicone is an organic-inorganic hybrid material and has a low free surface energy. For this reason, when a resin composition containing reactive silicone and a binder resin (further, the above-described polymerizable compound) is applied on a substrate, the reactive silicone is in contrast to the binder resin (further described below). It is unevenly distributed on the surface without being compatible, and forms an uneven shape.
A resin having a polysiloxane structure also corresponds to a compound containing at least one of a fluorine atom and a silicon atom.

  Reactive silicone resin is a reactive type modified by substitution of substituents such as amino group, epoxy group, carboxyl group, hydroxyl group, methacryl group, mercapto group, phenol group at the side chain, one end or both ends of polysiloxane. Silicone resin. Specific examples of the amino-modified silicone resin include KF-860, KF-861, X-22-161A, X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3331, FM-3325 (and above, Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins KF-6001, KF-6003 (Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) as the resin, KF-2001 (made by Shin-Etsu Chemical Co., Ltd.) as the mercapto-modified silicone resin, and X-22-1821 as the phenol-modified silicone resin (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxyl group-modified silicone resin include FM-4411, FM-4421, FM-DA21, and FM-DA26 (manufactured by Chisso Corporation).

  In addition, one-terminal reactive silicone resins X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can also be used as the reactive silicone resin.

  Moreover, the content mass ratio (binder resin: reactive silicone) of reactive silicone with respect to binder resin from the point which expresses uneven | corrugated shape stably and better and the stability of a coating liquid is 100: 1-100: 30. It is preferable that it is 100: 5 to 100: 30.

When the reactive silicone is contained in the resin composition B, the content is preferably 0.2 to 20% by mass, and 0.5 to 15% by mass with respect to the total solid content in the composition. More preferably, it is 1 to 15% by mass, further preferably 1 to 10% by mass.
Resin composition B may contain only one type of reactive silicone or two or more types of reactive silicone. When two or more types are included, the total amount is preferably within the above range.

[Method for Preparing Resin Compositions A and B]
Resin compositions A and B can be prepared by mixing the aforementioned components, respectively.
In preparing the resin compositions A and B, the respective components constituting the resin compositions A and B may be mixed together, or may be sequentially mixed after each component is dissolved or dispersed in a solvent. In addition, the charging sequence and working conditions when blending are not particularly limited. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, each component is appropriately used as two or more solutions or dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The resin compositions A and B are preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth resin composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

[Production method of resin film]
Next, a method for manufacturing a resin film will be described.
The resin film of the first embodiment is preferably manufactured using the resin composition A or the resin composition B.
When manufacturing the resin film of 1st Embodiment using the resin composition A or B, as a manufacturing method of a resin film, the process of providing the resin composition A or B on a board | substrate and forming a resin film ( It is preferable to have at least a resin film forming step.
When the resin composition A or B is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, the resin composition A or B is a substrate as a method for producing a resin film. It is preferable to have a process of forming a coating film (coating film forming process) and a process of exposing the coating film (exposure process).
Furthermore, when the resin composition A or B is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, a patterned resin film can be formed. Specifically, the coating film forming step, the step of exposing the coating film in a pattern (pattern exposure step), and the step of developing and removing unexposed portions to form a patterned resin film (developing step) ).
Hereinafter, the manufacturing method of the resin film which has a coating-film formation process, a pattern exposure process, and a image development process as a representative example among the said procedures is explained in full detail.
As will be described in detail later, the procedure itself of the resin film forming step is the same as the procedure of the coating film forming step. The exposure process and the pattern exposure process are the same procedure except that the exposure is performed in a pattern in the pattern exposure process.

<Coating film formation process>
In this step, a coating film is formed on the substrate using the resin composition A or B.
The coating film is a film formed by the resin composition A or B. When the resin composition A is used, a coating film having the above-described titanium nitride-containing particles, a binder resin, a filler, and an actinic radiation curable material such as a polymerization initiator and a polymerizable compound is formed. Further, when the resin composition B is used, the activity of the above-described titanium nitride-containing particles, a binder resin, a resin having a polysiloxane structure formed from reactive silicone, and the like, a polymerization initiator, a polymerizable compound, and the like A coating film having a wire curable material is formed.
Examples of the substrate include a transparent substrate made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like. A thin film transistor for driving an organic electroluminescence (organic EL) element may be formed on these transparent substrates.
In addition, a solid-state imaging device substrate in which a solid-state imaging device (light receiving device) such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is provided on the substrate can be used.
As a method for applying the resin composition A or B on the substrate, various methods such as a slit coating method, an ink jet method, a spin coating method, a spray coating method, a casting coating method, a roll coating method, and a screen printing method are used. be able to.
From the point that the film thickness of the coating film can be obtained uniformly, the spin coating method and the spray coating method are preferable. In the case where the substrate surface is not flat, the spray coating method and the ink jet method are preferable because the film thickness is uniform.

In addition, you may heat-process (prebaking) with respect to the coating film formed on the board | substrate, and the temperature in this case has preferable 150 degrees C or less, 120 degrees C or less is more preferable, 100 degrees C or less is still more preferable.
The pre-bake time is preferably 10 to 300 seconds, and more preferably 40 to 250 seconds. Heating can be performed with a hot plate, oven, or the like.

  As described above, when the resin composition A or B does not contain an actinic radiation curable material, a resin film is formed on the substrate by performing the procedure described in the coating film forming step. be able to.

<Pattern exposure process>
This step is a step of exposing the coating film obtained in the coating film forming step in a pattern. As an exposure method, for example, pattern exposure can be performed by exposing through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, more preferably 80~500mJ / cm ^2.
In the exposed portion, the actinic radiation curable material is cured.

<Development process>
This step is a step of developing and removing an unexposed portion to form a patterned resin film. The development removal of the unexposed portion can be performed using a developer. Thereby, the coating film of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part (resin film) remains.
The developer is preferably an organic alkali developer that does not damage the underlying solid-state imaging device and circuit.
As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An aqueous solution in which these alkali agents are dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.005 to 6% by mass, particularly preferably 0.01 to 5% by mass.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metasuccinate is preferable.
Further, a surfactant may be used for the developer. As an example of the surfactant, a nonionic surfactant is preferable.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash | clean (rinse) with a pure water after image development.

[Layer structure of resin film]
The resin film may be composed of one layer of a pigment layer containing titanium nitride-containing particles, or may have a plurality of pigment layers. From the viewpoint of further improving the low reflectivity and moisture resistance, it is preferable that the pigment layer X1 and the pigment layer X2 each containing titanium nitride-containing particles are laminated adjacently. At this time, the concentration of the titanium nitride-containing particles contained in the pigment layer X2 is smaller than the concentration of the titanium nitride-containing particles contained in the pigment layer X1, and the surface roughness of the surface on the pigment layer X2 side of the resin film Ra is preferably 100 to 2000 cm. That is, the pigment layer (pigment layer X2) having the smallest concentration of titanium nitride-containing particles is located on the outermost surface side (layer position farthest from the substrate) of the resin film, so It can exhibit excellent light scattering with respect to light and can be more excellent in low reflectivity.
Here, “the concentration of the titanium nitride-containing particles contained in the pigment layer X1” and “the concentration of the titanium nitride-containing particles contained in the pigment layer X2” are titanium nitride relative to the total solid content of each pigment layer. This corresponds to the content of the contained particles.

  When the resin film has a two-layer structure of the pigment layer X1 and the pigment layer X2, the concentration of the titanium nitride-containing particles in the pigment layer X1 having a high concentration is preferably 10 to 65% by mass. More preferably, it is mass%. On the other hand, the concentration of the titanium nitride-containing particles in the pigment layer X2 having a low concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 40% by mass. Further, (concentration of titanium nitride-containing particles contained in pigment layer X1) − (concentration of titanium nitride-containing particles contained in pigment layer X2) is preferably 5 to 40% by mass.

[Second embodiment: a resin film in which at least one of fluorine atoms and silicon atoms is unevenly distributed on the surface]
The resin film according to the second embodiment is adjacent to a pigment layer (hereinafter simply referred to as “pigment layer”) including a titanium nitride-containing particle containing one or more metal atoms other than the above-described titanium atoms. And a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom (hereinafter simply referred to as “surface layer”).
The thickness in particular of a resin film is not restrict | limited, 0.2-25 micrometers is preferable and 1.0-10 micrometers is more preferable. The above thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the resin film and arithmetically averaging them.
The thickness of the surface layer in the resin layer is preferably 0.050 to 0.200 μm.

  The resin film contains at least a titanium nitride-containing particle containing at least one metal atom other than the titanium atom described above, a binder resin, and a compound containing at least one of a fluorine atom and a silicon atom ( Hereinafter, it can be formed by preparing “resin composition C”) and applying it onto a substrate.

As described above, the resin composition C uses a compound containing at least one of a fluorine atom and a silicon atom described below (preferably a resin containing at least one of a fluorine atom and a silicon atom). Indicates surface free energy. Therefore, for example, in a coating film formed by applying the resin composition C on a substrate, the compound is likely to be concentrated in the vicinity of the coating film surface on the side opposite to the substrate. This surface uneven distribution is particularly prominent when a resin containing at least one of a fluorine atom and a silicon atom is used as the compound. As a result, the resulting coating film has a pigment layer (lower layer) containing titanium nitride-containing particles that are black pigments, and a surface layer (including a compound containing at least one of fluorine atoms and silicon atoms). It has a two-layer structure with the upper layer). When such a two-layer structure is formed, the light reflected on the surface of the surface layer and the light reflected on the interface between the surface layer and the pigment layer are canceled out by interference, and low reflectivity is achieved. Can do.
Further, the resin film includes titanium nitride-containing particles as a black pigment in the pigment layer, and the titanium nitride-containing particles and the compound containing at least one of fluorine atoms and silicon atoms synergize. It has been confirmed that it exhibits excellent moisture resistance.
Resins such as (meth) acrylic polymers contain a small amount of radical initiators and unreacted monomers. In a humid heat environment, the polymer is cleaved by heat, oxygen, and moisture, and the chain caused by radicals generated at the time of cleaving. Cause degradation of haze and transparency due to yellowing of the resin due to mechanical decomposition (see paragraph [0017] of JP 2011-65146 A).
A compound containing at least one of a hydrophobic fluorine atom and a silicon atom is unevenly distributed on the surface, thereby preventing moisture from being mixed into the film and preventing the resin from deteriorating.
Further, although the mechanism is not clear, it is considered that even if there is moisture mixed in the film, titanium nitride-containing particles containing one or more metal atoms other than titanium atoms supplement the generated radicals.

Moreover, the said resin composition C can also be used as the photosensitive resin composition which has exposure and developability. In this case, a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition C. Furthermore, a binder resin, a polymerizable compound, a dispersion resin, or the like may be used as the alkali-soluble material.
Hereinafter, various materials and manufacturing methods of the resin composition C will be described.

[Resin composition C]
<Compound containing at least one of fluorine atom and silicon atom>
Resin composition C contains a compound containing at least one of a fluorine atom and a silicon atom.
The compound containing at least one of a fluorine atom and a silicon atom (hereinafter also referred to as “specific compound”) is not particularly limited, and may have at least one of a fluorine atom and a silicon atom, and a curable functional group. preferable. In addition, it is preferable that a specific compound has a fluorine atom from a viewpoint that the reflectance of a resin film is lower, the pattern linearity of a resin film is more excellent, and the crack of a resin film does not produce more easily.
The specific compound may be a monomer, a multimer, or a polymer. When the specific compound is a polymer, it is preferably a (meth) acrylate polymer, more preferably a (meth) acrylate polymer having a fluorine atom.
One preferred embodiment of the specific compound is a compound having no benzene ring structure, and more preferably a compound having a fluorine atom and not having a benzene ring structure.
In addition, the silane coupling agent mentioned above is not contained in a specific compound.

When the specific compound contains a fluorine atom, the specific compound is at least one selected from the group consisting of an alkylene group substituted with a fluorine atom, an alkyl group substituted with a fluorine atom, and an aryl group substituted with a fluorine atom. It is preferable to have one.
The alkylene group substituted with a fluorine atom is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
The alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
The number of carbon atoms in the alkylene group substituted with a fluorine atom and the alkyl group substituted with a fluorine atom is preferably 1-20, more preferably 1-10, and even more preferably 1-5. preferable.
In the aryl group substituted with a fluorine atom, the aryl group is preferably directly substituted with a fluorine atom or substituted with a trifluoromethyl group.
The alkylene group substituted with a fluorine atom, the alkyl group substituted with a fluorine atom, and the aryl group substituted with a fluorine atom may further have a substituent other than the fluorine atom.
As examples of the alkyl group substituted with a fluorine atom and the aryl group substituted with a fluorine atom, for example, paragraphs 0266 to 0272 of JP2011-100089A can be referred to, and the contents thereof are described in this specification. Incorporated.

Among these, from the viewpoint of lower reflectivity of the resin film, better pattern linearity of the resin film, and less likely to cause chipping of the resin film, the specific compound includes an alkylene group substituted with a fluorine atom and an oxygen atom. And a group X (group represented by the formula (X) (repeating unit)) linked to each other, and more preferably a perfluoroalkylene ether group.
Formula _{(X) - (L A -O} ) -
L _A represents an alkylene group substituted with a fluorine atom. In addition, it is preferable that it is 1-20, as for carbon number in an alkylene group, it is more preferable that it is 1-10, and it is still more preferable that it is 1-5. The alkylene group substituted with the fluorine atom may contain an oxygen atom.
The alkylene group substituted with a fluorine atom may be linear or branched.
The “perfluoroalkylene ether group” intends that L _A is a perfluoroalkylene group. The “perfluoroalkylene group” intends a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms.
The group represented by formula (X) (repeating unit) may be linked repeatedly, and the number of repeating units is not particularly limited, and is preferably 1 to 50 in terms of more excellent effects of the present invention. ~ 20 is more preferred.
That is, the group represented by the formula (X-1) is preferable.
Formula _{(X-1) - (L} A -O) r -
Wherein (X-1), L _A is as defined above, r is represents the number of repeating units, the preferred range is as described above.
The plurality of _{- (L A -O) - L} A medium may be different even in the same.

When the specific compound contains a silicon atom, an alkylsilyl group, an arylsilyl group, or the following partial structure (S) (* represents a bonding site with another atom) is preferable.
Partial structure (S)

As for carbon number of the alkyl chain which an alkyl silyl group has, 1-20 are preferable in total, 1-10 are more preferable, and 1-6 are still more preferable. Alkylsilyl groups and trialkylsilyl groups are preferred.
Examples of the aryl group in the arylsilyl group include a phenyl group.
When the partial structure (S) is included, a cyclic structure may be formed including the partial structure (S). The partial structure (S) preferably employed in the present invention is preferably —Si (R) ₂ —O—Si (R) ₂ — (R is an alkyl group having 1 to 3 carbon atoms) or an alkoxysilyl group. As an example of the structure including the partial structure (S), for example, paragraphs 0277 to 0279 of JP 2011-100089 A can be referred to, and the contents thereof are incorporated in this specification.

  The specific compound should just have at least 1 or more of a fluorine atom and a silicon atom, and may have 2 or more. Moreover, the specific compound may have a combination of a fluorine atom and a silicon atom.

The specific compound preferably has one or more curable functional groups, and may have two or more curable functional groups. Only one type of curable functional group may be used, or two or more types may be used. The curable functional group may be a thermosetting functional group or a photocurable functional group.
The curable functional group is (meth) acryloyloxy group, epoxy group, oxetanyl group, isocyanate group, hydroxyl group, amino group, carboxyl group, thiol group, alkoxysilyl group, methylol group, vinyl group, (meth) acrylamide group It is preferably at least one selected from the group consisting of styryl group and maleimide group, and at least one selected from the group consisting of (meth) acryloyloxy group, epoxy group and oxetanyl group Is more preferable.
In addition, when an ethylenically unsaturated group is contained as a curable functional group, the amount of the ethylenically unsaturated group in the specific compound is preferably 0.001 to 10.0 mmol / g, and 0.01 to 5.00 mmol / g. Is more preferable.

When the specific compound is a monomer, the number of one or more groups selected from a fluorine atom and a silicon atom in one molecule is preferably 1-20, and more preferably 3-15.
In addition, the number of curable functional groups in one molecule is not particularly limited, and is preferably 2 or more and more preferably 4 or more in terms of more excellent effects of the present invention. The upper limit is not particularly limited and is often 10 or less, more often 6 or less.

  When the specific compound is a polymer, the structure preferably includes a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group, and is represented by the following formula (B1). And a repeating unit represented by the following formula (B2) and a repeating unit represented by the formula (B3).

In formulas (B1) to (B3), R ^{1 to} R ¹¹ each independently represents a hydrogen atom, an alkyl group, or a halogen atom. L ^{1 to} L ⁴ each independently represents a single bond or a divalent linking group. X ¹ represents a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group, and X ² represents an alkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, an alkylsilyl group, an arylsilyl group, or Represents a group containing the partial structure (S), and X ³ represents a repeating unit represented by the formula (X-1).

In formulas (B1) to (B3), R ^{1 to} R ¹¹ are preferably each independently a hydrogen atom or an alkyl group.
When R < ¹ > -R < ¹¹ > represents an alkyl group, a C1-C3 alkyl group is preferable. When R ^{1 to} R ¹¹ represent a halogen atom, a fluorine atom is preferable.
In formulas (B1) to (B3), when L ^{1 to} L ⁴ represent a divalent linking group, the divalent linking group includes an alkylene group which may be substituted with a halogen atom, and a halogen atom substituted. which may be an arylene ^{group, -NR 12 -, - CONR 12} -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof Is mentioned. Among them, at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms that may be substituted by a halogen atom and an arylene group having 6 to 12 carbon atoms that may be substituted by a halogen atom, or , At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. group is preferred, which consist of a combination of one group, alkylene group which may C2-10 be halogen atoms _{substituted, -CO 2 -, - O -} , - CO -, - CONR 12 -, or A group consisting of a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.

  Specific examples of the repeating unit represented by the formula (B1) include the following, but the present invention is not limited thereto.

Specific examples of the repeating unit represented by the formula (B2) include the following, but the present invention is not limited thereto. In specific examples, X ¹ represents a hydrogen atom, —CH ₃ , —F or —CF _3, and more preferably a hydrogen atom or a methyl group. Me represents a methyl group.

  Specific examples of the repeating unit represented by the formula (B3) include the following, but the present invention is not limited to these. In specific examples, l, m, n, h, j, and k represent an integer of 1 to 100.

The content of the repeating unit represented by the formula (B1) is preferably 5 to 98 mol% and more preferably 30 to 95 mol% with respect to all the repeating units in the specific compound.
The total content of the repeating unit represented by the formula (B2) and the repeating unit represented by the formula (B3) is preferably 1 to 70 mol% with respect to all the repeating units in the specific compound, More preferably, it is 5 to 60 mol%.
In addition, when the repeating unit represented by Formula (B2) is not included and the repeating unit represented by Formula (B3) is included, the content of the repeating unit represented by Formula (B2) is 0 mol%. The content of the repeating unit represented by the formula (B3) is preferably in the above range.

  Moreover, the specific compound may have other repeating units other than the repeating unit represented by the said formula (B1)-(B3). The content of other repeating units is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units in the specific compound.

When the specific compound is a polymer, the weight average molecular weight (Mw: polystyrene conversion) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the specific compound is a polymer, the dispersity (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90. .
The GPC (gel permeation chromatography) method uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID × 15 cm) manufactured by Tosoh Corporation as columns. Based on a method using THF (tetrahydrofuran) as an eluent.

  As a commercial item of a specific compound, for example, as a specific compound having a fluorine atom, MegaFac RS-72-K, MegaFac RS-75, MegaFac RS-76-E, MegaFac RS-76- manufactured by DIC NS, Megafax RS-77, BYK-UV 3500 manufactured by BYK, BYK-UV 3530, BYK-UV3570 manufactured by BYK, TEGO Rad 2010, TEGO Rad 2011, TEGO Rad 2100 manufactured by EVONIK TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, TEGO Rad 2600, TEGO Rad 2650, TEGO Rad 2700, and the like can be used.

The specific compound is preferably capable of forming a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm with the specific compound alone. That is, it is preferable that the refractive index at a wavelength of 550 nm of a film formed only from the specific compound is 1.1 to 1.5.
The preferred range of the refractive index is preferably 1.2 to 1.5, more preferably 1.3 to 1.5, from the viewpoint of low reflectivity of the resin film.

  Moreover, the reactive silicone contained in the resin composition B can also be used as a compound containing at least one of a fluorine atom and a silicon atom. The preferred embodiment of the reactive silicone is as described above.

The content of the specific compound in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 1 to 15% by mass with respect to the total solid content in the resin composition. More preferred is 1 to 10% by mass.
The composition may contain one specific compound or two or more specific compounds. When a composition contains 2 or more types of specific compounds, the total should just be in the said range.

<Other materials>
The material in the resin composition C is the same except that the filler in the resin composition A is a compound containing at least one of a fluorine atom and a silicon atom, and the same applies to preferred embodiments.

[Method for Preparing Resin Composition C]
Resin composition C can be prepared by mixing the aforementioned components. The method for preparing the resin composition C is also the same as that of the resin compositions A and B described above, and the preferred embodiment is also the same.

The resin composition of the present invention preferably does not contain impurities such as metals other than those contained in titanium nitride-containing particles, metal salts containing halogens, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
Examples of the method for removing impurities such as metals from various materials include filtration using a filter or purification steps by distillation (particularly thin film distillation, molecular distillation, etc.). The purification process by distillation is, for example, “<Factory Operation Series> Augmentation / Distillation, Issued July 31, 1992, Chemical Industry Co., Ltd.” or “Chemical Engineering Handbook, Issued September 30, 2004, Asakura Shoten, pages 95-102” Page ". The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The filter material is preferably a polytetrafluoroethylene, polyethylene or nylon filter. The filter may be a composite material combining these materials and ion exchange media. You may use the filter previously wash | cleaned with the organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
Moreover, as a method of reducing impurities such as metals contained in various materials, a raw material having a low metal content is selected as a raw material constituting each material, filter filtration is performed on the raw materials constituting various materials, or Examples of the method include distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, and an organic adsorbent such as activated carbon can be used.

[Production method of resin film]
Next, a method for manufacturing a resin film will be described.
The resin film of the second embodiment is preferably manufactured using the resin composition C. In addition, after forming a pigment layer, the method of forming a surface layer using the compound containing at least one of a fluorine atom and a silicon atom on the upper surface of a pigment layer is not prevented.
When manufacturing the resin film of 2nd Embodiment using the resin composition C, the resin composition C is provided on a board | substrate, and the process (resin layer formation) which forms the resin film which consists of a pigment layer and a surface layer It is preferable to have at least a step.
When the resin composition C is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, as a method for producing a resin film, the resin composition C is applied on a substrate. It is preferable to have a step of forming a coating film (coating layer forming step) and a step of exposing the coating film (exposure step).
Furthermore, when the resin composition C is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, a patterned resin film can be formed. Specifically, the coating film forming step, the step of exposing the coating film in a pattern (pattern exposure step), and the step of developing and removing unexposed portions to form a patterned resin film (developing step) ).
The specific procedure of each step is the same as the procedure of each step in the first embodiment, and the preferred mode is also the same.

[Third embodiment: a resin film in which Ra is 100 to 2000 、 and a compound containing at least one of a fluorine atom and a silicon atom is unevenly distributed on the surface]
Furthermore, as a modification of the first embodiment (third embodiment), the resin film of the first embodiment is made of titanium nitride-containing particles containing at least one metal atom other than the above-described titanium atoms. The surface of the surface layer that is the outermost surface of the resin film, and has a two-layer structure including a pigment layer that includes and a surface layer that includes a compound containing at least one of a fluorine atom and a silicon atom disposed adjacently on the pigment layer The roughness Ra may be 100 to 2000 mm.
When the resin film has the above-described configuration, it exhibits excellent moisture resistance and also exhibits excellent low reflectivity.

When setting it as the said aspect, what is necessary is just to mix | blend the compound which contains at least one of a fluorine atom and a silicon atom with the resin composition A mentioned above.
In addition, the compound containing at least one of a fluorine atom and a silicon atom is the same as that of what was mentioned above with the resin composition C, and the same also about a suitable aspect (a compounding quantity is included).
Moreover, the manufacturing method of the resin film of 3rd Embodiment is the same as that of 1st Embodiment, The suitable aspect is also the same.

[Fourth Embodiment: Resin Film Laminated with Pigment Layers with Different Optical Densities]
The resin film in the fourth embodiment is a resin film in which a pigment layer Y1 and a pigment layer Y2 each containing titanium nitride-containing particles containing at least one metal atom other than the above-described titanium atom are laminated adjacently. Yes, the concentration of titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 is different from each other.
Here, “the concentration of the titanium nitride-containing particles contained in the pigment layer Y1” and “the concentration of the titanium nitride-containing particles contained in the pigment layer Y2” are titanium nitride relative to the total solid content of each pigment layer. This corresponds to the content of the contained particles.

The method for producing the resin film in the fourth embodiment is not particularly limited, and the pigment layer is formed on the substrate using a resin composition for forming the pigment layer Y1 (hereinafter also referred to as “resin composition D”). The pigment layer Y2 is formed on the pigment layer Y1 using a step of forming Y1 (pigment layer Y1 formation step) and a resin composition (hereinafter also referred to as “resin composition E”) that forms the pigment layer Y2. Step (pigment layer Y2 forming step).
The concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other, and either the pigment layer Y1 or the pigment layer Y2 is a pigment layer having a smaller concentration of titanium nitride-containing particles. When such a two-layer structure is formed, low reflectivity is exhibited with respect to light incident from the pigment layer side where the concentration of titanium nitride-containing particles is smaller. For example, when the pigment layer Y2 is a pigment layer having a smaller concentration of titanium nitride-containing particles and light is incident from the pigment layer Y2 side, the light reflected from the surface of the pigment layer Y1, the pigment layer Y1 and the pigment layer Y2 The light reflected at the interface with the light is canceled out by the interference, so that low reflectivity can be achieved. On the other hand, the same effect can be obtained when the pigment layer Y1 on the substrate side is a pigment layer having a smaller concentration of titanium nitride-containing particles and light is incident from the pigment layer Y1 side.

  The concentration of titanium nitride-containing particles in the pigment layer having a high concentration is preferably 10 to 65% by mass, and more preferably 30 to 55% by mass. The concentration of titanium nitride-containing particles in the pigment layer at a low concentration is preferably 1 to 45% by mass, and more preferably 1 to 40% by mass. The absolute value of (concentration of titanium nitride-containing particles contained in pigment layer Y1) − (concentration of titanium nitride-containing particles contained in pigment layer Y2) is preferably 5 to 40% by mass.

  The film thicknesses of the pigment layers Y1 and Y2 are each preferably 0.3 to 1.2 μm, and more preferably 0.4 to 1.0 μm. Moreover, it is preferable that it is 0.5-2.0 micrometers, and, as for the whole film thickness which match | combined both layers, it is more preferable that it is 1.0-1.5 micrometers. The above-mentioned thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the film and arithmetically averaging them.

  The optical density (optical density, hereinafter referred to as “OD value”) of the resin film is preferably 3 or more, and more preferably 4 to 5 in the visible light region having a wavelength of 380 to 700 nm. If the overall OD value is less than 3, part of the light from the backlight is transmitted, causing a reduction in contrast. On the other hand, when it exceeds 5, the addition amount of the black pigment increases and the reflectance tends to be relatively high.

  The OD value of the pigment layer at which the concentration of titanium nitride-containing particles is low is preferably 0.5 to 2.0, and more preferably 0.8 to 1.5. On the other hand, the OD value of the pigment layer in which the concentration of the titanium nitride-containing particles is high is preferably 1.0 to 5.0, and more preferably 2.0 to 3.5.

Examples of the materials included in the resin compositions D and E include the materials included in the resin composition A of the first embodiment, and the preferred ranges are also the same.
In the case where the resin compositions D and E are curable compositions containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, the method further comprises a step of exposing the pigment layer (exposure step). May be. When the exposure step is a step of exposing the pigment layer in a pattern, a step (development step) of forming a colored pattern by developing and removing unexposed portions after the exposure step may be further provided.
The preferred embodiments of the coating film forming step, the exposure step, and the developing step are the same as the pigment layer forming step, the exposing step, and the developing step in the first embodiment, respectively, and the preferred embodiments are also the same.

[Color filter, light shielding film]
The resin film of the first to fourth embodiments of the present invention can be preferably used as a color filter or a light shielding film. In particular, a film obtained by curing the resin film by exposure can be preferably used. In addition, as will be described later, the light shielding film is appropriately disposed on each member, and may be disposed in a frame shape, for example.

  The color filter can be suitably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. It is. For example, the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

  The color filter can be preferably used for an organic EL element. As the organic EL element, a white organic EL element is preferable. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate. The lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region. The organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked. For example, the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer. The organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light. In that case, the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, a spectrum excellent in color reproducibility can be obtained, and a clearer image or image can be displayed.

The light shielding film is formed and used on various members in the image display device or the sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a back surface of a solid-state imaging device, etc.). it can.
Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
The thickness of the light shielding film is not particularly limited and is preferably 0.2 to 25 μm, more preferably 1.0 to 10 μm. The thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light shielding film and arithmetically averaging them.
The reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High Technology.

[Solid-state image sensor]
The solid-state imaging device of the present invention includes the resin film (color filter, light shielding film, etc.) of the first to fourth embodiments described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as the configuration includes the resin film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

On the substrate, there are a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and the photodiodes receive light on the photodiodes and transfer electrodes. A light-shielding film having an opening only in the part, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, and a color filter on the device protective film It is the composition which has.
Further, it may be a configuration having a light collecting means (for example, a microlens) on the device protective layer and under the color filter (on the side close to the substrate), a structure having the light collecting means on the color filter, or the like. . In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image sensor having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

(Image display device)
The cured film (color filter, light-shielding film, etc.) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.

  For the definition of the display device or details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is not limited to a liquid crystal display device such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and an STN (Super-Twist). Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), R-OCB (Reflective Optics), etc.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device with high resolution and excellent long-term durability. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device of the present invention may be composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlights, in addition to SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005 pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. It is described in.

  Moreover, the cured film obtained by curing the curable composition is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an OA (Office Automation) device such as a printer multifunction device or a scanner; , Barcode readers, automated teller machines (ATMs), high-speed cameras, or industrial devices such as personal authentication using facial image authentication; in-vehicle camera devices; endoscopes, capsule endoscopes, catheters, etc. Medical camera equipment; space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather / ocean observation cameras, land resource exploration cameras, or exploration cameras for space astronomy and deep space targets Shielding member and shielding layer for optical filter or module It can be used for anti-reflective member or anti-reflective layer.

Moreover, the cured film obtained by hardening | curing a curable composition can also be used for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). It does not specifically limit, In addition to the optical filter or optical film used for micro LED or micro OLED, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
Examples of the micro LED or the micro OLED include those disclosed in JP-T-2015-500562 or JP-A-2014-533890.

Moreover, the cured film obtained by hardening | curing a curable composition can be used also for uses, such as a quantum dot display. It does not specifically limit, In addition to the optical filter or optical film used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
Examples of quantum dot displays include those of U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, or U.S. Patent Application Publication No. 2014/0035960. Can be mentioned.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Unless otherwise specified, “part” and “%” are based on mass.

  Hereinafter, each component used in the Examples and Comparative Examples will be described in detail.

(Pigment)
(Black Pigment Pig-1)
A black pigment Pig-1 was produced under the following conditions.
High frequency power 5.5kW
Plasma gas flow rate Argon 5L / min + Nitrogen 5L / min
Spray gas flow rate Nitrogen 20L / min
Powder supply JEOL powder supply equipment TP-99010FDR
Supply gas Nitrogen 15L / min
Supply amount 15g / min
Powder Ti powder TC-200 made by Toho Titanium
Ag powder Mitsui Kinzoku SPQ03R
Fe powder JIP steel JIP 270M

After the plasma-treated particles are allowed to stand for 24 hours in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 30 ° C., the O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. And allowed to stand at 30 ° C. for 24 hours.

About the obtained titanium nitride containing particle | grains (black pigment Pig-1), content of a titanium (Ti) atom and a metal atom was measured by the ICP emission spectroscopy analysis method.
The content of Ti atoms was 60% by mass, the content of Ag atoms was 15% by mass, and the content of Fe atoms was 1% by mass with respect to the total amount (100% by mass) of the black pigment Pig-1. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
In addition, the content of nitrogen atoms and oxygen atoms is measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and is calculated by an inert gas melting-thermal conductivity method. did. As a result, the nitrogen atom content is 19% by mass with respect to the total amount (100% by mass) of the black pigment Pig-1, and the oxygen atom content is the total amount (100% by mass) of the black pigment Pig-1. It was 5 mass% with respect to.

The black pigment Pig-1 was subjected to an X-ray diffraction test by the following method.
X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min. The diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ = 46 ° was measured.
As a result, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-1 was 42.5 °.

The specific surface area of the black pigment Pig-1 uses a Nippon Bell Co., Ltd. precision fully automatic gas adsorption apparatus ( "BELSORP" 36), after vacuum degassing at 100 ° C., _{N 2} gas liquid nitrogen temperature (77K) The adsorption isotherm in was measured, and this isotherm was determined by the BET method. As a result, the specific surface area of the black pigment Pig-1 obtained by using the BET method was 29 m ² / g.

(Black Pigment Pig-2)
A black pigment Pig-2 was produced under the following conditions.
High frequency power 5.5kW
Plasma gas flow rate Argon 5L / min + Nitrogen 5L / min
Spray gas flow rate Nitrogen 20L / min
Powder supply JEOL powder supply equipment TP-99010FDR
Supply gas Nitrogen 15L / min
Supply amount 15g / min
Powder Ti powder TC-200 made by Toho Titanium
Ag powder Mitsui Kinzoku SPQ03R
Ni powder Toho Titanium

After the plasma-treated particles are allowed to stand for 24 hours in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 30 ° C., the O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. And allowed to stand at 30 ° C. for 24 hours.

About the obtained titanium nitride containing particle | grains (black pigment Pig-2), content of a titanium (Ti) atom and a metal atom was measured by ICP emission spectroscopy analysis.
The content of Ti atoms was 65% by mass, the content of Ag atoms was 8% by mass, and the content of Ni atoms was 2% by mass with respect to the total amount (100% by mass) of the black pigment Pig-2. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
In addition, the content of nitrogen atoms and oxygen atoms is measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and is calculated by an inert gas melting-thermal conductivity method. did. As a result, the content of nitrogen atoms is 20% by mass with respect to the total amount of black pigment Pig-2 (100% by mass), and the content of oxygen atoms is the total amount of black pigment Pig-2 (100% by mass). It was 5 mass% with respect to.

Moreover, about the black pigment Pig-2, the X-ray-diffraction test was done with the following method.
X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min. The diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ = 46 ° was measured.
As a result, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-2 was 42.6 °.

The specific surface area of the black pigment Pig-2 uses a Nippon Bell Co., Ltd. precision fully automatic gas adsorption apparatus ( "BELSORP" 36), after vacuum degassing at 100 ° C., _{N 2} gas liquid nitrogen temperature (77K) The adsorption isotherm in was measured, and this isotherm was determined by the BET method. As a result, the specific surface area of the black pigment Pig-2 determined using the BET method was 33 m ² / g.

(Black Pigment Pig-3)
A black pigment Pig-3 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. V powder refers to vanadium powder.
Powder Ti powder TC-200 made by Toho Titanium
Ag powder Mitsui Kinzoku SPQ03R
V powder made by Taiyo Mining Co., Ltd. VN200

After the plasma-treated particles are allowed to stand in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 100 ° C. for 24 hours, O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. And left at a temperature of 100 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-3) was measured by the same method as that of the black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-3, the content of Ti atoms was 50% by mass, the content of Ag atoms was 20% by mass, and the content of V atoms was 1% by mass. .
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 19% by mass with respect to the total amount (100% by mass) of the black pigment Pig-3, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-3. It was 10 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-3 was 42.8. °.

When the specific surface area of the black pigment Pig-3 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 25 m ² / g.

(Black Pigment Pig-4)
A black pigment Pig-4 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Note that W powder refers to tungsten powder.
Powder Ti powder TC-200 made by Toho Titanium
W powder Nippon New Metal W-H
Fe powder JIP steel JIP 270M

After the plasma-treated particles are allowed to stand for 24 hours under an Ar gas atmosphere at an O ₂ concentration of 50 ppm or less and 200 ° C., the O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. And left at a temperature of 200 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-4) was measured by the same method as that of the black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-4, the content of Ti atoms is 50% by mass, the content of W atoms is 12.99% by mass, and the content of Fe atoms is 0.01% by mass. %Met.
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 20% by mass with respect to the total amount (100% by mass) of the black pigment Pig-4, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-4. It was 17 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the peak diffraction angle 2θ derived from the TiN (200) plane of the black pigment Pig-4 was 43.0. °.

When the specific surface area of the black pigment Pig-4 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 27 m ² / g.

(Black Pigment Pig-5) A black pigment Pig-5 was produced in the same manner as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder TC-200 made by Toho Titanium
Ni powder Toho Titanium
Fe powder JIP steel JIP 270M

After the plasma-treated particles are allowed to stand for 24 hours under an Ar gas atmosphere at an O ₂ concentration of 50 ppm or less and 200 ° C., the O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. And left at a temperature of 200 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-5) was measured by the same method as that of the black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-5, the content of Ti atoms was 52% by mass, the content of Ni atoms was 5% by mass, and the content of Fe atoms was 2% by mass. .
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 20% by mass with respect to the total amount of black pigment Pig-5 (100% by mass), and the content of oxygen atoms is the total amount of black pigment Pig-5 (100% by mass). It was 21 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the peak diffraction angle 2θ derived from the TiN (200) plane of the black pigment Pig-5 was 43.5. °.

When the specific surface area of the black pigment Pig-5 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 34 m ² / g.

(Black Pigment Pig-6)
A black pigment Pig-6 was produced in the same manner as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder TC-200 made by Toho Titanium
Ag powder Mitsui Kinzoku SPQ03R
W powder Nippon New Metal W-H
V powder made by Taiyo Mining Co., Ltd. VN200

After the plasma-treated particles are allowed to stand for 24 hours in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 30 ° C., the O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. And left at a temperature of 30 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-6) was measured by the same method as that for black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-6, the content of Ti atoms is 57% by mass, the content of Ag atoms is 10% by mass, the content of W atoms is 7.9% by mass, The V atom content was 0.01% by mass.
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 18% by mass with respect to the total amount of black pigment Pig-6 (100% by mass), and the content of oxygen atoms is the total amount of black pigment Pig-6 (100% by mass). It was 7 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-6 was 42.7. °.

When the specific surface area of the black pigment Pig-6 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 32 m ² / g.

(Black Pigment Pig-7)
A black pigment Pig-7 was produced in the same manner as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder TC-200 made by Toho Titanium
Ag powder Mitsui Kinzoku SPQ03R
Fe powder JIP steel JIP 270M

After the plasma-treated particles are allowed to stand in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 300 ° C. for 24 hours, O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. And left at a temperature of 300 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-7) was measured by the same method as that of the black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-7, the content of Ti atoms was 50% by mass, the content of Ag atoms was 5% by mass, and the content of Fe atoms was 2% by mass. .
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 20% by mass with respect to the total amount of black pigment Pig-7 (100% by mass), and the content of oxygen atoms is the total amount of black pigment Pig-7 (100% by mass). It was 23 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-7 was 43.7. °.

When the specific surface area of the black pigment Pig-7 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 30 m ² / g.

(Black Pigment Pig-8)
A black pigment Pig-8 was produced in the same manner as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder TC-200 made by Toho Titanium
Ni powder Toho Titanium
V powder made by Taiyo Mining Co., Ltd. VN200

After the plasma-treated particles are allowed to stand in an Ar gas atmosphere under an O ₂ concentration of 50 ppm or less and 300 ° C. for 24 hours, O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. And left at a temperature of 300 ° C. for 24 hours.

The content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-8) was measured by the same method as that for the black pigment Pig-2.
As a result, with respect to the total amount (100% by mass) of the black pigment Pig-8, the Ti atom content was 47% by mass, the Ni atom content was 10% by mass, and the V atom content was 2% by mass. .
Further, the content of nitrogen atoms and oxygen atoms was also measured by the same method as that for the black pigment Pig-2. As a result, the content of nitrogen atoms is 18% by mass with respect to the total amount (100% by mass) of the black pigment Pig-8, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-8. It was 23 mass% with respect to.

  When the diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the black pigment Pig-8 was 43.7. °.

When the specific surface area of the black pigment Pig-8 was determined by the same method as that for the black pigment Pig- ² , the specific surface area was 26 m ² / g.

  The composition, production method and physical properties of the black pigment Pig-1 to black pigment Pig-8 are shown in Table 1 below.

(Preparation method of pigment dispersion A)
Components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion A.
The resin (X-1) described below was synthesized with reference to the description in JP2013-249417A. The weight average molecular weight of the resin (X-1) was 30,000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

-Composition 1-
Black pigment Pig-1: 25 parts by mass A solution of resin (X-1) in 30% by mass of propylene glycol monomethyl ether acetate: 25 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) (solvent): 23 parts by mass (BA) (solvent): 27 parts by mass

The obtained dispersion A was subjected to a dispersion treatment under the following conditions using NPM Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a pigment dispersion A.
(Distribution condition)
・ Bead diameter: φ0.05mm
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 11m / s
・ Amount of liquid mixture for dispersion treatment: 15.0 g
・ Circulating flow rate (pump supply amount): 60 kg / hour
・ Processing liquid temperature: 20-25 ° C
・ Cooling water: tap water 5 ℃
・ Bead mill annular passage internal volume: 2.2L
・ Number of passes: 84 passes

(Preparation method of pigment dispersion B)
A pigment dispersion B was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with Pig-2.

(Preparation method of pigment dispersion C)
A pigment dispersion C was prepared in the same manner as the preparation of the pigment dispersion A except that the black pigment Pig-1 was changed to “13M-T (trade name)” manufactured by Mitsubishi Materials Corporation.
In addition, the pigment particle contained in "13M-T (trade name)" manufactured by Mitsubishi Materials Corporation is titanium oxynitride.

(Preparation method of pigment dispersion D)
A pigment dispersion D was prepared in the same manner as the pigment dispersion A, except that the resin (X-1) was replaced with a resin (X-2) having the following structure.

(Resin (X-2))

  The weight average molecular weight of the resin (X-2) was 25000, the acid value was 53 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 72.

(Preparation method of pigment dispersion E)
A pigment dispersion E was prepared by the same method as that for preparing the pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-3.

(Preparation method of pigment dispersion F)
A pigment dispersion F was prepared by the same method as the above-mentioned pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-4.

(Preparation method of pigment dispersion G)
A pigment dispersion G was prepared by the same method as the above-mentioned pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-5.

(Preparation method of pigment dispersion H)
A pigment dispersion H was prepared in the same manner as the preparation of the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-6.

(Preparation method of pigment dispersion I)
A pigment dispersion I was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-7.

(Preparation method of pigment dispersion J)
A pigment dispersion J was prepared in the same manner as the preparation of the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-8.

(Red pigment dispersion)
Next, a red pigment dispersion was prepared with reference to paragraph <0409> of the literature (International Publication No. 2015/029643).

(Binder resin)
・ P-1: Acrybase FF-187 (Fujikura Kasei Co., Ltd.)
・ P-2: ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

・ P-3:
4,4′-diaminophenyl ether (0.30 molar equivalent), paraphenylenediamine (0.65 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent), γ-butyrolactone 850 g And 850 g of N-methyl-2-pyrrolidone to obtain a mixture, and then 3,3 ′, 4,4′-oxydiphthalcarboxylic dianhydride (0.9975 molar equivalent) was further added to the mixture. Then, the mixture was reacted at 80 ° C. for 3 hours. Maleic anhydride (0.02 molar equivalent) was further added to the obtained reaction product and reacted at 80 ° C. for 1 hour to obtain a polyamic acid (polymer concentration 20% by mass) solution as polymer 3.

・ P-4:
After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Japanese Patent No. 3120476; Example 1), 40 parts by mass of glycidyl methacrylate was added. Then, after reprecipitating with purified water, the solid content is collected by filtration, and the solid content is dried to obtain an acrylic polymer having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g) as polymer 4. A powder was obtained.

・ P-5: Acrybase FF-426 (Fujikura Kasei Co., Ltd.)

(Filler)
Hollow silica: Thruria 5320, particle distribution maximum value: 75 nm, manufactured by JGC Catalysts & Chemicals (20 wt% MIBK (methyl isobutyl ketone) solution)
Silica 1: FF-D-B1, particle distribution maximum value: 300 nm, manufactured by Koshin Chemical Co., Ltd. (72 wt% PGME solution)
Silica 2: FF-B-B1, maximum particle distribution: 30 nm, manufactured by Koshin Chemical Co., Ltd. (60 wt% PGME solution)
Acrylic particles 1: MX-80H3wT, particle distribution maximum: 800 nm, manufactured by Soken Chemical Co., Ltd. (powder)
Acrylic particle 2: MP-300, particle distribution maximum value: 100 nm, manufactured by Soken Chemical Co., Ltd.

(Compound containing at least one of fluorine atom and silicon atom)
・ S-1: Megafuck RS-72-K (manufactured by DIC)
・ S-2: Mega-Fac RS-55 (containing fluorine atom and silicon atom, manufactured by DIC)
S-3: KF-6001 (hydroxyl group-containing silicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
Note that S-1 and S-2 are high molecular compounds each including a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group in the side chain.

(Surfactant)
F-1: Mixture represented by the following structural formula (Mw = 14000)

(solvent)
-PGMEA: Propylene glycol monomethyl ether acetate-PGME: 1-methoxy-2-propanol-High boiling point solvent: Hisolv BDM (diethylene glycol butyl methyl ether, boiling point 212 ° C, manufactured by Toho Chemical Co., Ltd.)

(Polymerization initiator)
・ K-1: Irgacure OXE02 (manufactured by BASF Japan)
-K-2: Compound represented by the following structure-K-3: NCI-831 (manufactured by Adeka Corporation)
・ K-4: Irgacure 369 (manufactured by BASF)
・ K-5: KAYACURE DETX-S (manufactured by Shoji Sangyo Co., Ltd.)

(Polymerizable compound)
M-1: Compound having the following structure (made by Nippon Kayaku Co., Ltd.)

・ M-2: OGSOL EA-0200 (Osaka Gas Chemical Co., Ltd.)
・ M-3: Aronix TO-2349 (Toagosei Co., Ltd.)
Note that M-2 corresponds to a polymerizable compound having a cardo structure and having a 9,9-bisarylfluorene skeleton.

(Silane coupling agent)
・ Epoxysilane: LS-2940 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Production and Evaluation of Resin Film 1]
(1) Preparation of resin composition Each component as shown in Tables 2 and 3 described later was stirred and mixed to prepare a resin composition.
In addition, all the resin compositions of Examples 1-16 were prepared so that the solid content in a composition might be 27.5 mass%. In addition, the resin compositions of Examples 1 to 16 were prepared so that the pigment concentration with respect to the total solid content in the composition was 50% by mass except for Example 7, and 30% by mass for Example 7. Moreover, as for the resin composition of Examples 8-14 and Example 1A, 2A, all are the mass ratio (M / M) of content (M) of the polymeric compound with respect to the total content (B) of dispersion resin and binder resin. B) was prepared to be about 0.9, and Examples 15 and 16 were prepared to be 0.39 and 1.1, respectively.

(Example 1)
In a 200 g container (dispo cup), 14 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 10 g of PGMEA, 21 g of thruria 5320 (20% MIBK solution), 55 g of pigment dispersion A, In this order, the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 2)
Resin composition as in Example 1 except that Surria 5320 (20% MIBK solution) was changed to Silica 1 (FF-D-B1, particle distribution maximum: 300 nm, manufactured by Koshin Chemical Co., Ltd.) (72 wt% PGME solution). A product was prepared. In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

Example 3
A resin composition was prepared in the same manner as in Example 1, except that through rear 5320 (20% MIBK solution) was replaced with acrylic particles 2 (MP-300, particle distribution maximum value: 100 nm, manufactured by Soken Chemical Co., Ltd.). In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

(Example 4)
To a 200 g container (disposable cup), add 6 g of P-1, 35 g of PGMEA, 4 g of KF-6001 (S-3), 55 g of pigment dispersion A in this order, and stir with a stirrer for 30 minutes for resin composition A product was prepared.

(Example 5)
A resin composition was prepared in the same manner as in Example 1 except that the pigment dispersion A was changed to the pigment dispersion B.

(Example 6)
In a 200 g container (dispo cup), add 6 g of P-4, 28 g of PGMEA, 7 g of ethyl lactate, 4 g of KF-6001 (S-3), 55 g of pigment dispersion A in this order, and add 30 minutes with a stirrer. The resin composition was prepared by stirring.

(Comparative Example 1)
A resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the pigment dispersion A was changed to the pigment dispersion C.

(Comparative Example 2)
In a 200 g container (dispo cup), add 24 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 21 g of PGMEA, and 55 g of pigment dispersion A in this order, and stir with a stirrer for 30 minutes. A resin composition was prepared.

(Example 7)
In a 200 g container (dispo cup), 30 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 13 g of NMP (N-methylpyrrolidone), P-3 (20% PGMEA (propylene glycol monomethyl ether) 7 g of acetate) solution), 17 g of thruria 5320 (20% MIBK solution), pigment dispersion A (black pigment: 8.2 g, resin X-1: 2.5 g, PGMEA: 13 g, butyl acetate: 9.1 g) Were added in this order and stirred for 30 minutes with a stirrer to prepare a resin composition.

(Example 8)
In a 200 g container (dispo cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 22 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

Example 9
In a 200 g container (dispo cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 32 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), silica 1 (FF-D-B1, particle distribution maximum: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, silica is 42 wt% in the solid content) 4 g, pigment dispersion A 55 g in this order, add 30 in this order. The resin composition was prepared by stirring for a minute.

(Example 10)
A resin composition was prepared in the same manner as in Example 8, except that through rear 5320 (20% MIBK solution) was replaced with acrylic particles 1 (MX-80H3wT, particle distribution maximum value: 800 nm, manufactured by Soken Chemical Co., Ltd.) (powder). . In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

(Example 11)
In a 200 g container (dispo cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 33 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), KF- 3 g of 6001 (S-3) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 12)
A resin composition was prepared in the same manner as in Example 8 except that the pigment dispersion A was changed to the pigment dispersion B.

(Example 13)
In a 200 g container (disposable cup), 5 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 17 g of PGMEA, 1 g of K-2, Thruria 5320 (20% MIBK) Solution) 13 g, red dispersion (prepared by the method of paragraph <0409> of WO2015 / 029643) 12 g, pigment dispersion A 50 g (black pigment: 12 g, resin X-1: 3.7 g, PGMEA: 21.3 g, butyl acetate: 13 g) were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 14)
In a 200 g container (dispo cup), 5 g of M-1 and 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), P-5 (40% PGMEA (propylene glycol monomethyl ether acetate) solution) 1 g, 34 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), 3 g of KF-6001 and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 15)
In a 200 g container (dispo cup), 3 g of M-1, 9 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 18 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 16)
In a 200 g container (dispo cup), 5 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 24 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

Example 1A
In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 32 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), silica 2 (FF-B-B1, particle distribution maximum: 30 nm, manufactured by Koshin Chemical Co., Ltd., 60 wt% PGME solution, silica is 10 wt% in solid content) 7 g, pigment dispersion A 55 g in this order, 30 The resin composition was prepared by stirring for a minute.

(Example 2A)
In a 200 g container (dispo cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 31.7 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Add 0.3 g of silica 1 (FF-D-B1, particle distribution maximum: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, silica is 42 wt% in the solid content), and 55 g of pigment dispersion A in this order. The resin composition was prepared by stirring with a stirrer for 30 minutes.

(2) Production of Resin Film After spin coating each of the resin compositions of Examples and Comparative Examples on a glass substrate (Corning 1737 [trade name], manufactured by Corning), using a hot plate at 100 ° C. for 2 minutes Heat treatment (pre-baking) was performed. Then, the exposure process (exposure apparatus UX3100-SR (made by USHIO INC.), Exposure amount 1000 mJ / cm < ² >) was implemented with respect to the coating film obtained above through a predetermined mask.
Thereafter, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to produce a substrate with a resin film.

(3) Evaluation <Evaluation of contact angle>
The contact angle was evaluated using the produced substrate with a resin film. Specifically, after dropping one drop of pure water onto the resin film on the substrate, the static contact angle when 5 seconds have elapsed is measured by an automatic contact angle meter (Drop Master 500 [trade name, manufactured by Kyowa Interface Chemical Co., Ltd.] ]) Was automatically measured by the θ / 2 method (measurement temperature: 25 ° C.). The same measurement was performed 5 times, and the average value was defined as a static contact angle with respect to pure water.
The results are shown in Tables 2 and 3.

<Evaluation of reflectance>
The reflectance was evaluated using the produced substrate with a resin film. Specifically, 400-700 nm light was incident on the resin film at an incident angle of 5 ° with respect to the produced substrate with resin film, and the reflectance was measured with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. . In the table, the smaller the value of reflectance, the lower the reflectivity.
The results are shown in Tables 2 and 3.

<Evaluation of surface roughness (arithmetic mean roughness Ra)>
The surface roughness (arithmetic average roughness Ra) was evaluated using the produced substrate with a resin film. Specifically, the surface roughness at a distance of 1 mm of the resin film on the substrate was measured using DektakXT manufactured by BRUKER (resolution: 1 μm / point), and the arithmetic average roughness Ra was determined.
The results are shown in Tables 2 and 3.

<Evaluation of moisture resistance>
Using the produced substrate with a resin film, the moisture resistance was evaluated. Specifically, a high-temperature and high-humidity test for 750 hours was performed under the conditions of a temperature of 85 ° C. and a humidity of 95% using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.).
About the substrate with the resin film before and after the moisture resistance test, the change rate of the reflectance at a wavelength of 400 nm (the spectroscope “UV4100 (trade name)” manufactured by Hitachi High-Technologies Corporation was used for the reflectance measurement) was 3 in absolute value. % Is “D”, the rate of change is 1% to less than 3%, “C”, the rate of change is 0.5% to less than 1%, “B”, the rate of change is Evaluation was made with “A” being less than 0.5%.
The decrease in reflectance due to the moisture resistance test is because a phenomenon such as film surface roughness occurs on the surface, and the decrease in reflectance due to the moisture resistance test is not preferable.
The results are shown in Tables 2 and 3.

<Rubbing test evaluation>
Using the produced substrate with a resin film, a rubbing test was evaluated. Specifically, the rubbing cloth was rubbed 10 times with a force of 1 kgf, and scratches on the resin film surface were visually observed. The same evaluation was performed three times, and the scratches could be confirmed in any of the evaluations, C was the one in which the scratches were confirmed on any one of the three evaluations, and the scratches were observed in any of the evaluations. A that could not be confirmed was designated as A.
The results are shown in Tables 2 and 3.

  In Example 7, the contact angle was 110 ° C., the reflectance was 2% (the reflectance at 400 nm), and the surface roughness was 300 mm. The moisture resistance of Example 7 was “B”, and the rubbing test was “A”.

From the above results, a resin film containing titanium nitride-containing particles containing metal atoms other than titanium atoms and a binder resin, and having a surface roughness (arithmetic average roughness Ra) of 100 to 2000 mm, It was confirmed that it was excellent in low reflectivity and also in moisture resistance.
In particular, when hollow silica was used as the filler (Examples 1, 5, 7, 8, 12, 13, 15, 16), it was confirmed that the material was more excellent in low reflectivity.
Further, from the comparison between Example 1 and Example 5, when titanium nitride-containing particles containing metal atoms other than titanium atoms were used, particles containing silver and iron as metal atoms were used due to moisture resistance. It was confirmed to be excellent.
Further, Example 8 (M / B: about 0.9) in which the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin is different, respectively. Comparing Example 15 (M / B: 0.39) and Example 16 (M / B: 1.1), Example 8 and Example in which M / B is in the range of 0.45 to 1.5 In 16, it was confirmed that the abrasion resistance was superior.

  In Example 16, the total amount of the binder resin and the polymerizable compound was not changed, and the photosensitive resin was similarly prepared except that the amount of the binder resin and the polymerizable compound was adjusted so that M / B was 1.6. A composition was prepared. When the same evaluation as in Example 16 was performed, the same result as in Example 16 was obtained except that the result of the rubbing test was “B”.

  Moreover, when Example 9 and 1A were contrasted, it was confirmed that Example 1A in which the maximum value in the maximum distribution of the added filler is 30 nm is low in moisture resistance. Further, when Examples 9 and 10 were compared, in Example 10 in which the maximum value in the maximum distribution of the added filler was 800 nm, the result of the rubbing test was low.

  Moreover, when Example 9 and Example 2A were contrasted, in Example 2A whose filler content is less than 1.0 mass%, moisture resistance became low.

  On the other hand, since the resin film of Comparative Example 1 did not contain titanium nitride-containing particles containing metal atoms other than titanium atoms, the moisture resistance was lower than that of the resin film of Examples. As described above, trace amounts of radical initiators and unreacted monomers are present in (meth) acrylic polymer-based resin films, and these generate radicals by heat, oxygen, and moisture in a humid heat environment. In addition, the polymer may be cleaved and chain decomposition may occur due to radicals generated during the cleaving. The resin film of the example contains titanium nitride-containing particles containing metal atoms other than titanium atoms, and radicals generated in the film are trapped by the metal atoms, so that the film is hardly deteriorated. Presumably excellent in moisture resistance. On the other hand, the resin film of Comparative Example 1 was surface-affected by radicals, resulting in poor moisture resistance.

Moreover, since the resin film of Comparative Example 2 did not have a predetermined uneven structure on the surface, neither the low reflectivity nor the moisture resistance satisfied a desired level.
In addition, it is assumed that the filler (particularly silica particles) contained as an unevenness forming component is unevenly distributed on the surface of the resin film and has a function of suppressing contact between the titanium nitride-containing particles and moisture. ing. In Comparative Example 2, the fact that this filler was not included is considered to reduce the moisture resistance.

  From the comparison between Comparative Example 1 and Comparative Example 2 and the Examples, it is clear that the resin films of the Examples have significantly improved low reflectivity and moisture resistance.

[Production and Evaluation of Resin Film 2]
(1) Preparation of resin composition Each component as shown in Tables 4 and 5 described below was mixed to prepare resin compositions (Examples 17 to 22, Examples 1B to 3B, Comparative Examples 2 and 3). In addition, all the resin compositions of Examples 17-22 were prepared so that the solid content in the composition was 27.5% by mass and the pigment concentration with respect to the total solid content in the composition was 50% by mass. In addition, the resin compositions of Examples 20 to 22 had a mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin of about 0.9. It was prepared as follows. Further, the resin compositions of Examples 1B and 2B in Table 5 have the same composition as Example 20, except that (M / B) is 0.37 and 1.2, respectively.

  Moreover, each component as shown in Table 6 mentioned later was mixed, and the resin composition (Example 1C-6C) was prepared. The compositions of Examples 1C to 6C are the same as those of Example 20 except that the dispersion liquid type is different.

(Example 17)
In a 200 g container (dispo cup), 20 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 20 g of PGMEA, MegaFac RS-72-K (S-1) (30 wt% PGMEA solution) 5 g and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 18)
Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 5 g, Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 1.7 g and Megafuck RS-55 (S -2) (100 wt% solution) The resin composition was prepared similarly to Example 17 except having replaced with 1g. In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

(Example 19)
Resin composition as in Example 17 except that 20 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution) was replaced with 40 g of P-3 (20% PGMEA (propylene glycol monomethyl ether acetate) solution). Was prepared. In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

(Example 20)
In a 200 g container (dispo cup), 5 g of M-1, 4 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 29 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Mega Fuck 6 g of RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 21)
Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) is replaced with Megafuck RS-55 (S-2) (100 wt% solution), and the polymerization initiator is Irgacure OXE02 (manufactured by BASF Japan). A resin composition was prepared in the same manner as in Example 20 except that K-2 was used. In addition, it was set as the desired solid content density | concentration by adjusting PGMEA.

(Example 22)
A resin composition was prepared in the same manner as in Example 20 except that 5 g of the polymerizable compound M-1 was changed to 3 g of the polymerizable compound M-1 and 2 g of M-2.

(Comparative Example 2)
Comparative Example 2 used the same composition as Comparative Example 2 described in Table 2 above.

(Comparative Example 3)
A resin composition of Comparative Example 3 was prepared in the same manner as in Example 17 except that the pigment dispersion A was changed to the pigment dispersion C.

(Example 1B)
In a 200 g container (dispo cup), 3 g of M-1, 10 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 25 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Mega Fuck RS-72-K (S-1) (30 wt% PGMEA solution) 6 g, pigment dispersion A 55 g were added in this order, and stirred with a stirrer for 30 minutes to prepare a resin composition (M / B = 0.37). ).

(Example 2B)
In a 200 g container (dispo cup), 6 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 30 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Mega Fuck 6 g of RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition (M / B = 1. 2).

(Example 3B)
A resin composition of Example 3B was prepared in the same manner as in Example 20 except that the dispersion A was changed to the dispersion B.

(Example 1C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion E.

(Example 2C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion F.

(Example 3C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion G.

(Example 4C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion H.

(Example 5C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion I.

(Example 6C)
A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion J.

(2) Production of Resin Film After spin coating each of the resin compositions of Examples and Comparative Examples on a glass substrate (Corning 1737 [trade name], manufactured by Corning), using a hot plate at 100 ° C. for 2 minutes Heat treatment (pre-baking) was performed. Then, the exposure process (exposure apparatus UX3100-SR (made by USHIO INC.), Exposure amount 1000 mJ / cm < ² >) was implemented with respect to the coating film obtained above through a predetermined mask.
Thereafter, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to produce a substrate with a resin film.

(3) Evaluation Using the produced substrate with a resin film, various evaluations on the contact angle, the reflectance, the moisture resistance, and the rubbing test were performed on the resin film 2 in the same manner as the resin film 1. The results are shown in Tables 4, 5, and 6.

  Each of the resin films of the above-described embodiments has a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom adjacent to each other on a substrate. It was confirmed that it was excellent in low reflectivity and also in moisture resistance.

  Further, Example 20 (M / B: about 0.9) in which the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin is different, respectively. Comparing Example 1B (M / B: 0.37) and Example 2B (M / B: 1.2), Example 20 and Example in which M / B is in the range of 0.45 to 1.5 In 2B, more excellent abrasion resistance was confirmed.

In Example 2B, the total amount of the binder resin and the polymerizable compound was not changed, and the photosensitive resin was similarly prepared except that the amount of the binder resin and the polymerizable compound was adjusted so that M / B was 1.6. A composition was prepared. When the same evaluation as in Example 2B was performed, the same result as in Example 2B was obtained except that the result of the rubbing test was B.
Further, from comparison between Example 20 and Example 3B, when particles containing silver and iron as metal atoms were used as titanium nitride-containing particles containing metal atoms other than titanium atoms, moisture resistance It was confirmed to be excellent.

In the resin film of Comparative Example 2, since a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom was not formed, neither the low reflectivity nor the moisture resistance satisfied a desired level.
On the other hand, the resin film of Comparative Example 3 also had a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom adjacent to each other on the substrate. Since the nitride-containing particles did not contain metal atoms other than titanium atoms, the moisture resistance was poor.
Furthermore, it is clear from the comparison between the comparative example 2 and the comparative example 3 and the example that the resin film of the example significantly improves the low reflectivity and the moisture resistance.

Also in Examples 1C to 6C, good low reflectivity and moisture resistance were obtained as in Example 20.
Moreover, although it turned out that the optical density of Example 3C falls a little and optical density falls further in Example 5C and Example 6C, there was no problem practically.

[Production and Evaluation of Resin Film 3]
(1) Preparation of Resin Composition Each component as shown in Tables 7 and 8 described below is mixed to prepare resin compositions (Examples 23 to 37, Examples 1D and 2D, Comparative Examples 4, 5, and 6). did. In addition, as for the resin composition of Examples 23-37 and Comparative Examples 4, 5, and 6, all have a solid content in the composition of 27.5% by mass, and the total content of dispersed resin and binder resin (B ) And the mass ratio (M / B) of the polymerizable compound content (M) to about 0.9.
Moreover, the resin composition of Examples 23-37 made the pigment concentration with respect to the total solid in a composition 50 mass% except the resin composition of Examples 24 and 27. About Example 24 and 27, it prepared so that the pigment concentration with respect to the total solid in a composition might be 40 mass%.

  The resin film 3 corresponds to a patterned resin film obtained by exposing and developing the resin film 1 or the resin film 2 described above.

(Example 23)
In a 200 g container (dispo cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 21 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 24)
A resin composition was prepared in the same manner as in Example 23 except that the polymerization initiator K-1 was changed to the polymerization initiator K-2.

(Example 25)
A resin composition was prepared in the same manner as in Example 23 except that the polymerization initiator K-1 was changed to the polymerization initiator K-3.

(Example 26)
In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 16 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 20.7 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 0.3 g of LS-2940, and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes. A composition was prepared.

(Example 27)
A resin composition was prepared in the same manner as in Example 23 except that the polymerizable compound M-1 was changed to the polymerizable compound M-2.

(Example 28)
In a 200 g container (dispo cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, 2 g of Highsolve BDM, Irgacure OXE02 (manufactured by BASF Japan) 1 g, 21 g of thruria 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition. .

(Example 29)
A resin composition was prepared in the same manner as in Example 23 except that 1 g of the polymerization initiator K-1 was changed to 0.8 g of the polymerization initiator K-4 and 0.2 g of K-5.

(Example 30)
Resin in the same manner as in Example 23 except that the polymerization initiator K-1 was changed to the polymerization initiator K-3, and the polymerizable compound M-1 4 g was changed to the polymerizable compounds M-12g and M-22g. A composition was prepared.

(Example 31)
Polymerization initiator K-1 is replaced with polymerization initiator K-3, PGMEA 15 g is replaced with PGMEA 7 g and PGME 8 g, and polymerizable compound M-1 4 g is replaced with polymerizable compounds M-1 2 g and M-3 2 g. A resin composition was prepared in the same manner as in Example 23 except that.

(Example 32)
Example except that the pigment dispersion A was changed to the pigment dispersion D, the polymerization initiator K-1 was changed to the polymerization initiator K-2, and the polymerizable compound M-1 was changed to the polymerizable compound M-2. A resin composition was prepared in the same manner as in No. 23.

(Example 33)
In a 200 g container (dispo cup), 5 g of M-1, 7 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 20 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 21 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 44 g of pigment dispersion A were added in this order, and the mixture was stirred for 30 minutes with a stirrer to prepare a resin composition.

(Example 34)
In a 200 g container (dispo cup), 5 g of M-1, 4 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 27 g of PGMEA, F-1 (1% PGMEA) 2 g of the solution), 6 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of the pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 1D)
In a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1.5 g of K-2, 29 g of PGMEA, F-1 (1 % PGMEA solution) 2 g, MegaFac RS-72-K (S-1) (30 wt% PGMEA solution) 0.5 g, and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes. (Content of S-1 with respect to the total solid content of the composition: 0.5% by mass).

(Example 2D)
In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 22 g of PGMEA, F-1 (1% PGMEA) 2 g of the solution), 15 g of MegaFac RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of the pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition ( S-1 content based on the total solid content of the composition: 17% by mass).

(Example 35)
A resin composition was prepared in the same manner as in Example 34 except that the polymerization initiator K-2 was changed to the polymerization initiator K-3.

(Example 36)
In a 200 g container (disposable cup), 4 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 27 g of PGMEA, F-1 (1% PGMEA) 2 g of solution), 1 g of LS-2940, 55 g of pigment dispersion A, and MegaFac RS-72-K (S-1) (30 wt% PGMEA solution): 6 g in this order, and stirred and mixed with a stirrer for 30 minutes Thus, a resin composition was prepared.

(Example 37)
A resin composition was prepared in the same manner as in Example 34 except that the polymerization initiator K-2 was changed to the polymerization initiator K-1, and the polymerizable compound M-1 was changed to the polymerizable compound M-2.

(Comparative Example 4)
In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 16 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 21 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 55 g of pigment dispersion C were added in this order, and the mixture was stirred for 30 minutes with a stirrer to prepare a resin composition.

(Comparative Example 5)
In a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of Irgacure OXE02 (BASF Japan), 30 g of PGMEA, F-1 2 g of (1% PGMEA solution) and 55 g of pigment dispersion C were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Comparative Example 6)
A resin composition of Comparative Example 6 was prepared in the same manner as in Example 34 except that the pigment dispersion A was changed to the pigment dispersion C.
(2) Production and evaluation of resin film <Evaluation of adhesion>
Each of the resin compositions of Examples and Comparative Examples was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning), and then heat-treated (prebaked) for 2 minutes using a hot plate at 100 ° C. It was. In addition, the following evaluation was performed with the film thickness that the OD value at this time was 2.
Proxy exposure (exposure apparatus UX3100-SR (manufactured by Ushio Electric Co., Ltd.), exposure amount 1000 mJ / cm ² ) was performed on the substrate after pre-baking through a predetermined mask (150 μm □ type island pattern).
Thereafter, using a TMAH (tetramethylammonium hydroxide) 2.38 wt% developer, the obtained substrate was subjected to paddle development for 10 to 60 seconds (the time required for resolution when pattern exposure was performed). . After washing with water and drying, the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to produce a substrate having a pattern.
The obtained island pattern was subjected to a tape pull test in accordance with JIS-K5400. The case where the entire pattern was left was A, the case where a part of the pattern was peeled off was B, and the case where the whole pattern was peeled was C.
The results are shown in Tables 7 and 8.

<Evaluation of resolution>
Each of the resin compositions of Examples and Comparative Examples was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning), and then heat-treated (prebaked) for 2 minutes using a hot plate at 100 ° C. It was.
Thereafter, proxy exposure (exposure apparatus UX3100-SR (manufactured by Ushio Electric Co., Ltd.), exposure amount 500 mJ / cm ² ) is applied to the substrate after pre-baking through predetermined masks having various line and space line widths. went.
Thereafter, using a TMAH (tetramethylammonium hydroxide) 2.38 wt% developer, the obtained substrate was subjected to paddle development for 10 to 60 seconds (the time required for resolution when pattern exposure was performed). . After washing with water and drying, the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to produce a substrate having a pattern.
The obtained pattern was observed with an optical microscope, and the minimum line width (μm) where the line and space pattern was not peeled was taken as the resolution value.
For example, when a line and space of 100 μm is resolved and peeling does not occur, it is determined that the resolution is 100 μm.
The results are shown in Tables 7 and 8.
In addition, about each resin film of Examples 23-33, it has confirmed that the surface roughness (arithmetic mean Ra) is 100-2000 mm before an exposure process. The method for measuring the surface roughness (arithmetic mean Ra) is as described above. In Examples 34 to 35, it was confirmed that a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom were formed adjacent to each other on the substrate. ing.

  Further, in Example 33, the reflectance was 2% (the reflectance at 400 nm), the moisture resistance was “A”, and the adhesion was “A”.

All of the resin films of the examples were excellent in low reflectivity, excellent in moisture resistance, and good results were obtained with respect to adhesion. In particular, it was confirmed that the resin films of Examples 34 to 35 were excellent in resolution.
On the other hand, from the results of Comparative Examples 4, 5, and 6, it was confirmed that when the titanium nitride-containing particles containing metal atoms other than titanium atoms were not contained, the moisture resistance and adhesion were inferior. Further, for example, by comparing Example 34 with Comparative Example 6, it was found that the resolution was poor when no titanium nitride-containing particles containing metal atoms other than titanium atoms were contained. In Comparative Example 4, it is presumed that the addition of the filler also causes unevenness on the side wall of the pattern, which also reduces the resolution.
Moreover, it turned out by the comparison of Examples 34-37 that resolution can be improved more by using K-2 or K-3 as a polymerization initiator.
Further, by comparing Example 34 and Examples 1D and 2D with a resin having at least one of a fluorine atom and a silicon atom in an amount of 1 to 15% by mass based on the total solid content of the composition, moisture resistance and resolution are achieved. It was confirmed that the properties can be compatible with each other.

[Production and Evaluation of Resin Film 4]
(Example 38)
After spin-coating the resin composition of Example 34 (pigment concentration 50%) on a glass substrate (Corning 1737 [trade name], manufactured by Corning), heat treatment (prebaking) for 2 minutes using a hot plate at 100 ° C. Went. Then, the exposure process (exposure apparatus UX3100-SR (made by USHIO INC.), Exposure amount 1000 mJ / cm < ² >) was implemented with respect to the coating film obtained above through a predetermined mask.
Thereafter, the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to prepare a pigment layer Y1. Application was performed with a film thickness at which the OD value was 1.0.
Further, the resin composition of Example 33 (pigment concentration 40%) was spin-coated on the obtained pigment layer Y1, and then heat-treated (prebaked) for 2 minutes using a 100 ° C. hot plate. Then, the exposure process (exposure apparatus UX3100-SR (made by USHIO INC.), Exposure amount 1000 mJ / cm < ² >) was implemented with respect to the coating film obtained above through a predetermined mask.
Thereafter, the substrate was subjected to a heat treatment (post-bake) for 300 seconds using a 220 ° C. hot plate to form the pigment layer Y2, and a resin film having the pigment layer Y1 and the pigment layer Y2 adjacent to each other was obtained. . In addition, it apply | coated with the film thickness from which OD in the pigment layer Y2 single becomes 0.5.

The OD value is a value obtained by the following method.
A pigment layer having a desired film thickness is formed on an alkali-free glass having a thickness of 0.7 mm, and the intensities of incident light and transmitted light are measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.). Calculated.
OD value = log ₁₀ (I ₀ / I)
I ₀ : Incident light intensity I: Transmitted light intensity

With respect to the produced substrate with resin film, light of 400 to 700 nm was incident on the resin film at an incident angle of 5 °, and the reflectance was measured with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.
At this time, the reflectance at 400 nm was 3.0.
Further, a high-temperature and high-humidity test for 750 hours was performed on the substrate with the resin film using a high acceleration life test apparatus (EHS-221 manufactured by Espec) at a temperature of 85 ° C. and a humidity of 95%.
When the transmittance at a wavelength of 400 nm of the substrate with the resin film before and after the moisture resistance test was measured with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation, the change rate ΔT (%) was less than 1%.

(Example 39)
In accordance with the method for producing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced. In Example 39, the pigment layer Y1 was applied and formed with a film thickness such that the OD value was 0.5, and then the pigment layer Y2 was applied thereon so that the OD of the pigment layer Y2 alone was 1.0. Formed.
With respect to the produced substrate with a resin film, light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° from the side of the substrate surface opposite to Example 38, and the reflectance was measured.
At this time, the reflectance at 400 nm was 2.5%.
Further, a high-temperature and high-humidity test for 750 hours was performed on the substrate with the resin film using a high acceleration life test apparatus (EHS-221 manufactured by Espec) at a temperature of 85 ° C. and a humidity of 95%.
When the transmittance at a wavelength of 400 nm of the substrate with the resin film before and after the moisture resistance test was measured, the change rate ΔT (%) was less than 0.5%.

  As shown in Examples 38 and 39, excellent low reflectivity even when the titanium nitride-containing particles containing two or more kinds of metal atoms are included and the pigment layers having different pigment concentrations in the layer have a multilayer structure. It was confirmed that moisture resistance was exhibited.

(Example 40)
In a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of Irgacure OXE02 (BASF Japan), 30 g of PGMEA, F-1 2 g of (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Production of laminated film)
In accordance with the method for producing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced.
In the present example, the resin composition prepared above was used, and a coating film was laminated on a glass substrate so as to be OD1.0 (pigment layer Y1) and OD0.5 (pigment layer Y2) in this order.
With respect to the produced substrate with resin film, light of 400 to 700 nm was incident on the resin film at an incident angle of 5 °, and the reflectance was measured with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. At this time, the reflectance at 400 nm was 4.0%.
In addition, a high-temperature and high-humidity test for 750 hours was performed on the substrate with a resin film using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.) at a temperature of 85 ° C. and a humidity of 95%. The change rate ΔT (%) was less than 1%.

(Example 41)
In accordance with the method for producing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced.
In this example, the resin composition prepared in Example 40 was used, and a coating film was laminated on a glass substrate so as to be OD0.5 (pigment layer Y1) and OD1.0 (pigment layer Y2) in this order.
In the same manner as in Example 39, light having a wavelength of 400 to 700 nm was incident on the resin film from the substrate surface side at an incident angle of 5 °, and the reflectance was measured. At this time, the reflectance at 400 nm was 4.0.
In addition, a high-temperature and high-humidity test for 750 hours was performed on the substrate with a resin film using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.) at a temperature of 85 ° C. and a humidity of 95%. The change rate ΔT (%) was less than 1%.

Claims (28)

Titanium nitride-containing particles containing at least one metal atom other than titanium atoms;
A binder resin,
A resin composition comprising a filler and at least one selected from a compound containing at least one of a fluorine atom and a silicon atom.   When the X-ray diffraction spectrum of the titanium nitride-containing particles is measured using CuKα rays as an X-ray source, the peak diffraction angle 2θ derived from the TiN (200) plane of the titanium nitride-containing particles is 42.5 ° or more. The resin composition of Claim 1 which exists in the range of 43.5 degrees or less.   The resin composition according to claim 1 or 2, wherein the filler is at least one of silica particles and acrylic particles.   The resin composition according to claim 3, wherein the filler is hollow silica.   The resin composition according to any one of claims 1 to 4, wherein a maximum value in a particle size distribution of the filler is 50 to 500 nm.   A compound containing at least one of the fluorine atom and silicon atom is contained, and the content of the compound containing at least one of the fluorine atom and silicon atom is from 1 to the total solid content in the resin composition. The resin composition of any one of Claims 1-5 which is 15 mass%.   The compound containing at least one of the fluorine atom and the silicon atom is a polymer compound containing a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group. The resin composition of any one of -6.   The resin composition according to any one of claims 1 to 6, wherein the compound containing at least one of a fluorine atom and a silicon atom is a reactive silicone.   Furthermore, the resin composition of any one of Claims 1-8 containing a dispersion resin.   Furthermore, the resin composition of any one of Claims 1-9 containing a polymerization initiator.   The resin composition according to claim 10, wherein the polymerization initiator is an oxime compound.   Furthermore, the resin composition of any one of Claims 1-11 containing the silane coupling agent which has an epoxy group.   Furthermore, the resin composition of any one of Claims 1-12 containing the polymeric compound which has a cardo frame | skeleton.   The resin composition according to claim 13, wherein the polymerizable compound having a cardo skeleton is a polymerizable compound having a 9,9-bisarylfluorene skeleton.   The resin composition according to any one of claims 1 to 14, wherein a content of the titanium nitride-containing particles is 30 to 60% by mass with respect to a total solid content in the resin composition. Titanium nitride-containing particles containing at least one metal atom other than titanium atoms;
A resin film containing a binder resin,
The resin film whose surface roughness Ra of the outermost surface of the said resin film is 100-2000 mm.   Furthermore, the resin film of Claim 16 containing a filler.   The resin film according to claim 17, wherein a maximum value in a particle size distribution of the filler is 50 to 500 nm.   Furthermore, the resin film of any one of Claims 16-18 containing resin which has a polysiloxane structure. The resin film is a resin film in which the pigment layer X1 and the pigment layer X2 each containing the titanium nitride-containing particles are laminated adjacently,
The concentration of the titanium nitride-containing particles contained in the pigment layer X2 is smaller than the concentration of the titanium nitride-containing particles contained in the pigment layer X1,
The resin film according to any one of claims 16 to 19, wherein the surface roughness Ra of the surface of the resin film on the pigment layer X2 side is 100 to 2000 mm. A pigment layer containing titanium nitride-containing particles containing at least one metal atom other than titanium atoms;
And a surface layer including a compound containing at least one of a fluorine atom and a silicon atom, which is disposed adjacent to the pigment layer.   The resin film according to claim 21, wherein the compound containing at least one of a fluorine atom and a silicon atom includes a resin containing at least one of a fluorine atom and a silicon atom.   The resin film according to claim 22, wherein the resin containing at least one of a fluorine atom and a silicon atom contains a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group. . It is a resin film in which a pigment layer Y1 and a pigment layer Y2 each containing titanium nitride-containing particles containing at least one metal atom other than a titanium atom are laminated adjacently,
Resin films having different concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2.   A color filter comprising any one selected from the resin film formed from the resin composition according to any one of claims 1 to 15 and the resin film according to any one of claims 16 to 24.   The light shielding film provided with either the resin film formed from the resin composition of any one of Claims 1-15, and the resin film of any one of Claims 16-24.   A solid-state imaging device comprising any one selected from the resin film formed from the resin composition according to any one of claims 1 to 15 and the resin film according to any one of claims 16 to 24. An image display device comprising any one selected from the resin film formed from the resin composition according to any one of claims 1 to 15 and the resin film according to any one of claims 16 to 24.