JP6800949B2 - Resin composition, resin film, color filter, light-shielding film, solid-state image sensor, and image display device - Google Patents

Description

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

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

JP-A-2007-115921

On the other hand, the light-shielding film is required to have various characteristics in recent years.
For example, as the solid-state image sensor becomes smaller, thinner, and more sensitive, the light-shielding film is required to have even lower reflection.
In addition, the present inventors have come to find that when a light-shielding film containing titanium black is exposed to high temperature and high humidity, its spectral performance deteriorates (that is, it is inferior in "moisture resistance"). If the spectral performance of the light-shielding film deteriorates, the desired light-shielding ability may not be exhibited, so 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 having excellent low reflectivity and moisture resistance, a color filter provided with the resin film, a light-shielding film, a solid-state image sensor, and an image display device.

As a result of diligent studies to achieve the above problems, the present inventors have selected at least a compound containing at least one of a predetermined titanium nitride-containing particle, a binder resin, a filler, and a fluorine atom and a silicon atom. We have found that the above problems can be solved by using a resin composition in combination with any of them, and have completed the present invention.
That is, it was found that the above object can be achieved by the following configuration.

(1) Titanium nitride-containing particles containing at least one kind of metal atom other than titanium atom and
Binder resin and
A resin composition containing a filler and at least one selected from compounds 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-ray as an X-ray source, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the titanium nitride-containing particles is 42. The resin composition according to (1), which is in the range of 5 ° or more and 43.5 ° 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) The content of the compound containing at least one of the fluorine atom and the silicon atom and the content of the compound containing at least one of the fluorine atom and the 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 a fluorine atom and a 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), which further contains a dispersed resin.
(10) The resin composition according to any one of (1) to (9), further containing a polymerization initiator.
(11) The resin composition according to (10), wherein the polymerization initiator is an oxime compound.
(12) The resin composition according to any one of (1) to (11), further containing a silane coupling agent having an epoxy group.
(13) The resin composition according to any one of (1) to (12), further containing 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. Stuff.
(16) Titanium nitride-containing particles containing at least one kind of metal atom other than titanium atom and
A resin film containing a binder resin and
A resin film having a surface roughness Ra of the outermost surface of the resin film of 100 to 2000 Å.
(17) The resin film according to (16), further containing 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 comprising a resin having a polysiloxane structure.
(20) The resin film is a resin film in which a pigment layer X1 and a pigment layer X2 each containing the titanium nitride-containing particles are laminated adjacent to each other.
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 Å.
(21) A pigment layer containing titanium nitride-containing particles containing at least one kind of metal atom other than titanium atom, and a pigment layer.
A resin film containing a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom, which is arranged 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 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, according to (22). 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 kind of metal atom other than a titanium atom are laminated adjacent to each other.
A resin film in which the concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other.
(25) A color having a resin film formed from the resin composition according to any one of (1) to (15) and any one selected from the resin film according to any one of (16) to (24). filter.
(26) Light-shielding provided with a resin film formed from the resin composition according to any one of (1) to (15) and any one selected from the resin film according to any one of (16) to (24). film.
(27) A solid comprising a resin film formed from the resin composition according to any one of (1) to (15) and any one selected from the resin film according to any one of (16) to (24). Image sensor.
(28) An image including a resin film formed from the resin composition according to any one of (1) to (15) and any one selected from the resin film according to any one of (16) to (24). Display device.

According to the present invention, it is possible to provide a resin composition capable of forming a resin film having excellent low reflectivity and also excellent moisture resistance.
Further, according to the present invention, it is also possible to provide a resin film having excellent low reflectivity and also excellent moisture resistance, a color filter provided with the resin film, a light-shielding film, a solid-state image sensor, and an image display device.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes those which do not have a substituent and those which 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) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl.
The "pigment" in the present invention means, for example, an insoluble pigment compound that is insoluble in a solvent. Here, the "solvent" includes a solvent exemplified in the column of solvent described later. Therefore, pigment compounds that are insoluble in these solvents fall under the pigments in the present invention.
Further, the “active ray” or “radiation” in the present specification means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. .. Further, in the present invention, "light" means active light rays or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Draw with lines is also included in the exposure.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
Further, in the present invention, "1 Å" is synonymous with "0.1 nanometer (nm)".

[First embodiment: resin film having Ra of 100 to 2000 Å]
The resin film in the first embodiment contains titanium nitride-containing particles containing at least one kind of metal atom other than titanium atoms and a binder resin, and the surface roughness Ra of the outermost surface thereof is 100 to 2000 Å. It is characterized by.
Now, the present inventors have set the surface roughness of the outermost surface of a resin film containing titanium nitride-containing particles containing at least one kind of metal atom other than a titanium atom within the above numerical range. Has been found to have excellent low reflectivity and moisture resistance. In particular, it can be 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 is used (Embodiments 1A and 1B described later, respectively). It has been confirmed that the low reflection performance of the film is further improved and the moisture resistance is remarkably excellent.

The surface roughness of the resin film (arithmetic mean roughness Ra) is preferably 300 to 2000 Å (angstrom), more preferably 300 to 1500 Å, 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 at 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, in that the effect of the present invention is more excellent. The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thicknesses of any five or more points of the resin film and arithmetically averaging them.

Hereinafter, various materials and manufacturing methods for forming the resin film of the first embodiment will be described.
In the following, first, as a method of roughening the film surface, a mode in which a filler is contained in the resin film will be described.

[Embodiment 1A]
Examples of the material constituting the resin film include titanium nitride-containing particles containing at least one kind of metal atom other than titanium atom, a binder resin, and a filler. The resin film can be formed by applying a resin composition containing the above-mentioned constituent material or a precursor material thereof onto a substrate.
Further, the resin composition may be a photosensitive resin composition having exposure and developability. In this case, a polymerization initiator, a polymerizable compound, or the like may be further added to the resin composition. Further, a binder resin, a polymerizable compound, a dispersion resin described later, or the like may be used as an alkali-soluble material.
Hereinafter, various materials contained in the above-mentioned 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 atom>
The resin composition A contains titanium nitride-containing particles (hereinafter, also referred to as “titanium nitride-containing particles”) containing at least one kind of metal atom other than titanium atom as a black pigment. The titanium nitride-containing particles contain a titanium atom and at least one kind of metal atom other than the titanium atom. Further, 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. The “composite fine particles” refer to particles in which titanium nitride particles and metal fine particles are compounded or highly dispersed. Here, "composite" means that the particles are composed of both titanium nitride and metal components, and "highly dispersed state" means that the titanium nitride particles and the metal particles are present. It means that the particles exist individually and the particles of a small amount of components are uniformly and uniformly dispersed without agglomeration.
Moreover, the "titanium nitride particles" includes titanium nitride as a main component, usually, lower titanium oxide represented by titanium oxide _{TiO 2, Ti n O 2n-} 1 (1 ≦ n ≦ 20) as a sub-component And Titanium oxynitride represented by TiN _{yO 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 spectroscopic analysis, and the content of nitrogen atoms is analyzed by the inert gas melting-thermal conductivity method, and the content of oxygen atoms is contained. The amount can be analyzed by the 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 for producing fine particles, atoms other than the above titanium atom, nitrogen atom, oxygen atom, and metal atom may be contained as impurities, but if the amount of impurities is small and it is difficult to specify, impurities are considered. Calculate without doing.
From the viewpoint of dispersion stability and light-shielding property, the specific surface area of the titanium nitride-containing particles is preferably 5 m ² / g or more and 100 m ² / g or less, and more preferably 10 m ² / g or more and 60 m ² / g or less. The specific surface area can be determined by the BET method.

The metal atom (metal fine particle) is not particularly limited, and for example, copper, silver, gold, vanadium, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantal, calcium, titanium, bismus, antimony and lead, and at least one selected from these alloys. Among them, copper, silver, gold, iron, platinum, palladium, nickel, vanadium, tin, cobalt, rhodium and iridium, and at least one selected from these alloys are preferable, and 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 being more excellent in moisture resistance, at least one selected from silver and iron is more preferable, and silver is particularly preferable.
The content of metal atoms (metal fine particles) in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 50% by mass, preferably 0.01% by mass, based on the total mass of the titanium nitride-containing particles. It is more preferably% or more and 30% by mass or less, and particularly preferably 0.2% by mass or more and 30% by mass or less. When a plurality of types of metal atoms (metal fine particles) are contained, it means that the total content thereof 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 content of the metal atom is less than 50% by mass, the moisture resistance and the rubbing resistance are excellent. Excellent corrosion resistance of the electrode due to the cured film. That is, it is possible to prevent the cured film from corroding the electrodes.
The metal atoms contained in the titanium nitride-containing particles had excellent adhesion to the electrodes and the substrate, and the titanium nitrides in the titanium nitride-containing particles adhered to the electrodes and the substrate via the metal atoms. Conceivable. Therefore, it is considered that the metal atoms remain on the electrode and the substrate after the patterning of the cured film such as the developing process, and the titanium nitride is easily removed. Therefore, it is presumed that the patterning property of the cured film is improved by increasing the content of metal atoms in the titanium nitride-containing particles to a predetermined amount or more.

In addition, when stored 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 corrosion resistance of the electrode was improved by reducing the content of metal atoms in the titanium nitride-containing particles to less than 0.4% by mass. When this effect is obtained, 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 any treatment such as surface coating.
In order to obtain higher light-shielding properties as metal fine particles, it is preferable to make the metal fine particles appropriately. The crystallite size determined from the half width of the main peak, which has the strongest intensity 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 half width of the X-ray diffraction peak using Scheller's formula.
For example, in the X-ray diffraction spectrum of silver, when CuKα ray is used as an X-ray source, a peak derived from the (111) plane is observed 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 the light-shielding property.
In the X-ray diffraction spectrum of titanium nitride, when CuKα ray is used as the X-ray source, the peak derived from the (200) plane of TiN is observed in the vicinity of 2θ = 42.5 ° as the strongest peak, and TiO is (200). ) A peak derived from the plane is observed near 2θ = 43.4 °. On the other hand, although it is not the strongest peak, anatase-type TiO ₂ has a peak derived from the (200) plane observed near 2θ = 48.1 °, and rutile-type TiO ₂ has a peak derived from the (200) plane. It is observed near 2θ = 39.2 °. Therefore, the titanium compound having a crystal structure having a nitrogen atom and an oxygen atom has the strongest peak in the diffraction angle 2θ in the 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 shifts to the higher angle side with respect to 42.5 °.

From the viewpoint of light-shielding property, the titanium nitride particles preferably contain TiN as a main component, and the diffraction angle 2θ of the peak derived from the (200) plane thereof is preferably 42.5 ° or more and 43.5 ° or less, 42. It is more preferably 5.5 ° or more and 42.8 ° or less, and further preferably 42.5 ° or more and less than 42.7 °. Titanium nitride particles usually contain some oxygen atoms due to oxidation of the particle surface or the like and take the form of an oxynitride. Usually, the mixing of oxygen during the synthesis of titanium nitride particles becomes particularly remarkable when the particle size is small. It is preferable that the amount of oxygen contained is small because higher light-shielding property can be obtained, and it is particularly preferable that TiO ₂ is not contained as an auxiliary component. The content of oxygen atoms is preferably 10% by mass or less, more preferably 6.0% by mass or less, based on the mass of the titanium nitride particles.

From the viewpoint of light-shielding property, 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 ratio of the active particle surface to the particle volume becomes small, and a good balance is obtained. As a result, titanium nitride-containing particles having remarkably excellent 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 property, in order to enhance the light-shielding property. Is more preferably 42.5 ° or more and 42.8 ° or less, and further preferably 42.5 ° or more and less than 42.7 °. Further, when titanium oxide TiO ₂ is contained as a sub-component, a peak derived from anatase-type TiO ₂ (101) is observed in the vicinity of 2θ = 25.3 ° as the strongest peak, and rutile-type TiO ₂ (110). The peak derived from 2θ = 27.4 ° is observed. However, since TiO ₂ is white and causes a factor of lowering the light-shielding property, it is preferable that it is 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 vapor phase state, and are produced by a thermal plasma method using a nitrogen-containing gas as a plasma gas. Is more preferable.

As the titanium nitride-containing particles, those described in International Publication No. 2010/147098, JP-A-2007-153662, and the like can be further referred to.
The content of the 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. Is more preferable.

As a method for producing the titanium nitride-containing particles, those described in paragraphs <0037> to <089> of International Publication No. 2010/147098 can be referred to.
Further, the titanium nitride-containing particles are kept in a closed container in which the oxygen concentration is controlled for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours) without being immediately exposed to the atmosphere after the particles are produced. , More preferably 12 to 24 hours). At that time, it is more preferable that the water content is controlled. It is presumed that this stabilizes the surface and grain boundaries of the titanium nitride-containing particles and improves the performance of the composition. Specifically, it is possible to suppress the occurrence of pinholes in the cured film obtained by using the composition of the present invention.
The oxygen (O ₂ ) concentration and the water content in the closed container in which the oxygen concentration is controlled are preferably 100 mass ppm or less, more preferably 10 mass ppm or less, and 1 mass ppm or less. Is more preferable. 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, nitrogen gas is more preferable. It is presumed that this stabilizes the surface and grain boundaries of the titanium nitride-containing particles and improves the performance of the composition. Specifically, titanium nitride-containing particles having a high optical density can be obtained, and the generation of pinholes in a cured film obtained by using the composition of the present invention can be suppressed. Further, the temperature at which the product is allowed to stand for a predetermined time is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 100 ° C. or lower. Within this range, titanium nitride-containing particles having a higher optical density can be obtained.

The titanium powder material used for producing the titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited, and a material having a purity of titanium element of 99.99% by mass or more is preferable, and a material having a purity of 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, and substantially contained in the total amount of the titanium powder material. Not particularly preferred.
The water content in the titanium powder material is preferably less than 1% by mass, more preferably less than 0.1% by mass, and substantially not contained in the total amount of the titanium powder material. Especially preferable. Within the above range, the desired effect can be obtained more remarkably.

Examples of the process of dispersing the titanium nitride-containing particles include a process of using compression, squeezing, impact, shearing, cavitation, or the like as the mechanical force used for dispersion. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion and microfluidizers. In addition, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" or "Dispersion technology centered on suspension (solid / liquid dispersion system) and practical comprehensive data collection of industrial applications, Management Development Center Publishing Department The process and disperser described in "Published October 10, 1978" can be suitably used. The pigment may be miniaturized by a salt milling step. As the materials, equipment, processing conditions, etc. used in the salt milling step, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used, for example.
Of these, a sand mill (bead mill) is preferable. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter or to process under conditions where the pulverization efficiency is increased by increasing the filling rate of the beads, and further filtering after the pulverization treatment. , It is preferable to remove elementary particles by centrifugation or the like.

The titanium nitride-containing particles described above are also suitably used in the process of dispersing the pigment described later.

<Binder resin>
The 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 the respective contents are 3 with respect to the total mass of the resin. It is preferably 1% by mass or less, and more preferably 0.1% by mass or less.

The binder resin is not particularly limited, and it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be arbitrarily used.
The molecular weight of the binder resin is not particularly specified, and the weight average molecular weight (Mw) is preferably 5000 to 100,000 as a polystyrene-equivalent value by the GPC (gel permeation chromatography) method. The number average molecular weight (Mn) is preferably 1000 to 20,000.
In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) is used as an eluent. ) Is used.

As described above, the resin composition A can have exposure and developability. Therefore, when the resin composition A is a photosensitive resin composition, the binder resin is preferably a resin capable of water development or weak alkaline water development, and is soluble or swellable in water or weak alkaline water. More preferably, it is a linear organic polymer. Among them, 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 specified, and the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000. The weight average molecular weight and the number average molecular weight can be measured by the above-mentioned method.
The alkali-soluble resin may be a linear organic high molecular polymer, and promotes at least one alkali solubility in the molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from the alkali-soluble resins having a group to be used.

As the alkali-soluble resin, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable from the viewpoint of heat resistance, and from the viewpoint of developability control, the alkali-soluble resin is preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins 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, which are soluble in an organic solvent and developed with a weak alkaline aqueous solution. What is possible is preferable. The acid group may be only one type or two or more types.

For the 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 the radical polymerization method can be easily set by those skilled in the art, and the conditions are experimentally determined. You can also do it.

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 Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak type 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. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. α-Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer, etc., N-position substitution described in JP-A-10-300922. Examples of the maleimide monomer include N-phenylmaleimide and N-cyclohexylmaleimide. The other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

Further, in order to improve the cross-linking 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 or the like having a polymerizable group in the side chain is useful.
Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing, polyurethane acylicolomer. Diamond Shamlock Co. Ltd., manufactured), Viscort R-264, KS resist. 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebeclyl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD -F8 (manufactured by Nippon Catalyst Co., Ltd.) and the like.

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-polymer copolymer composed of / (meth) acrylic acid / other monomer 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 / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene Macromonomers / benzyl methacrylate / methacrylic acid copolymers and the like can also be preferably used.
Further, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

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 dimer"). It is also preferable to include the polymer (a) obtained by polymerizing the monomer component.

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

In the 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-A-2010-168539 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 for example, a methyl group, an ethyl group, and the like. 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 Oryl group such as cyclohexyl group, tert-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group and other alicyclic groups; 1- Examples thereof include an alkyl group substituted with an alkoxy such as a methoxyethyl group and a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these, a primary or secondary carbon substituent such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like, which is difficult to be desorbed by acid or heat, is particularly preferable in terms of heat resistance.

As a specific example of the ether dimer, for example, paragraph 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be only one type or two or more types. 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 the 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 and may contain 1 to 20 carbon atoms. Represents the alkyl group of. 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. Further, the alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain 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. In addition, "Me" means a methyl group.

As for the alkali-soluble resin, the descriptions in paragraphs 0558 to 0571 of JP2012-208494A (<0685> to <0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to. The content is incorporated herein by reference.
Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in Examples, and paragraph numbers 0088 to 0098 of JP2012-208474A. The binder resin described and the binder resin used in Examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A, and the binder resin used in Examples, JP2013-024934. Binder resins described in paragraphs 0132 to 0143 of Japanese Patent Application Laid-Open No. 0132 to 0143 and binder resins used in Examples, paragraph numbers 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and binder resins used in Examples The binder resin described in paragraphs 0030 to 0072 of Japanese Patent Application Laid-Open No. -032770 can also be used. These contents are incorporated in the specification of the present application.

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 even 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 another resin, the polyimide resin described in International Publication No. 2008/123097 is also useful.

The content of the binder resin in the resin composition A is preferably 0.01 to 40% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, further 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, further preferably 20% by mass or less. In the resin composition A, only one kind of binder resin may be contained, or two or more kinds of binder resins may be contained. When two or more types are included, the total amount is preferably in the above range.

<Filler>
The resin composition A contains a filler. Here, the "filler" is a particle given for the purpose of roughening the surface. The titanium nitride-containing particles described above are not included in the filler. Further, the particles used for imparting colorability of other pigments and the like are not contained in the filler, and the filler is preferably non-colorable.
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 structure inside.
The organic particles are not particularly limited, and the materials thereof include, for example, homopolymers or copolymers of cellulose derivatives, acrylic resins, polyolefins, polyamides, polycarbonates, polystyrenes, vinyl acetates, vinyl alcohols, vinyl chlorides or vinyl butyral. Examples thereof include vinyl polymers such as coalescing, homopolymers of diene, and resins such as copolymers.
From the viewpoint of low reflectivity, silica particles and acrylic particles are preferable, 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 Nanotrack UPA-EX manufactured by Microtrac Bell.

When the filler is contained in the resin composition A, 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. It is more preferably 3 to 15% by mass.
In the resin composition A, only one kind of filler may be contained, or two or more kinds of fillers may be contained. When two or more types are included, the total amount is preferably in the above range.

<Dispersed resin>
The resin composition A may contain a dispersed resin. The dispersed resin contributes to improving the dispersibility of colored pigments such as the above-mentioned titanium nitride-containing particles (hereinafter, also appropriately referred to as “black pigment”) and other pigments used in combination as desired.
Examples of the dispersed resin include polyamide amine 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, and naphthalene. Formalin sulfonate condensate and the like can be mentioned.
Dispersed resins (hereinafter, also referred to as “polymer compounds”) can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

The polymer compound acts to prevent reaggregation by adsorbing on the surface of the dispersion to be dispersed, such as a black pigment and a pigment to be used in combination if desired. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface can be mentioned as preferable 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 addition, in this specification, "structural unit" is synonymous with "repeating unit".
A polymer compound having a structural unit having such a graft chain has an affinity for a solvent due to the graft chain, and therefore has excellent dispersibility of coloring pigments such as black pigments and dispersion stability after aging. Is. Further, in the composition, 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, it is difficult to generate a residue in alkaline development.
When the graft chain is long, the steric repulsion effect is high and the dispersibility is improved, while when the graft chain is too long, the adsorptivity to a coloring pigment such as a black pigment is lowered and the dispersibility tends to be lowered. Therefore, the graft chain preferably has an atomic number in the range of 40 to 10,000 excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and atoms excluding hydrogen atoms. Those having a number of 60 to 500 are more preferable.
Here, the "graft chain" indicates from the root of the main chain of the copolymer (atom bonded to the main chain in the 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, and 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 and the like.
In order to improve the interoperability between the graft chain and the solvent, thereby increasing the dispersibility, the graft chain shall be at least one selected from the group consisting of polyester structure, polyether structure and poly (meth) acrylate structure. It is preferably a graft chain having, and more 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 preferably a macromonomer having a reactive double bond group can be preferably used.

Commercially available macromonomers that correspond to the structural unit having the graft chain of the polymer compound and are preferably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Synthesis Co., Ltd.) and AA-10 (AA-10). Product name, Toa Synthetic Co., Ltd.), AB-6 (Product name, Toa Synthetic Co., Ltd.), AS-6 (Product name, Toa Synthetic Co., Ltd.), AN-6 (Product name, Toa Synthetic Co., Ltd.) Made by Toa Synthetic Co., Ltd.), AW-6 (trade name, manufactured by Toa Synthetic Co., Ltd.), AA-714 (trade name, manufactured by Toa Synthetic Co., Ltd.), AY-707 (trade name, manufactured by Toa Synthetic Co., Ltd.), AY-714 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-5 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-30 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-32 (product name) Name, manufactured by Toa Synthetic Co., Ltd., Aronix M-110 (trade name, manufactured by Toa Synthetic Co., Ltd.), Aronix M-5300 (trade name, manufactured by Toa Synthetic Co., Ltd.), Aronix M-5400 (trade name, manufactured by Toa Synthetic Co., Ltd.) Toa Synthetic Co., Ltd.), Aronix M-5700 (trade name, manufactured by Toa Synthetic Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nichiyu Co., Ltd.), Brenmer PP-500 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer PP-800 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-1000 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer 55-PET-800 (trade name, manufactured by Nichiyu Co., Ltd.) Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-400 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-1300 (trade name, manufactured by Nichiyu Co., Ltd.) ), Blemmer 43 PAPE-600B (trade name, manufactured by Nichiyu Co., Ltd.) and the like are used. Of these, preferably AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.). , AS-6 (trade name, Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), Aronix M-110 (trade name, manufactured by Toagosei Co., Ltd.), Aronix M-5300 (Product name, manufactured by Toagosei Co., Ltd.), Bremmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.) and the like are used.

The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit having a graft chain, and the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any of the following formula (3A), the following formula (3B), and the following formula (4).

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ independently represent an oxygen atom or NH, respectively. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms.
In 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. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively, and are independent of each other. In addition, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

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

In 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 specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group and the like. Can be 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 preferable from the viewpoint of improving dispersibility, and each of them has 5 to 24 carbon atoms independently. 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 are particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

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

In the formula (3), R ³ represents a branched or linear 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, R ³ existing in plural numbers may be different from one another the same.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly structurally limited. Preferred as R ^4, a hydrogen atom, an alkyl group, an aryl group, and include heteroaryl groups, 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 further 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 can have two or more structural units having graft chains having different structures. That is, the molecule of the polymer compound may contain structural units represented by formulas (1) to (4) having different structures from each other, and n, m in formulas (1) to (4). When, p, and q each represent an integer of 2 or more, in the equations (1) and (2), j and k may contain different structures in the side chain, and the equations (3) and (3) and q may contain different structures. In the formula (4), a plurality of R ³ , R ⁴ and X ⁵ existing in the molecule may be the same or different from each other.

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

Further, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the 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 more 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 formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably contained in the range, more preferably in the range of 5 to 30%. When a structural unit having a graft chain is included in this range, the dispersibility of a coloring pigment such as a black pigment is high, and the developability when forming a colored layer is good.

Moreover, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, it does not correspond 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 (corresponding) structural unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and more preferably derived from a compound having a ClogP value of 1.2 to 8. It is a structural unit. Thereby, the effect of the present invention can be more reliably exhibited.

The ClogP value is determined by Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" available from. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, and the logP value of the compound is estimated by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medical Chemistry, Vol. 4, C.I. Hansch, P.M. G. Sammenens, J. Mol. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constituents For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Cofficient), and quantitatively describes 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 expressed by the following formula.
logP = log (Coil / Water)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Water represents the molar concentration of the compound in the aqueous phase.
When the logP value increases positively across 0, it means that oil solubility increases, and when it becomes negative and the absolute value increases, it means that water solubility increases, and there is a negative correlation with the water solubility of organic compounds, and the affinity of organic compounds It is widely used as a parameter for estimating water content.

The polymer compound preferably has at least one structural unit selected from the structural units derived from the monomers represented by the following general formulas (i) to (iii) as the hydrophobic structural unit.

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

L is a single bond or divalent linking group. The divalent linking group includes 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) and a divalent aromatic group (for example, an arylene group). , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{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. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and is preferably a saturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, a heterocyclic group and the like.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Moreover, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group and the like.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L may contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. 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.

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group) and an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, or a combination thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, an aromatic A group or a heterocyclic group) and a carbonyl group (-CO-) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a crosslinked ring-type hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group and a 4-cyclohexyl group. Includes phenyl groups and the like. Bicyclic hydrocarbon rings such as pinan, bornan, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Tricyclic hydrocarbon rings such as hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4] .4.0.1. ^2,5 . 17 and ¹⁰ ] Dodecane, 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings and the like can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroinden, and perhydro. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenanthrene ring are condensed is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Moreover, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

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

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are independently alkyl atoms having hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and carbon atoms having 1 to 6 atoms. Represents a group (eg, methyl group, ethyl group, propyl group, etc.), Z, or —LZ. Here, L and Z are synonymous with those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the above general formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a single bond or 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 as a divalent linking group containing.
Further, as the monomer represented by the above 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 above general formula (iii), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Certain compounds are preferred.

Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes and the like.
As examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 089 to 093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated in.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound in terms of mass. Sufficient pattern formation can be obtained when the content is in the above range.

The polymer compound can introduce a functional group capable of forming an interaction with a coloring pigment such as a black pigment. Here, it is preferable that the polymer compound further has a structural unit having a functional group capable of forming an interaction with a coloring pigment such as a black pigment.
Examples of the functional group capable of forming an interaction with the coloring pigment such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit having an acid group, a structural unit having a basic group, and a coordinating group, respectively. It is preferable to have a structural unit having the above, 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, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the resin composition A has the polymer compound as a dispersion resin that contributes to the dispersion of a coloring pigment such as a black pigment having alkali solubility. The composition containing such a polymer compound has excellent light-shielding properties in the exposed portion and improves the alkali developability of the unexposed portion.
Further, since the polymer compound has a structural unit having an acid group, the polymer compound tends to be easily compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit having an acid group easily interacts with the coloring pigment such as a black pigment, the polymer compound stably disperses the coloring pigment such as the black pigment, and the coloring pigment such as the black pigment is used. It is presumed that this is 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 structural unit having a graft chain described above or a different structural unit, and the alkali-soluble group as an acid group may be used. The structural unit to have is a structural unit different from the above-mentioned hydrophobic structural unit. That is, it does not correspond to the above-mentioned hydrophobic structural unit.

Examples of the acid group which is a functional group capable of forming an interaction with a coloring pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and a carboxylic acid is preferable. It is at least one of a group, a sulfonic acid group, and a phosphoric acid group, and a particularly preferable one is a carboxylic acid group having a good adsorption power to a coloring pigment such as a black pigment and a high dispersibility thereof. ..
That is, it is preferable that the polymer compound 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 based on the total mass of the polymer compound in terms of mass. It is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to the image intensity due to alkaline development.

Examples of the basic group which is a functional group capable of forming an interaction with a coloring pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocycle containing an N atom. There are amide groups and the like, and particularly preferable ones are tertiary amino groups having good adsorption power to coloring pigments such as black pigments and high dispersibility thereof. 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, and 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. It 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 developmental inhibition.

Examples of the coordinating group which is a functional group capable of forming an interaction with a coloring pigment such as a black pigment and the functional group having reactivity include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, and an acid anhydride. Examples thereof include acidified products. Particularly preferred is an acetylacetoxy group having good adsorption power to a coloring pigment such as a black pigment 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 when it is contained, the content of these structural units is mass. In terms of conversion, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developmental inhibition, with respect to the total mass of the polymer compound.

When the polymer compound in the present invention has a functional group capable of forming an interaction with a coloring pigment such as a black pigment in addition to the graft chain, it forms an interaction with a coloring pigment such as various black pigments as described above. It suffices to contain a possible functional group, 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 the structural units derived from the monomer.

In the general formula (iv) to the general formula (vi), R ¹¹ , R ¹² , and R ¹³ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), or carbon atoms. Represents an alkyl group having a number of 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, etc.).
In the general formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are more preferably independent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably. Are independently hydrogen atoms or methyl groups. In the general formula (iv), it is particularly preferable that R ¹² and R ¹³ are hydrogen atoms, respectively.

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

Further, L ₁ in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 31} '- , wherein R ^{31 'is} an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), or combinations thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Moreover, the aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups.

L ₁ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. 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 the general formula (iv) to the general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a coloring pigment such as a black pigment other than the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable, and it is more preferable that it is a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently alkyl atoms having hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) and carbon atoms having 1 to 6 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. As R ¹⁴ , R ¹⁵ , and R ¹⁶ , hydrogen atoms or alkyl groups having 1 to 3 carbon atoms are preferable, and hydrogen atoms are more preferable.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are independently hydrogen atoms or methyl groups, and L ₁ is an alkylene group or an oxyalkylene structure. A compound having a divalent linking group containing the above, 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 a methine. The compound that is the group is preferable.
Further, as the monomers represented by the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms or methyl groups, and L ₁ is a single bond or an alkylene group. A compound in which Z is a carboxylic acid group is preferable.

Hereinafter, typical examples of the monomers (compounds) represented by the general formulas (iv) to the general formulas (vi) are 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 and phthalic acid anhydride, and a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic acid 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 crotonic acid anhydride, Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylate and the like.

The content of the structural unit having a functional group capable of forming an interaction with a coloring pigment such as a black pigment is determined from the viewpoint of interaction with a coloring pigment such as a black pigment, dispersion stability, and permeability to a developing solution. It is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, still more preferably 10 to 70% by mass, based on the total mass of the polymer compound.

Further, the polymer compound is used as a structural unit having a graft chain, a hydrophobic structural unit, and a coloring pigment such as a black pigment for the purpose of improving various performances such as image intensity, as long as the effects of the present invention are not impaired. Other structural units having various functions (for example, structural units having functional groups having an affinity with the dispersion medium used for the dispersion), which are different from the structural units having functional groups capable of forming an interaction. You may also have more.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitrile, methacrylonitrile, and the like.
The polymer compound can use one or more of these other structural units, and its content is preferably 0% or more and 80% or less with respect to the total mass of the polymer compound in terms of mass. It is particularly preferable that it is 10% or more and 60% or less. Sufficient pattern formation is maintained when the content is in the above range.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g or more and 160 mgKOH / g, more preferably 10 mgKOH / g or more and 140 mgKOH / g or less, and further preferably 20 mgKOH / g or more and 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 during formation of the resin layer can be more effectively suppressed. Further, when the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH / g or more, the precipitation of coloring pigments such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the stability of the composition over time can be 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. Further, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the polymer compound.

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene equivalent value by the GPC (gel permeation chromatography) method from the viewpoint of suppressing pattern peeling during development and developability when forming a resin film. It is preferably 300,000 or more, 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 preferable to have.
In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) is used as an eluent. ) Is used.

The polymer compound can be synthesized based on a known method, and examples of the solvent used in 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, dimethylsulfoxide, toluene, Examples thereof 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 Kusunoki Kasei Co., Ltd., "Disperbyk-101 (polypolyamine phosphate), 107 (carboxylic acid ester)" and 110 (acid group) manufactured by BYK Chemie. Copolymers containing), 111 (phosphate-based dispersant), 130 (polyamide), 161 and 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", EFKA" EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester) Amid), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine Techno Co., Ltd." Azispar PB821, PB822, PB880, PB881 ", Kyoeisha "Floren TG-710 (urethane oligomer)" manufactured by Kagaku Co., Ltd., "Polyflow No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, # 2150 (fat) manufactured by Kusumoto Kasei Co., Ltd." Group polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonate formalin polycondensate), MS, C, SN-B (aromatic sulfonate formalin polycondensate) "," homogenol L-18 (polymer polycarboxylic acid) "," emalgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", "Acetamine 86 (stearylamine acetate)", Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (terminal part) (Polymer having a functional part), 24000, 28000, 32000, 38500 (graft copolymer) ”, Nikko Chemicals Co., Ltd.“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ) ”, Kawaken Fine Chemicals Co., Ltd. Hinoact T-8000E, etc., Shinetsu Chemical Industry Co., Ltd., Organoshi Loxan Polymer KP341, Yusho Co., Ltd. "W001: Cationic Surfactant", Polyoxyethylene Lauryl Ether, Polyoxyethylene Stearyl Ether, Polyoxyethylene Oleyl Ether, Polyoxyethylene Octylphenyl Ether, Polyoxyethylene Nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46" manufactured by Morishita Sangyo Co., Ltd., EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", Sannopco Co., Ltd." Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 Polymer dispersants such as "Adecapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121," manufactured by ADEKA Co., Ltd. Examples thereof include "P-123" and "Ionet (trade name) S-20" manufactured by Sanyo Kasei Co., Ltd. Further, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used.
As commercially available amphoteric resins, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno's Ajispar PB821, Ajispar PB822, Ajispar PB881 and the like.
These polymer compounds may be used alone or in combination of two or more.

As a specific example 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-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding paragraphs 0075 to 0133 of US2011 / 0214824) can be used, and these are used. The content may be incorporated and incorporated herein by reference.
In addition to the above, the structure has a side chain structure in which acidic groups of paragraphs 0028 to 0084 of JP2011-153283 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular weight compounds containing the components can be used, the contents of which are incorporated herein by reference.

The content of the dispersed resin in the resin composition A is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 1 to 30% by mass, based on the total solid content of the composition.

Examples of the process of dispersing the pigment include a process of using compression, squeezing, impact, shearing, cavitation, or the like as the mechanical force used for the dispersion. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, microfluidizers, and the like. In addition, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" or "Dispersion technology centered on suspension (solid / liquid dispersion system) and practical comprehensive data collection of industrial applications, Management Development Center Publishing Department The process and disperser described in "Published October 10, 1978" can be suitably used. The pigment may be miniaturized by a salt milling step. As the materials, equipment, processing conditions, etc. used in the salt milling step, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used, for example.
Of these, a sand mill (bead mill) is preferable. Further, in the pulverization of pigments in a sand mill (bead mill), it is preferable to use beads having a small diameter and to increase the pulverization efficiency by increasing the filling rate of the beads, etc. It is preferable to remove elementary particles by separation or the like.

<Polymer initiator>
The resin composition A may contain a polymerization initiator.
The polymerization initiator is not particularly limited and may be appropriately selected from known polymerization initiators. For example, a photosensitive initiator (so-called photopolymerization initiator) is preferable.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays visible from the ultraviolet region are preferable. Further, it may be an activator that causes some action with a photoexcited sensitizer to generate an active radical, or may be an initiator that initiates cationic polymerization depending on the type of monomer.
Further, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the 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, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), British Patent No. 1388492, Compound described in JP-A-53-133428, German Patent No. 3337024, F.I. C. J. by Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. No. 4,212,976. Examples include the compounds described in the specification.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivative, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxaziazole compound, and a 3-aryl substituted coumarin compound is preferable. ..

More preferably, it is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallyl imidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, a trihalomethyltriazine compound, an α-aminoketone. At least one compound selected from the group consisting of a compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferable.

In particular, when the resin film of the present invention is used for producing a light-shielding film for a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. It is preferable to be done. From this point of view, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state image sensor, 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 consideration of these points, it is particularly preferable to use an oxime compound as the photopolymerization initiator in order to form a fine pattern such as a solid-state image sensor. Further, by using the oxime compound, the color transfer property can be further improved.
As a specific example 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, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based 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, the compound described in JP-A-2009-191179, in which the 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, a commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both 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), ^Ra 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 ^cs are independent of each other. , Hydrogen atom, alkyl group, or group represented by −OR ^h . R ^h represents an electron-attracting group or an alkyl ether group. However, at least one of the plurality of R ^c represents a group represented by −OR ^h .

In the formula (I), ^Ra represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, and an aryl group or a heterocyclic group is preferable, and a heterocyclic group is more preferable.
The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 15. Examples of the acyl group include an acetyl group and a benzoyl group.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aryl group may be a monocyclic 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 monocyclic ring or a condensed ring. The number of condensations is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and even more preferably 3 to 20. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. 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-mentioned group represented by ^Ra may be unsubstituted or may have a substituent. Substituents include alkyl groups, aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , Examples thereof include -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. 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.
Alkyl group as a substituent, and the carbon number of the alkyl group represented by R ^X1 and R ^X2 are, 1-20 preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a part or all of hydrogen atoms substituted with halogen atoms (preferably fluorine atoms). Further, in the alkyl group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.
Aryl group as a substituent, and the carbon number of the aryl group represented by R ^X1 and R ^X2 are 6-20, more preferably 6 to 15, 6 to 10 is more preferable. The aryl group may be a monocyclic ring or a condensed ring. Further, in the aryl group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.
The heterocyclic group as a substituent and the heterocyclic group represented by ^RX1 and ^RX2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Further, in the hetero group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.

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

In formula (II), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent, R ³ represents an alkyl group or an aryl group, and * represents a bond position. Represents.
In formula (II), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent.
The aromatic hydrocarbon ring may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the ring of the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. As the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable. Among them, it is preferable that at least one of Ar ¹ and Ar ² is a benzene ring, and it is more preferable that Ar ¹ is 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 preferable. The alkyl group and the aryl group may be unsubstituted or have a substituent. Examples of the substituent include the substituents described in the above-mentioned R ^a.
The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring.

In the formula (I), R ^b represents an alkyl group, an aryl group or a heterocyclic group, and an alkyl group or an aryl group is preferable, and an alkyl group is more preferable. Alkyl groups, aryl groups and heterocyclic groups are synonymous with the groups described in ^Ra . These groups may be unsubstituted or have substituents. Examples of the substituent include the substituent described in ^Ra .

In the formula (I), each of the plurality of R ^cs independently represents a hydrogen atom, an alkyl group, or a group represented by −OR ^h . R ^h represents an electron-attracting 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 replaced with a fluorine atom is preferable. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, further 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, further preferably 1 to 10 carbon atoms, and 1 to 4 carbon atoms. Is particularly preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
The total number of carbon atoms of the alkyl ether group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

Of the plurality of R ^cs , 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, It is preferably a hydrogen atom. 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 the formula (I) or the formula (II) include the following compounds.

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

In formula (III), R ¹ and R ² are 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 an aryl group having 6 to 30 carbon atoms. It represents an arylalkyl group having 7 to 30 carbon atoms, and when 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 independent of each other. 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 formula (III), R ⁵ is -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , Represents −OCSR ⁶ , −COSR ⁶ , −CSO R ⁶ , −CN, halogen atom or hydroxyl group, where R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. It represents an arylalkyl group or a heterocyclic group having 4 to 20 carbon atoms, and a represents an integer of 0 to 5.

In the above formula (III), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xsilyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. Direct binding is preferable for X.
Specific examples of the compound represented by the formula (III) include the compounds described in paragraphs 0076 to 0079 of JP-A-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.

The commercially available polymerization initiator is not particularly limited, and IRGACURE OXE 01 (1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] manufactured by BASF Japan Corporation. ), IRGACURE OXE 02 (Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) Thioxanthene-9-one, O-acyloxime compounds (for example, ADEKA Adecaoptomer N-1919, ADEKA ARKULS NCI-831), ADEKA ARKULS NCI-930, etc. are also mentioned. Incorporated into the specification.

The content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, still more preferably 1 to 10% by mass, based on the total solid content of the composition. Particularly preferably, it is 1 to 7% by mass.
The resin composition A may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators. When two or more types are included, the total amount is preferably in the above range.

<Silane coupling agent>
The resin composition A may contain a silane coupling agent.
The "silane coupling agent" is a compound having a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The "hydrolyzable group" refers to a substituent that is directly linked 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 thereof 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.
Further, 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 the silicon atom to which a hydrolyzable group is bonded), and the fluorine atom, Includes silicon atom (excluding silicon atom to which a hydrolyzable group is bonded), alkylene group substituted with silicon atom, linear alkyl group having 8 or more carbon atoms, and branched alkyl group having 3 or more carbon atoms. It is preferable that there is no such thing.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents the bond position.
Formula (Z) * -Si- (R _Z1 ) ₃
In formula (Z), R _Z1 represents a hydrolyzable group, the definition of which 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 the linking group. Of these, an epoxy group is preferable from the viewpoint of improving adhesion, developing resistance, and solvent resistance.
In addition, a radical polymerizable group is also mentioned as a preferable embodiment 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 often 100 to 1000 from the viewpoint of handleability, and 270 or more is preferable, and 270 to 1000 is more preferable, from the viewpoint of more excellent effect of the present invention.

One of the preferred embodiments of the silane coupling agent is the silane coupling agent X represented by the formula (W).
Equation (W) R _Z2- Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, the definition of which 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. Among them, at least one selected from the group consisting of an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group optionally substituted with a halogen atom having 6 to 12 carbon atoms, or at least one selected from the group. these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S-, and SO ₂ -, at least selected from the group consisting of group is preferred, which consist of a combination of one group, an alkylene group optionally substituted with 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 preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and N-β-aminoethyl-γ-aminopropyl-trimethoxy. Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), γ-aminopropyl-trimethoxysilane (Product name manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBM-903), γ-aminopropyl-triethoxysilane (Product name manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBE-903), 3-Methoxyloxypropyltrimethoxysilane (Product name manufactured by Shin-Etsu Chemical Industry Co., Ltd.) KBM-503), 3-glycidoxypropylmethyldimethoxysilane (trade name KBM-402 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (trade name LS-2940 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Glyco Examples thereof include sidoxyoctyltrimethoxysilane (trade name KBM-4803 manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

Another preferred embodiment of the silane coupling agent is 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. Can be mentioned.
The silane coupling agent Y may 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. The atoms and substituents that can be bonded are hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group, alkynyl group, aryl group, alkyl group and / or amino group substitutable with aryl group, silyl. Examples thereof include a group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents are further substituted with 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. , Alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxyl group, or a salt thereof, a sulfo group, or a salt thereof.
At least one hydrolyzable group is bonded to the silicon atom. The definition of 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 preferably has at least one nitrogen atom in the molecule, and the nitrogen atom preferably exists 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 structure of the amino group may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present 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, and the substituents 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. Examples thereof include a group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group and the like.
Further, the nitrogen atom is preferably bonded to a curable functional group via an arbitrary organic linking group. Preferred organic linking groups include the above-mentioned nitrogen atom and substituents 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 preferable range is also as described above.
The silane coupling agent Y may 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. Has 2 to 20 curable functional groups, more preferably 4 to 15 curable functional groups, and even more preferably 6 to 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 examples thereof include the above-mentioned range (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, and 1.0, based on the total solid content in the composition. ~ 6% by mass is more preferable.
The resin composition A may contain one type of silane coupling agent alone, or may contain two or more types. When the composition contains two or more kinds of silane coupling agents, the total may be within the above 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 two or more, further preferably three or more, and particularly preferably five or more. The upper limit is, for example, 15 or less. 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 of chemical forms such as, for example, monomers, prepolymers and oligomers, or mixtures thereof and multimers thereof. Monomers are preferred.
The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500.
The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof. The esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof are preferable. 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 an epoxy, or the above-mentioned unsaturated carboxylic acid. A dehydration condensation reaction product of an acid ester or amide and a monofunctional or polyfunctional carboxylic acid is also preferably used. Further, a reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen group or a tosyloxy group. A reaction product of an unsaturated carboxylic acid ester or amide having a desorbing substituent such as, and a monofunctional or polyfunctional alcohol, amines, or thiols is also suitable. Further, instead of the unsaturated carboxylic acid described above, it is also possible to use a compound group in which a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like is replaced.
As these specific compounds, the compounds described in paragraphs [0995] to [0108] of JP2009-288705A can be preferably used in the present invention.

In the present invention, as the polymerizable compound, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. As an example thereof, the compounds described in paragraphs 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available 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 and SR499 commercially available from Sartmer). preferable. These oligomer types can also be used. Further, 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.
The 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 an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polymerizable compound having a group is more preferable, and more preferably, 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.

The 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 developing and dissolving properties 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.

As the polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc. Examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Of these, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

In the general formula (Z-1), all 6 Rs are groups represented by the following general formula (Z-2), or 1 to 5 of the 6 Rs are the following general formulas (Z). -2) is a group, and the residue is a group represented by the following general formula (Z-3).

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

In the general formula (Z-3), R ¹ indicates a hydrogen atom or a methyl group, and "*" indicates a bond.

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

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

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

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
Further,-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (Z-4) or the general formula (Z-5) is oxygen. A form in which the terminal on the atomic side is bonded to X is preferable.

The compounds represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), all 6 Xs are acryloyl groups, in the general formula (Z-5), all 6 Xs are acryloyl groups, and 6 Xs. Of 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.

The total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) is obtained by ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known step. It can be synthesized from a step of binding a ring-opening skeleton by a reaction and a step of reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. 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 is more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplified compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferable.

Commercially available products of the 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 Sartmer, and 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, manufactured by Co., Ltd.

Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, use of addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Therefore, the resin composition A having a very high photosensitive speed can be obtained.
Commercially available products include urethane oligomer UA-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- Examples thereof include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha).

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

Further, the resin composition A preferably 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 above general formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represent 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 represent 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. It is a value obtained by subtracting a, b, c or d from the number of substituents that can be possessed. However, when Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the fused rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are respectively. It may be independently replaced with a benzene ring surrounded by a broken line, or may be replaced with a ring other than the benzene ring surrounded by a broken line.

In the above general formula (Q3), the aryl group containing the benzene ring represented by Ar ^{11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and is preferably 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 above general formula (Q3), X ^{1 to} X ⁴ each represent a substituent having a polymerizable group independently, and the carbon atom in the above 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 is an alkylene group having 2 to 10 carbon atoms. It is more preferably a group, and even more preferably an alkylene group having 2 to 5 carbon atoms.
Further, in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ , when the aliphatic group is substituted with a hetero atom, it is substituted with -NR- (R is a substituent), an oxygen atom and a sulfur atom. it is preferable that the, -CH not adjacent in the aliphatic group 2 _- is more preferably is substituted with an oxygen atom or a sulfur atom, -CH 2 nonadjacent in the aliphatic group _- is It is more preferred that it is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted at 1 to 2 sites by a hetero atom, more preferably at 1 site by a hetero atom, and Ar ^{11 to} Ar. It is more preferable that one site adjacent to the aryl group containing the benzene ring surrounded by the broken line represented by ¹⁴ is substituted with a heteroatom.
The polymerizable group contained in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is 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 preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and a suitable one can be a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, specifically. Examples include a vinyl group and a (meth) acryloyloxy group. Among them, the (meth) acryloyloxy group is preferable, and the acryloyloxy group is more preferable.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and vinyloxy. The group can be mentioned. Of these, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable.
The polymerizable group contained in the substituents 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 polycyclic aromatic hydrocarbon groups each containing a benzene ring independently surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are benzenes independently surrounded by a broken line. It may be replaced with a ring or a ring other than the benzene ring surrounded by a broken line.

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

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

In the above 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 are substituents that Ar ^{11 to} Ar ¹⁴ can have, respectively. It is a 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 even more preferably 0.
When Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring independently 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 above formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound having a 9,9-bisarylfluorene skeleton, the compounds described in JP-A-2010-254732 can also be preferably used.

Commercially available polymerizable compounds having a cardo skeleton are not limited, and examples thereof include Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

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, further preferably 2% by mass or more. The upper limit is, for example, more preferably 35% by mass or less, further preferably 30% by mass or less.
The polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above 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 to 2. 0 is preferable, and 0.45 to 1.5 is more preferable from the viewpoint of being more excellent in 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 coatability of the resin composition A, and the solubility, coatability, and safety of the polymerizable compound, binder resin, etc. are taken into consideration. It is preferable to be selected.

Examples of the organic solvent 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, etc.)), 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, etc.) )), 2-Oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, 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 (eg, 2) -Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2, -Ethyl oxobutate 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, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3 -Heptanone, etc., and As the aromatic hydrocarbons, for example, toluene, xylene and the like are preferably mentioned.

It is also preferable to mix two or more of these organic solvents from the viewpoints of solubility of the polymerizable compound, binder resin and the like, improvement of the coated surface, and the like. 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 kinds 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.

From the viewpoint of coatability, the content of the organic solvent in the resin composition A is preferably such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, and 10 It is more preferably ~ 50% by mass.
The resin composition A may contain only one kind of organic solvent, or may contain two or more kinds of organic solvents. When two or more types are included, the total amount is preferably in the above range.

<Other additives>
The resin composition A contains various additives such as a filler, an adhesion accelerator, an antioxidant, a polymerization inhibitor, an anti-aggregation agent, a surfactant, an infrared absorber, an ultraviolet absorber, and the like, if necessary. Can be contained. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, and these contents are incorporated in the present specification.
The resin composition A can contain, for example, the sensitizer or photostabilizer described in paragraph 0078 of JP-A-2004-295116, the thermal polymerization inhibitor described in paragraph 1981 of the same publication, and the like.
In addition, 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 various conventionally known inorganic pigments or organic pigments.
Examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and tungsten, as well as composite oxides of the above metals.
Examples of the organic pigment include the following. 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, 129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, 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>
In addition, as the dye, various conventionally known dyes can be mentioned.

Examples of the dye include Japanese Patent Application Laid-Open No. 64-9043, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent No. 2592207, and US Pat. No. 4,808.501. , U.S. Pat. No. 5,667,920, U.S. Patent No. 505950, U.S. Patent No. 566,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 and JP-A-6- Dyes disclosed in Japanese Patent Application Laid-Open No. 194828 can be used. When classified as a chemical structure, pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonor compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethine compound, etc. Can be used. Moreover, you may use a dye multimer as a dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.

These organic pigments or dyes can be used alone or in various combinations to increase the color purity. Two or more types may be used together.

For example, from the viewpoint of adjusting the color, it is preferable to use the red pigment and the titanium nitride-containing particles in combination, and the red pigment is preferably Pigment Red 254, although it is not particularly limited. Further, from the viewpoint of enhancing the light-shielding property, it is preferable to use the yellow pigment and the titanium nitride-containing particles in combination, and the yellow pigment is preferably Pigment Yellow 150, although it is not particularly limited.

<Surfactant>
The composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. 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 containing a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. That is, when a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. It is improved and the applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by 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 property, and has good solubility in the composition.

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC- 103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like can be 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 groups and propyleneoxy groups) (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 compounds is preferably 3,000 to 50,000, for example 14,000.
The 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 nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, and polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF's Pluronic L10, L31, L61, L62, Examples thereof include 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), and NCW-101 manufactured by Wako Pure Chemical Industries, Ltd. NCW-1001 and NCW-1002 can also be used.

Specifically, as cationic surfactants, 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-based (meth) acrylic acid-based (meth) Co) Polymer Polyflow No. 75, No. 90, No. Examples include 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

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

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like. The resin having a polysiloxane structure and the reactive silicone described later are not included in the silicone-based surfactants 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% by mass, more preferably 0.005 to 1.0% by mass, and 0.005 to 0.005 to the total solid content of the composition of the present invention. 0.98% by mass is most preferable.

[Embodiment 1B]
Next, as a method of 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 above-mentioned titanium nitride-containing particles, a binder resin, and a resin having a polysiloxane structure. The resin film can be formed by forming a resin composition containing the above-mentioned constituent material or a precursor material thereof and applying the resin composition onto a substrate.
Further, the resin composition may be a photosensitive resin composition having exposure and developability. In this case, a polymerization initiator, a polymerizable compound, or the like may be further added to the resin composition. Further, a binder resin, a polymerizable compound, a dispersion resin described later, or the like may be used as an alkali-soluble material.
Hereinafter, various materials contained in the above-mentioned resin composition (hereinafter referred to as “resin composition B”) will be described in detail.
The material in the resin composition B is the same except that the filler in the resin composition A is reactive silicone, and the same applies to the preferred embodiment.

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

The reactive silicone resin is a reactive type modification in which a substituent such as an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a methacryl group, a mercapto group, or a phenol group is substituted on the side chain, one end or both ends of the polysiloxane. It is a 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-3311, FM-3325 (or more, (Manufactured by Chisso Co., Ltd.), as epoxy-modified silicone resins, KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), polyether-modified Silicone resins are X-22-4272 and X-22-4952, carboxyl-modified silicone resins are X-22-3701E and X-22-3710 (manufactured by Shin-Etsu Chemical Co., Ltd.), and carbinol-modified silicone resins are used. Is KF-6001, KF-6003 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164C (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as a methacrylic-modified silicone resin, and KF-2001 as a mercapto-modified silicone resin. (The above is manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of the phenol-modified silicone resin include X-22-1821 (above, 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 (all manufactured by Chisso Corporation).

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

In addition, the mass ratio of reactive silicone to the binder resin (binder resin: reactive silicone) is 100: 1 to 100: 30 because of the stable and better expression of the uneven shape and the stability of the coating liquid. It is preferably 100: 5 to 100:30, and more preferably 100: 5 to 100:30.

When the reactive silicone is contained in the resin composition B, the content thereof is preferably 0.2 to 20% by mass, preferably 0.5 to 15% by mass, based on the total solid content in the composition. It is more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass.
The resin composition B may contain only one type of reactive silicone, or may contain two or more types of reactive silicone. When two or more types are included, the total amount is preferably in the above range.

[Method for preparing resin compositions A and B]
The resin compositions A and B can be prepared by mixing the above-mentioned components, respectively.
When preparing the resin compositions A and B, the components constituting the resin compositions A and B may be collectively blended, or each component may be dissolved or dispersed in a solvent and then sequentially blended. In addition, the order of charging and working conditions at the time of blending are not particularly limited. For example, all the components may be dissolved or dispersed in a solvent at the same time to prepare a composition, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions during 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. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon-6 and nylon-6,6, polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight) and the like. There is a filter by. Among these materials, polypropylene (including high-density polypropylene) is preferable.
The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, it is possible to reliably remove fine foreign substances that hinder the preparation of a uniform and smooth resin composition in the subsequent step.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more.
Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. can do.
As the second filter, one 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 liquid, and the second filtering may be performed after mixing the other components.

[Manufacturing method of resin film]
Next, a method for producing the resin film will be described.
The resin film of the first embodiment is preferably produced by using the resin composition A or the resin composition B.
When the resin film of the first embodiment is produced using the resin composition A or B, the method for producing the resin film is a step of applying the resin composition A or B on the substrate to form the 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 active ray-curable material such as a polymerization initiator and a polymerizable compound, the resin composition A or B is used as a substrate as a method for producing the resin film. It is preferable to have a step of forming a coating film (coating film forming step) and a step of exposing the coating film (exposure step).
Further, when the resin composition A or B is a curable composition containing an active ray-curable material such as a polymerization initiator and a polymerizable compound, it is possible to form a patterned resin film. Specific procedures include the above-mentioned coating film forming step, a step of exposing the coating film in a pattern (pattern exposure step), and a step of developing and removing an unexposed portion to form a patterned resin film (development step). ) And is preferable.
Hereinafter, among the above procedures, a method for producing a resin film having a coating film forming step, a pattern exposure step, and a developing step will be described in detail as typical examples.
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. Further, the exposure step and the pattern exposure step are the same procedure except that the exposure is performed in a pattern in the pattern exposure step.

<Coating film forming 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-mentioned titanium nitride-containing particles, a binder resin, a filler, and an active ray-curable material such as a polymerization initiator and a polymerizable compound is formed. When the resin composition B is used, the above-mentioned titanium nitride-containing particles, a binder resin, a resin having a polysiloxane structure formed from a reactive silicone or the like, and the activity of the polymerization initiator, the polymerizable compound and the like are used. A coating film having a linear curable material is formed.
Examples of the substrate include a transparent substrate composed 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.
Further, a substrate for a solid-state image sensor in which a solid-state image sensor (light receiving element) such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor) is provided on the substrate can be used.
As a method of applying the resin composition A or B on the substrate, various methods such as a slit coating method, an inkjet method, a rotary coating method, a spray coating method, a casting coating method, a roll coating method, and a screen printing method are used. be able to.
The rotary coating method and the spray coating method are preferable from the viewpoint that a uniform film thickness can be obtained. When the surface of the substrate is not flat, the spray coating method and the inkjet method are preferable because a uniform film thickness can be obtained.

The coating film formed on the substrate may be heat-treated (prebaked), and the temperature at this time is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 100 ° C. or lower.
The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds. Heating can be performed on a hot plate, an oven, or the like.

As described above, when the resin composition A or B does not contain the active ray-curable material, a resin film is formed on the substrate by carrying out 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, a pattern exposure can be performed by using an exposure device such as a stepper to expose through a mask having a predetermined mask pattern. As a result, the exposed portion can be cured.
As the radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used (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 area, the active ray-curable material is cured.

<Development process>
This step is a step of developing and removing the unexposed portion to form a patterned resin film. The development and removal of the unexposed portion can be performed using a developing solution. As a result, the coating film on the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion (resin film) remains.
As the developer, an organic alkaline developer that does not damage the underlying solid-state image sensor and circuit is desirable.
The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds.

Examples of the alkaline agent used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. , Choline, pyrrol, piperidine, organic alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene. Examples thereof include an aqueous solution in which these alkaline agents are dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.005 to 6% by mass, and particularly preferably 0.01 to 5% by mass.
Moreover, you may use an inorganic alkali as a developer. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate and the like are preferable.
Moreover, you may use a surfactant as a developer. As an example of the surfactant, a nonionic surfactant is preferable.
When a developer composed of such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after 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 low reflectivity and moisture resistance, it is preferable that the pigment layer X1 and the pigment layer X2 containing titanium nitride-containing particles are laminated adjacent to each other. 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 of the resin film on the pigment layer X2 side is small. Ra is preferably 100 Å or more and 2000 Å or less. That is, the pigment layer (pigment layer X2) having the lowest content concentration of the titanium nitride-containing particles is located on the outermost surface side (the layer position farthest from the substrate) of the resin film, so that the pigment layer X2 enters from the surface on the pigment layer X2 side. It can exhibit excellent light scattering with respect to light and have excellent low reflectivity.
Here, the "concentration of titanium nitride-containing particles contained in the pigment layer X1" and the "concentration of titanium nitride-containing particles contained in the pigment layer X2" are the titanium nitrides with respect to the total solid content of each pigment layer. It corresponds to the content of the contained particles.

When the resin film has a two-layer structure of a pigment layer X1 and a pigment layer X2, the concentration of titanium nitride-containing particles in the pigment layer X1 having a high concentration is preferably 10 to 65% by mass, and is preferably 20 to 55. More preferably, it is by mass. On the other hand, the concentration of the titanium nitride-containing particles in the low-concentration pigment layer X2 is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass. Further, (concentration of titanium nitride-containing particles contained in the pigment layer X1)-(concentration of titanium nitride-containing particles contained in the pigment layer X2) is preferably 5 to 40% by mass.

[Second embodiment: Resin film in which at least one of fluorine atoms and silicon atoms is unevenly distributed on the surface]
The resin film in the second embodiment is adjacent to a pigment layer containing titanium nitride-containing particles containing one or more metal atoms other than the above-mentioned titanium atom (hereinafter, simply referred to as “pigment layer”) on the pigment layer. It is characterized in that it has a surface layer (hereinafter, simply referred to as “surface layer”) containing a compound containing at least one of a fluorine atom and a silicon atom.
The thickness of the resin film is not particularly limited, and is preferably 0.2 to 25 μm, more preferably 1.0 to 10 μm. The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thicknesses 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 is a resin composition containing at least titanium nitride-containing particles containing one or more metal atoms other than the above-mentioned titanium atoms, a binder resin, and a compound containing at least one of a fluorine atom and a silicon atom (a resin composition). Hereinafter, it can be formed by preparing "resin composition C") and applying it on 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 later (preferably a resin containing at least one of a fluorine atom and a silicon atom), but these compounds are low. Shows 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 and present in the vicinity of the coating film surface on the opposite side of the substrate. This uneven distribution of the surface is particularly remarkable 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 is formed of a pigment layer (lower layer) containing titanium nitride-containing particles which are black pigments and a surface layer (lower layer) containing a compound containing at least one of a fluorine atom and a silicon atom (a surface layer). 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 by interference to obtain low reflection. Can be done.
Further, the above resin film contains titanium nitride-containing particles as a black pigment in the pigment layer, and the titanium nitride-containing particles and a compound containing at least one of a fluorine atom and a silicon atom synergize with each other. , Has been confirmed to show excellent moisture resistance.
Resins such as (meth) acrylic polymers contain trace amounts of radical initiators and unreacted monomers, and are chained by radicals generated during cutting and cutting of the polymer due to heat, oxygen, and moisture in a moist heat environment. It causes haze accompanied by yellowing of the resin and deterioration of transparency due to radical decomposition (see paragraph [0017] of JP2011-65146A).
The uneven distribution of the compound containing at least one of a hydrophobic fluorine atom and a silicon atom on the surface prevents water from being mixed into the film and prevents the resin from being deteriorated.
Further, although the mechanism is not clear, it is considered that the titanium nitride-containing particles containing one or more metal atoms other than titanium atoms capture the generated radicals even if there is water mixed in the film.

Further, the resin composition C may be a photosensitive resin composition having exposure and developability. In this case, a polymerization initiator, a polymerizable compound, or the like may be further added to the resin composition C. Further, a binder resin, a polymerizable compound, a dispersed resin and the like may be used as an 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>
The 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. The specific compound preferably has a fluorine atom from the viewpoints that the reflectance of the resin film is lower, the pattern linearity of the resin film is more excellent, and the resin film is less likely to be chipped.
Further, 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, and more preferably a (meth) acrylate polymer having a fluorine atom.
One of the preferred embodiments of the specific compound is a compound having no benzene ring structure, and a compound having a fluorine atom and no benzene ring structure is more preferable.
The above-mentioned silane coupling agent is not included in the 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 to 20, more preferably 1 to 10, and further preferably 1 to 5. preferable.
As for the aryl group substituted with a fluorine atom, it is preferable that the aryl group is 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 JP-A-2011-100089 can be referred to, and the contents thereof are described in the present specification. Be incorporated.

Among them, from the viewpoints that the reflectance of the resin film is lower, the pattern linearity of the resin film is more excellent, and the resin film is less likely to be chipped, the specific compound is an alkylene group substituted with a fluorine atom and an oxygen atom. It is preferable to contain a group X (a group represented by the formula (X) (repeating unit)) linked with and, and more preferably a perfluoroalkylene ether group is contained.
Formula _{(X) - (L A -O} ) -
The L _A represents an alkylene group substituted with a fluorine atom. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. An oxygen atom may be contained in the alkylene group substituted with the fluorine atom.
Further, the alkylene group substituted with a fluorine atom may be linear or branched chain.
The "perfluoroalkylene ether group" is intended the L _A is a perfluoroalkylene group. The "perfluoroalkylene group" is intended to be a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms.
The group (repeating unit) represented by the formula (X) may be repeatedly linked, and the number of repeating units thereof is not particularly limited, and 1 to 50 is preferable because the effect of the present invention is more excellent. ~ 20 is more preferable.
That is, it is preferable that the group is represented by the formula (X-1).
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, it preferably contains an alkylsilyl group, an arylsilyl group or the following partial structure (S) (* represents a binding site with another atom).
Partial structure (S)

The total number of carbon atoms of the alkyl chain contained in the alkylsilyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Alkylsilyl group and trialkylsilyl group are preferable.
Examples of the aryl group in the arylsilyl group include a phenyl group.
When the partial structure (S) is included, the cyclic structure may be formed by including the partial structure (S). As the partial structure (S) preferably adopted in the present invention, −Si (R) _2- O—Si (R) _2- (R is an alkyl group having 1 to 3 carbon atoms) and an alkoxysilyl group are preferable. As an example of the structure including the partial structure (S), for example, paragraphs 0277 to 0279 of JP2011-100089A can be referred to, and the contents thereof are incorporated in the present specification.

The specific compound may have at least one of a fluorine atom and a silicon atom, and may have two or more. Further, 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. The curable functional group may be only one type or two or more types. 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, isocyanato group, hydroxyl group, amino group, carboxyl group, thiol group, alkoxysilyl group, methylol group, vinyl group, (meth) acrylamide group. , One or more selected from the group consisting of a styryl group and a maleimide group, and one or more selected from the group consisting of a (meth) acryloyloxy group, an epoxy group and an oxetanyl group. Is more preferable.
When an ethylenically unsaturated group is contained as the 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 fluorine atoms and silicon atoms in one molecule is preferably 1 to 20, and more preferably 3 to 15.
Further, the number of curable functional groups in one molecule is not particularly limited, and two or more are preferable, and four or more are more preferable, in that the effect of the present invention is more excellent. The upper limit is not particularly limited, and is often 10 or less, and more often 6 or less.

When the specific compound is a polymer, it preferably has a structure containing 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). It is preferable to have at least one of the repeating unit represented by the following formula (B2) and the repeating unit represented by the formula (B3).

In formulas (B1) to (B3), R ^{1 to} R ¹¹ independently represent a hydrogen atom, an alkyl group, or a halogen atom. L ^{1 to} L ⁴ each independently represent 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 is a fluorine atom-substituted alkyl group, a fluorine atom-substituted aryl group, an alkylsilyl group, an arylsilyl group, or , Represents a group containing the above partial structure (S), and X ³ represents a repeating unit represented by the formula (X-1).

In formulas (B1) to (B3), it is preferable that R ^{1 to} R ¹¹ are independently hydrogen atoms or alkyl groups, respectively.
When R ^{1 to} R ¹¹ represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable. When R ^{1 to} R ¹¹ represent a halogen atom, a fluorine atom is preferable.
In the formulas (B1) to (B3), when L ^{1 to} L ⁴ represent a divalent linking group, the divalent linking group is substituted with an alkylene group or a halogen atom which may be substituted with a halogen atom. which may be an arylene ^{group, -NR 12 -, - CONR 12} -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof Can be mentioned. Among them, at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms which may be substituted by a halogen atom and an arylene group having 6 to 12 carbon atoms which may be substituted by a halogen atom, or these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S-, and SO ₂ -, at least selected from the group consisting of 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 preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

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

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

Further, specific examples of the repeating unit represented by the above formula (B3) include, but the present invention is not limited thereto. In the specific example, l, m, n, h, j and k represent integers of 1 to 100.

The content of the repeating unit represented by the above formula (B1) is preferably 5 to 98 mol%, more preferably 30 to 95 mol%, based on all the repeating units in the specific compound.
The total content of the repeating unit represented by the above 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%.
When the repeating unit represented by the formula (B2) is not included and the repeating unit represented by the formula (B3) is included, the content of the repeating unit represented by the formula (B2) is 0 mol%. , The content of the repeating unit represented by the formula (B3) is preferably in the above range.

Further, the specific compound may have a repeating unit other than the repeating units represented by the above formulas (B1) to (B3). The content of the other repeating units is preferably 50 mol% or less, more preferably 30 mol% or less, based on all the 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, more preferably 2.00 to 2.90. ..
For the GPC (gel permeation chromatography) method, HLC-8020GPC (manufactured by Tosoh Corporation) was used, and TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) were used as columns. Based on the method using THF (tetrahydrofuran) as the eluent.

Commercially available products of the specific compound include, for example, Megafvck RS-72-K, Megafvck RS-75, Megafvck RS-76-E, and Megafvck RS-76- manufactured by DIC as specific compounds having a fluorine atom. NS, Megafvck RS-77, BYK-UV 3500, BYK-UV 3530, BYK-UV3570, EVONIK TEGO Rad 2010, TEGO Rad 2011, TEGO Rad 2100, as specific compounds having silicon atoms. 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.

As the specific compound, it is preferable that the specific compound alone can form a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm. That is, it is preferable that the refractive index of the film formed from only the specific compound at a wavelength of 550 nm is 1.1 to 1.5.
The preferred range of the refractive index is preferably 1.2 to 1.5, and more preferably 1.3 to 1.5, in terms of low reflectivity of the resin film.

Further, as the compound containing at least one of a fluorine atom and a silicon atom, the reactive silicone contained in the resin composition B can also be used. 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 preferably, 1 to 10% by mass is particularly preferable.
The composition may contain one specific compound alone, or may contain two or more. When the composition contains two or more specific compounds, the total may be within the above 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 a preferred embodiment.

[Method for preparing resin composition C]
The resin composition C can be prepared by mixing the above-mentioned components. The method for preparing the resin composition C is the same as that of the resin compositions A and B described above, and the preferred embodiments are 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, further preferably 100 pt or less, particularly preferably 10 pt or less, and substantially not contained (below the detection limit of the measuring device). That) is the most preferable.
Examples of the method for removing impurities such as metals from various materials include a purification step by filtration using a filter or distillation (particularly thin film distillation, molecular distillation, etc.). The purification process by distillation is, for example, "<Factory Operation Series> Augmentation / Distillation, published on July 31, 1992, Chemical Industry Co., Ltd." or "Chemical Engineering Handbook, published on September 30, 2004, Asakura Shoten, pp. 95-102". Page "is mentioned. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be a composite material in which these materials and an ion exchange medium are combined. The filter may be one that has been previously washed with an 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 pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
Further, as a method for reducing impurities such as metals contained in various materials, a raw material having a low metal content is selected as a raw material constituting various materials, a filter filtration is performed on the raw materials constituting various materials, or Examples of the method include lining the inside of the apparatus with Teflon (registered trademark) and performing distillation under conditions in which contamination is suppressed as much as possible. The preferred 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 by an adsorbent, and filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

[Manufacturing method of resin film]
Next, a method for producing the resin film will be described.
The resin film of the second embodiment is preferably produced by using the resin composition C. It should be noted that this does not prevent the method of forming the surface layer by using a compound containing at least one of a fluorine atom and a silicon atom on the upper surface of the pigment layer after the pigment layer is formed.
When the resin film of the second embodiment is produced using the resin composition C, a step of applying the resin composition C on a substrate to form a resin film composed of a pigment layer and a surface layer (resin layer formation). It is preferable to have at least a step).
When the resin composition C is a curable composition containing an active ray-curable material such as a polymerization initiator and a polymerizable compound, the resin composition C is applied onto the substrate as a method for producing the resin film. It is preferable to have a step of forming a coating film (coating film forming step) and a step of exposing the coating film (exposure step).
Further, when the resin composition C is a curable composition containing an active ray-curable material such as a polymerization initiator and a polymerizable compound, it is possible to form a patterned resin film. Specific procedures include the above-mentioned coating film forming step, a step of exposing the coating film in a pattern (pattern exposure step), and a step of developing and removing an unexposed portion to form a patterned resin film (development step). ) And is preferable.
The specific procedure of each step is the same as the procedure of each step in the first embodiment, and the preferred embodiment thereof is also the same.

[Third embodiment: a resin film in which Ra is 100 to 2000 Å and a compound containing at least one of a fluorine atom and a silicon atom is unevenly distributed on the surface]
Further, as a modification of the first embodiment (third embodiment), the resin film of the first embodiment contains titanium nitride-containing particles containing at least one metal atom other than the above-mentioned titanium atom. It has a two-layer structure including a pigment layer containing the pigment layer and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom arranged adjacently on the pigment layer, and is the surface of the surface layer which is the outermost surface of the resin film. The roughness Ra may be 100 to 2000 Å.
By having the resin film having the above structure, it exhibits excellent moisture resistance and further excellent low reflectivity.

In the case of the above aspect, a compound containing at least one of a fluorine atom and a silicon atom may be further added to the above-mentioned resin composition A.
The compound containing at least one of a fluorine atom and a silicon atom is the same as that described above in the resin composition C, and the same applies to a preferred embodiment (including a blending amount).
Further, the method for producing the resin film of the third embodiment is the same as that of the first embodiment, and the preferred embodiment thereof is also the same.

[Fourth Embodiment: Resin film in which pigment layers having different optical densities are laminated]
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 kind of metal atom other than the above-mentioned titanium atom are laminated adjacent to each other. It is characterized in that the concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other.
Here, the "concentration of titanium nitride-containing particles contained in the pigment layer Y1" and the "concentration of titanium nitride-containing particles contained in the pigment layer Y2" are the titanium nitrides with respect to the total solid content of each pigment layer. It corresponds to the content of the contained particles.

The method for producing the resin film in the fourth embodiment is not particularly limited, and a pigment layer is used on the substrate using a resin composition (hereinafter, also referred to as “resin composition D”) for forming the pigment layer Y1. A pigment layer Y2 is formed on the pigment layer Y1 by using a step of forming Y1 (a step of forming the pigment layer Y1) and a resin composition for forming the pigment layer Y2 (hereinafter, also referred to as “resin composition E”). It has at least a 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 one of the pigment layer Y1 and the pigment layer Y2 becomes 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 having a smaller concentration of titanium nitride-containing particles. 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 on the surface of the pigment layer Y1 and the pigment layer Y1 and the pigment layer Y2 The light reflected at the interface with the light is canceled by the interference, and the low reflectivity can be obtained. 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 the titanium nitride-containing particles in the pigment layer having a high concentration is preferably 10 to 65% by mass, more preferably 30 to 55% by mass. The concentration of the titanium nitride-containing particles in the low-concentration pigment layer is preferably 1 to 45% by mass, more preferably 1 to 40% by mass. The absolute value of (concentration of titanium nitride-containing particles contained in the pigment layer Y1)-(concentration of titanium nitride-containing particles contained in the pigment layer Y2) is preferably 5 to 40% by mass.

The film thicknesses of the pigment layers Y1 and Y2 are preferably 0.3 to 1.2 μm, and more preferably 0.4 to 1.0 μm, respectively. The total film thickness of both layers is preferably 0.5 to 2.0 μm, more preferably 1.0 to 1.5 μm. The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thicknesses of any five or more points of the film and arithmetically averaging them.

The optical density of the resin film (hereinafter referred to as “OD value”) 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 total OD value is less than 3, the light from the backlight is partially transmitted, which causes a decrease in contrast. On the other hand, when it exceeds 5, the amount of the black pigment added tends to increase and the reflectance tends to be relatively high.

The OD value of the pigment layer in which the concentration of the titanium nitride-containing particles is low is preferably 0.5 to 2.0, 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, more preferably 2.0 to 3.5.

Examples of the material contained in the resin compositions D and E include the material contained in the resin composition A of the first embodiment, and the preferred range is also the same.
When the resin compositions D and E are curable compositions containing an active ray-curable material such as a polymerization initiator and a polymerizable compound, they further include a step of exposing the pigment layer (exposure step). You may. When the exposure step is a step of exposing the pigment layer in a pattern, a step of developing and removing an unexposed portion to form a colored pattern (development step) may be further provided after the exposure step.
The preferred embodiments of the coating film forming step, the exposure step, and the developing step are the same as those of the pigment layer forming step, the exposure step, and the developing step in the first embodiment, and the preferred embodiments thereof 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 in which the resin film is cured by exposure can be preferably used. As will be described later, the light-shielding film is appropriately arranged on each member, and may be arranged in a frame shape, for example.

The color filter can be suitably used for a solid-state image sensor such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), and is particularly suitable for a high-resolution CCD or CMOS having more than 1 million pixels. Is. The color filter can be used, for example, by arranging it between a light receiving portion of each pixel constituting the CCD or CMOS and a microlens for condensing light.

Further, 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, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like. 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 transmission on one surface of a substrate. The lower electrode is preferably made of a material having sufficient reflectance in the wavelength range of visible light. The organic EL layer preferably includes a plurality of light emitting layers and has a laminated structure (tandem structure) in which the plurality of light emitting layers are laminated. The organic EL layer can include, for example, a red light emitting layer, a green light emitting layer, and a blue light emitting layer in a plurality of light emitting layers. Then, together with the plurality of light emitting layers, it is preferable that they also have a plurality of light emitting auxiliary layers for causing the light emitting layer to emit light. The organic EL layer can have, for example, a laminated structure in which light emitting layers and light emitting auxiliary layers are alternately laminated. 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 by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-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, spectroscopy having excellent color reproducibility can be obtained, and a clearer image or image can be displayed.

The light-shielding film may be formed and used on various members (for example, an infrared light cut filter, an outer peripheral portion of a solid-state image sensor, a wafer-level lens outer peripheral portion, a back surface of a solid-state image sensor, etc.) in an image display device or a sensor module. it can.
Further, an infrared light cut filter with a light shielding film may be formed by forming a light shielding film on at least a part of the surface of the 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 above-mentioned thickness is an average thickness, which 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, further preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light-shielding film is a value obtained by incident light of 400 to 700 nm into the light-shielding film at an incident angle of 5 ° and measuring the reflectance with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technology.

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

A transfer electrode made of a plurality of photodiodes, polyvinyl, etc. constituting a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and the photodiode receives light on the photodiode and the transfer electrode. It has a light-shielding film with only a portion open, a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part on the light-shielding film, and a color filter is placed on the device protective film. It is a structure to have.
Further, a configuration having a light collecting means (for example, a microlens) on the device protective layer and below the color filter (the side close to the substrate), a configuration having a light collecting means on the color filter, and the like may be used. .. Further, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.

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

For details on the definition of display devices or the details of each display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Issued in the first year) ”etc. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

The color filter in the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. A color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Publishing Co., Ltd. in 1996)". Further, the present invention includes a liquid crystal display device having an enlarged viewing angle such as a transverse electric field drive method such as IPS (In Plane Switching) and a pixel division method such as MVA (Multi-dominant Vertical Alginment), as well as STN (Super-Twist). It can also be applied to Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optical).
Further, the color filter in the present invention can also be used in 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 are required for the interlayer insulating film, that is, low dielectric constant and resistance to the stripping liquid, in addition to the usual 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 type liquid crystal display device having high resolution and excellent long-term durability. In addition, in order to satisfy the required characteristics of 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-Latest Trends in Technology and Market- (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 materials, for example, "'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima Co., Ltd., published in 1994)", "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)" (Omote Yoshikichi (Omote Yoshikichi) Fuji Chimera Research Institute, Inc., published in 2003) ”.
Regarding the backlight, in addition to SID meeting Digest 1380 (2005) (A.Konno et.al), pages 18 to 24 (Yasuhiro Shima) and pages 25 to 30 (Takaaki Yagi) of the December 2005 issue of Monthly Display. It is described in.

In addition, 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 compound machine or a scanner; a surveillance camera. , Bar code readers, automatic cash deposit machines (ATMs), high-speed cameras, or industrial equipment such as personal identification using face image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, catheters, etc. Medical camera equipment; biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological / ocean observation cameras, land resource exploration cameras, or space equipment such as exploration cameras for space astronomical / deep space targets. It can be used as a light-shielding member, a light-shielding layer, an antireflection member, or an antireflection layer of an optical filter or module used in

Further, the cured film obtained by curing the curable composition can also be used for applications such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). It is not particularly limited, and is preferably used for an optical filter or an optical film used for a micro LED or a micro OLED, as well as a member for which a light-shielding function or an antireflection function is provided.
Examples of the micro LED or the micro OLED include those of JP-A-2015-5572 or JP-A-2014-533890.

Further, the cured film obtained by curing the curable composition can also be used for applications such as quantum dot displays. It is not particularly limited, and is suitably used for an optical filter or an optical film used for a quantum dot display, as well as a member for which a light-shielding function or an antireflection function is imparted.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203 or US Patent Application Publication No. 2014/0035960. Can be mentioned.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

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

(Pigment)
(Black pigment Pig-1)
The 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 20 L / min
Powder supply JEOL powder supply equipment TP-99010FDR
Supply gas Nitrogen 15L / min
Supply amount 15g / min
Powder Ti powder Toho Titanium TC-200
Ag powder Mitsui Kinzoku SPQ03R
Fe powder JFE Steel JIP 270M

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. Was allowed to stand for 24 hours under the condition of 30 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-1) were measured by ICP emission spectroscopy.
The content of Ti atom was 60% by mass, the content of Ag atom was 15% by mass, and the content of Fe atom 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 method, an ICP emission spectroscopic analyzer "SPS3000" (trade name) manufactured by Seiko Instruments was used.
The contents of nitrogen atoms and oxygen atoms were measured using the oxygen / nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by Horiba Seisakusho, and calculated by the inert gas melting-thermal conductivity method. did. 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-1, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-1. It was 5% by mass with respect to.

Further, the black pigment Pig-1 was subjected to an X-ray diffraction test by the following method.
For X-ray diffraction, a powder sample was packed in an aluminum standard sample holder and measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Denki Co., Ltd.). As the 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 set to 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 the above was measured, and this isotherm was analyzed and obtained by the BET method. As a result, the specific surface area of the black pigment Pig-1 determined by the BET method was 29 m ² / g.

(Black pigment Pig-2)
The 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 20 L / min
Powder supply JEOL powder supply equipment TP-99010FDR
Supply gas Nitrogen 15L / min
Supply amount 15g / min
Powder Ti powder Toho Titanium TC-200
Ag powder Mitsui Kinzoku SPQ03R
Ni powder made by Toho Titanium

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. Was allowed to stand for 24 hours under the condition of 30 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-2) were measured by ICP emission spectroscopy.
The content of Ti atom was 65% by mass, the content of Ag atom was 8% by mass, and the content of Ni atom 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 method, an ICP emission spectroscopic analyzer "SPS3000" (trade name) manufactured by Seiko Instruments was used.
The contents of nitrogen atoms and oxygen atoms were measured using the oxygen / nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by Horiba Seisakusho, and calculated by the 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 (100% by mass) of the black pigment Pig-2, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-2. It was 5% by mass with respect to.

Further, the black pigment Pig-2 was subjected to an X-ray diffraction test by the following method.
For X-ray diffraction, a powder sample was packed in an aluminum standard sample holder and measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Denki Co., Ltd.). As the 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 set to 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 the above was measured, and this isotherm was analyzed and obtained by the BET method. As a result, the specific surface area of the black pigment Pig-2 determined by the BET method was 33 m ² / g.

(Black pigment Pig-3)
The black pigment Pig-3 was produced by the same method as the black pigment Pig-2 except that the following powder was used. The V powder refers to vanadium powder.
Powder Ti powder Toho Titanium TC-200
Ag powder Mitsui Kinzoku SPQ03R
V powder Taiyo Koko VN200

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 100 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. Was allowed to stand for 24 hours at a temperature of 100 ° C.

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

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

(Black pigment Pig-4)
The black pigment Pig-4 was prepared by the same method as the black pigment Pig-2 except that the following powder was used. In addition, W powder refers to tungsten powder.
Powder Ti powder Toho Titanium TC-200
W powder WH made by Japan New Metal
Fe powder JFE Steel JIP 270M

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 200 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. Was allowed to stand for 24 hours at a temperature of 200 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-4) were measured by the same method as that of the black pigment Pig-2.
As a result, the content of Ti atom was 50% by mass, the content of W atom was 12.99% by mass, and the content of Fe atom was 0.01% by mass with respect to the total amount (100% by mass) of the black pigment Pig-4. %Met.
The contents of nitrogen atoms and oxygen atoms were also measured by the same method as that of 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% by 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-4 was 43.0. It was °.

When the specific surface area of the black pigment Pig-4 was determined by the same method as that of 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 by the same method as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder Toho Titanium TC-200
Ni powder made by Toho Titanium
Fe powder JFE Steel JIP 270M

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 200 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. Was allowed to stand for 24 hours at a temperature of 200 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-5) were measured by the same method as that of the black pigment Pig-2.
As a result, the content of Ti atom was 52% by mass, the content of Ni atom was 5% by mass, and the content of Fe atom was 2% by mass with respect to the total amount (100% by mass) of the black pigment Pig-5. ..
The contents of nitrogen atoms and oxygen atoms were also measured by the same method as that of 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-5, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-5. It was 21% by 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-5 was 43.5. It was °.

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

(Black pigment Pig-6)
The black pigment Pig-6 was produced by the same method as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder Toho Titanium TC-200
Ag powder Mitsui Kinzoku SPQ03R
W powder WH made by Japan New Metal
V powder Taiyo Koko VN200

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 100 ppm. Was allowed to stand for 24 hours at a temperature of 30 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-6) were measured by the same method as that of the black pigment Pig-2.
As a result, the content of Ti atom was 57% by mass, the content of Ag atom was 10% by mass, and the content of W atom was 7.9% by mass with respect to the total amount (100% by mass) of the black pigment Pig-6. The content of V atom was 0.01% by mass.
The contents of nitrogen atoms and oxygen atoms were also measured by the same method as that of 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-6, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-6. It was 7% by 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-6 was 42.7. It was °.

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

(Black pigment Pig-7)
The black pigment Pig-7 was prepared by the same method as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder Toho Titanium TC-200
Ag powder Mitsui Kinzoku SPQ03R
Fe powder JFE Steel JIP 270M

The particles after plasma treatment are allowed to stand for 24 hours under the condition of O ₂ concentration of 50 ppm or less and 300 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. Was allowed to stand for 24 hours at a temperature of 300 ° C.

The contents of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-7) were measured by the same method as that of the black pigment Pig-2.
As a result, the content of Ti atom was 50% by mass, the content of Ag atom was 5% by mass, and the content of Fe atom was 2% by mass with respect to the total amount (100% by mass) of the black pigment Pig-7. ..
The contents of nitrogen atoms and oxygen atoms were also measured by the same method as that of 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-7, and the content of oxygen atoms is the total amount (100% by mass) of the black pigment Pig-7. It was 23% by 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-7 was 43.7. It was °.

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

(Black pigment Pig-8)
The black pigment Pig-8 was prepared by the same method as the black pigment Pig-2 except that the following powder was used.
Powder Ti powder Toho Titanium TC-200
Ni powder made by Toho Titanium
V powder Taiyo Koko VN200

The particles after plasma treatment are allowed to stand for 24 hours under the conditions of O ₂ concentration of 50 ppm or less and 300 ° C. in an Ar gas atmosphere, and then O ₂ gas is introduced into the Ar gas atmosphere so that the O ₂ concentration becomes 1000 ppm. Was allowed to stand for 24 hours at a temperature of 300 ° C.

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

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

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

(Method for producing pigment dispersion A)
The components shown in composition 1 below were mixed for 15 minutes using a stirrer (Eurostar manufactured by IKA) to obtain a 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 atoms in the graft chain (excluding hydrogen atoms) was 117.

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

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

(Method for producing pigment dispersion B)
The pigment dispersion liquid B was prepared by the same method as the above-mentioned production method of the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with Pig-2.

(Method for producing pigment dispersion C)
The pigment dispersion liquid C was prepared by the same method as the above-mentioned production method of the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with "13MT (trade name)" manufactured by Mitsubishi Materials Corporation.
The pigment particles contained in "13MT (trade name)" manufactured by Mitsubishi Materials Corporation are titanium oxynitride.

(Method for producing pigment dispersion D)
The pigment dispersion D was prepared by the same method as the method for producing the pigment dispersion A except that the resin (X-1) was replaced with the resin (X-2) having the following structure.

(Resin (X-2))

The weight average molecular weight of the resin (X-2) was 25,000, the acid value was 53 mgKOH / g, and the number of atoms in the graft chain (excluding hydrogen atoms) was 72.

(Method for producing pigment dispersion E)
The pigment dispersion E was prepared by the same method as the method for producing the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-3.

(Method for producing pigment dispersion F)
The pigment dispersion liquid F was prepared by the same method as the above-mentioned production method of the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-4.

(Method for producing pigment dispersion G)
The pigment dispersion liquid G was prepared by the same method as the above-mentioned production method of the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-5.

(Method for producing pigment dispersion H)
The pigment dispersion liquid H was prepared by the same method as the above-mentioned production method of the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-6.

(Method for producing pigment dispersion I)
The pigment dispersion I was prepared by the same method as the method for producing the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-7.

(Method for producing pigment dispersion J)
The pigment dispersion J was prepared by the same method as the method for producing 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> in the literature (International Publication No. 2015/029643).

(Binder resin)
・ P-1: Acrybase FF-187 (manufactured by 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 were mixed to obtain a mixture, and then 3,3', 4,4'-oxydiphthalcarboxylic acid dianhydride (0.975 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 the polymer 3.

・ P-4:
After synthesizing a methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Patent No. 312476; Example 1), 40 parts by mass of glycidyl methacrylate was added. Then, after reprecipitation with purified water, the solid content was recovered by filtration, and the solid content was 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. Obtained powder.

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

(Filler)
Hollow silica: thrulia 5320, maximum particle distribution: 75 nm, manufactured by Nikki Catalyst Kasei Co., Ltd. (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-BB1, particle distribution maximum value: 30 nm, manufactured by Koshin Chemical Co., Ltd. (60 wt% PGME solution)
-Acrylic particles 1: MX-80H3wT, maximum particle distribution: 800 nm, manufactured by Soken Chemical Co., Ltd. (powder)
-Acrylic particles 2: MP-300, maximum particle distribution: 100 nm, manufactured by Soken Chemical Co., Ltd.

(Compound containing at least one of fluorine atom and silicon atom)
・ S-1: Mega Fvck RS-72-K (manufactured by DIC Corporation)
-S-2: Megafuck RS-55 (containing fluorine and silicon atoms, manufactured by DIC Corporation)
-S-3: KF-6001 (Hydroxy group-containing silicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
Both S-1 and S-2 are polymer compounds containing 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: High solve BDM (diethylene glycol butyl methyl ether, boiling point 212 ° C, manufactured by Toho Chemical Industry Co., Ltd.)

(Polymer initiator)
・ K-1: Irgacure OXE02 (manufactured by BASF Japan Ltd.)
-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 with the following structure (manufactured by Nippon Kayaku Co., Ltd.)

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

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

[Preparation and evaluation of resin film 1]
(1) Preparation of Resin Composition A resin composition was prepared by stirring and mixing each component as shown in Tables 2 and 3 described later.
The resin compositions of Examples 1 to 16 were all prepared so that the solid content in the composition was 27.5% by mass. Further, 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 and that of Example 7 was 30% by mass except for Example 7. Further, in each of the resin compositions of Examples 8 to 14 and Examples 1A and 1A, the mass ratio (M /) of the content (M) of the polymerizable compound to the total content (B) of the dispersed resin and the 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 Sururia 5320 (20% MIBK solution), 55 g of pigment dispersion A, The resin composition was prepared by adding in this order and stirring with a stirrer for 30 minutes.

(Example 2)
The resin composition is the same as in Example 1 except that the thrulia 5320 (20% MIBK solution) is replaced with silica 1 (FF-D-B1, particle distribution maximum value: 300 nm, manufactured by Koshin Chemical Co., Ltd.) (72 wt% PGME solution). The thing was prepared. The desired solid content concentration was obtained by adjusting PGMEA.

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

(Example 4)
To a 200 g container (dispo 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 to form a resin composition. The thing was prepared.

(Example 5)
A resin composition was prepared in the same manner as in Example 1 except that the pigment dispersion liquid A was replaced with the pigment dispersion liquid 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 stirrer for 30 minutes. The resin composition was prepared by stirring.

(Comparative Example 1)
The resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the pigment dispersion liquid A was replaced with the pigment dispersion liquid C.

(Comparative Example 2)
To a 200 g container (dispo cup), add 24 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 21 g of PGMEA, 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), and P-3 (20% PGMEA (propylene glycol monomethyl ether)). Acetate) solution) 7 g, thruria 5320 (20% MIBK solution) 17 g, pigment dispersion A (black pigment: 8.2 g, resin X-1: 2.5 g, PGMEA: 13 g, butyl acetate: 9.1 g) Was added in this order in this order, and the mixture was stirred with a stirrer for 30 minutes 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 IrgacureOXE02 (manufactured by BASF Japan), 1 silica. (FF-DB1, particle distribution maximum value: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, silica is 42 wt% in solid content) was added in an order of 4 g, pigment dispersion A was added in this order, and 30 in a stirrer. A resin composition was prepared by stirring for minutes.

(Example 10)
A resin composition was prepared in the same manner as in Example 8 except that thruria 5320 (20% MIBK solution) was replaced with acrylic particles 1 (MX-80H3wT, maximum particle distribution: 800 nm, manufactured by Soken Kagaku Co., Ltd.) (powder). .. The desired solid content concentration was obtained 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 IrgacureOXE02 (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 liquid A was replaced with the pigment dispersion liquid B.

(Example 13)
In a 200 g container (dispo 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, and thrulia 5320 (20% MIBK). Solution) 13 g, red dispersion (prepared by the method of paragraph <0409> of International Publication No. 2015/029643) 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, 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, PGMEA was 34 g, IrgacureOXE02 (manufactured by BASF Japan) was 1 g, KF-6001 was 3 g, and pigment dispersion A was 55 g 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 IrgacureOXE02 (manufactured by BASF Japan), silica 2 (FF-BB1, particle distribution maximum value: 30 nm, manufactured by Koshin Chemical Co., Ltd., 60 wt% PGME solution, silica is 10 wt% in solid content) was added in 7 g, pigment dispersion A was added in this order, and 30 in a stirrer. A resin composition was prepared by stirring for minutes.

(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 IrgureOXE02 (manufactured by BASF Japan), Add 0.3 g of silica 1 (FF-D-B1, maximum particle distribution: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, 42 wt% of silica in solid content), 55 g of pigment dispersion A, in this order. , Stirrer was stirred for 30 minutes to prepare a resin composition.

(2) Preparation of Resin Film After spin-coating the resin compositions of each Example and Comparative Example on a glass substrate (Corning 1737 [trade name], manufactured by Corning Inc.), a hot plate at 100 ° C. was used for 2 minutes. Heat treatment (pre-baking) was performed. Then, an exposure treatment (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 1000 mJ / cm ² ) was carried out on the coating film obtained above via a predetermined mask.
After that, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to prepare a substrate with a resin film.

(3) Evaluation <Evaluation of contact angle>
The contact angle was evaluated using the prepared substrate with a resin film. Specifically, after dropping one drop of pure water on the resin film on the substrate, the static contact angle after 5 seconds has passed is automatically measured by the automatic contact angle meter (Drop Master 500 manufactured by Kyowa Surface Chemistry Co., Ltd. [Product name]. ]) Was used, and automatic measurement was performed by the θ / 2 method (measurement temperature: 25 ° C.). The same measurement was performed 5 times, and the average value was taken as the 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 prepared substrate with a resin film. Specifically, light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° on the produced substrate with a resin film, and the reflectance was measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. .. In the table, the smaller the reflectance value, the lower the reflectance.
The results are shown in Tables 2 and 3.

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

<Evaluation of moisture resistance>
Moisture resistance was evaluated using the prepared substrate with a resin film. Specifically, a high-temperature and high-humidity test was carried out for 750 hours under the conditions of a temperature of 85 ° C. and a humidity of 95% using a high-acceleration life test device (EHS-221 manufactured by ESPEC).
For the substrate with resin film before and after the moisture resistance test, the rate of change of reflectance at a wavelength of 400 nm (a spectroscope "UV4100 (trade name)" manufactured by Hitachi High-Technologies Corporation was used to measure the reflectance) was 3 in absolute value. % Or more is "D", the same change rate is 1% or more and less than 3% is "C", the same change rate is 0.5% or more and less than 1% is "B", the same change rate is Those less than 0.5% were evaluated as "A".
It should be noted that the decrease in reflectance due to the moisture resistance test is due to a phenomenon such as film surface roughness occurring 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>
A rubbing test evaluation was performed using the prepared substrate with a resin film. Specifically, the rubbing cloth was rubbed 10 times with a force of 1 kgf, and the scratches on the surface of the resin film were visually observed. The same evaluation was performed three times, and those with scratches confirmed in any of the evaluations were C, those with scratches on any one of the three evaluations were B, and all evaluations had scratches. Those that could not be confirmed were designated as A.
The results are shown in Tables 2 and 3.

Further, in Example 7, the contact angle was 110 ° C., the reflectance was 2% (reflectance at 400 nm), and the surface roughness was 300 Å. 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 mean roughness Ra) of 100 to 2000 Å can be obtained. It was confirmed that it has excellent low reflectivity and 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 low reflectivity was superior.
Further, from the comparison between Example 1 and Example 5, when particles containing silver and iron as metal atoms are used as the titanium nitride-containing particles containing a metal atom other than the titanium atom, the moisture resistance is increased. 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 dispersed resin and the binder resin is different from each other. Comparing Example 15 (M / B: 0.39) and Example 16 (M / B: 1.1), Example 8 and Example in which the M / B is in the range of 0.45 to 1.5 At No. 16, better scratch resistance was confirmed.

In Example 16, the total amount of the binder resin and the polymerizable compound was not changed, and the amount of the binder resin and the polymerizable compound was adjusted so that the M / B was 1.6. The 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".

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

Further, when Example 9 and Example 2A were compared, the moisture resistance was low in Example 2A in which the filler content was less than 1.0% by mass.

On the other hand, the resin film of Comparative Example 1 did not contain titanium nitride-containing particles containing metal atoms other than titanium atoms, and therefore had lower moisture resistance than the resin film of Example 1. As described above, trace amounts of radical initiators, unreacted monomers, etc. are present in resin films such as (meth) acrylic polymers, and these generate radicals due to heat, oxygen, and moisture in a moist 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 the radicals generated in the film are trapped by the metal atoms, so that the film is less likely to be altered. It is presumed to have excellent moisture resistance. On the other hand, the resin film of Comparative Example 1 was surface-altered by radicals, resulting in poor moisture resistance.

Further, since the resin film of Comparative Example 2 did not have a predetermined uneven structure on the surface, it did not satisfy the desired degree in both low reflectivity and moisture resistance.
In addition, it is presumed that the filler (particularly silica particles) contained as a component for forming irregularities is unevenly distributed on the surface of the resin film and has a function of suppressing contact between the titanium nitride-containing particles and water. ing. It is considered that the fact that this filler was not contained in Comparative Example 2 also reduced the moisture resistance.

From the comparison between Comparative Example 1 and Comparative Example 2 and Example, it is clear that the resin film of Example significantly improves low reflectivity and moisture resistance.

[Preparation and evaluation of resin film 2]
(1) Preparation of Resin Composition A resin composition (Examples 17 to 22, Examples 1B to 3B, Comparative Examples 2 and 3) was prepared by mixing each component as shown in Tables 4 and 5 described later. The resin compositions of Examples 17 to 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. Further, in the resin compositions of Examples 20 to 22, the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersed resin and the binder resin is about 0.9. It was prepared to be. The resin compositions of Examples 1B and 2B in Table 5 have the same composition as that of Example 20 except that (M / B) is 0.37 and 1.2, respectively.

Further, each component as shown in Table 6 described later was mixed to prepare a resin composition (Examples 1C to 6C). The compositions of Examples 1C to 6C are the same as those of Example 20 except that the dispersion liquid types are 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, Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 5 g 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 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) A resin composition was prepared in the same manner as in Example 17 except that the solution was replaced with 1 g. The desired solid content concentration was obtained by adjusting PGMEA.

(Example 19)
Resin composition similar to 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. The desired solid content concentration was obtained 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 IrgacureOXE02 (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)
Replace Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) with Megafuck RS-55 (S-2) (100 wt% solution), and further change the polymerization initiator from IrgacureOXE02 (manufactured by BASF Japan). A resin composition was prepared in the same manner as in Example 20 except that it was replaced with K-2. The desired solid content concentration was obtained 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 replaced with 3 g of the polymerizable compound M-1 and 2 g of M-22.

(Comparative Example 2)
As Comparative Example 2, the one having the same composition as Comparative Example 2 described in Table 2 above was used.

(Comparative Example 3)
The resin composition of Comparative Example 3 was prepared in the same manner as in Example 17 except that the pigment dispersion liquid A was replaced with the pigment dispersion liquid 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 IrgacureOXE02 (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 = 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 IrgacureOXE02 (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)
The resin composition of Example 3B was prepared in the same manner as in Example 20 except that the dispersion liquid A was changed to the dispersion liquid B.

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

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

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

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

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

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

(2) Preparation of Resin Film After spin-coating the resin compositions of each Example and Comparative Example on a glass substrate (Corning 1737 [trade name], manufactured by Corning Inc.), a hot plate at 100 ° C. was used for 2 minutes. Heat treatment (pre-baking) was performed. Then, an exposure treatment (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 1000 mJ / cm ² ) was carried out on the coating film obtained above via a predetermined mask.
After that, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to prepare a substrate with a resin film.

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

Each of the resin films of the above-mentioned examples 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 has excellent low reflectivity and 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 dispersed resin and the binder resin is different. Comparing Example 1B (M / B: 0.37) and Example 2B (M / B: 1.2), Example 20 and Example in which the M / B is in the range of 0.45 to 1.5 In 2B, better abrasion resistance was confirmed.

In Example 2B, the photosensitive resin was similarly prepared except that the total amount of the binder resin and the polymerizable compound was not changed and the amounts of the binder resin and the polymerizable compound were adjusted so that the M / B was 1.6. The 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 the comparison between Example 20 and Example 3B, when particles containing silver and iron as metal atoms are used as the titanium nitride-containing particles containing metal atoms other than titanium atoms, the moisture resistance is increased. It was confirmed to be excellent.

Since the resin film of Comparative Example 2 did not have a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom, neither low reflectivity nor moisture resistance satisfied the desired degree.
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, but titanium. Since the nitride-containing particles did not contain metal atoms other than titanium atoms, the moisture resistance was poor.
Further, from the comparison between Comparative Example 2 and Comparative Example 3 and Example, it is clear that the resin film of Example significantly improves low reflectivity and moisture resistance.

Also in Examples 1C to 6C, good low reflectivity and moisture resistance were obtained as in Example 20.
Further, it was found that the optical density of Example 3C was slightly lowered, and that the optical density was further lowered in Examples 5C and 6C, but there was no problem in practical use.

[Preparation and evaluation of resin film 3]
(1) Preparation of Resin Composition A resin composition (Examples 23 to 37, Examples 1D and 2D, Comparative Examples 4, 5 and 6) is prepared by mixing each component as shown in Tables 7 and 8 described later. did. The resin compositions of Examples 23 to 37 and Comparative Examples 4, 5 and 6 each had a solid content of 27.5% by mass in the composition, and the total content of the dispersed resin and the binder resin (B). ), The mass ratio (M / B) of the content (M) of the polymerizable compound was adjusted to be about 0.9.
The resin compositions of Examples 23 to 37 had a pigment concentration of 50% by mass with respect to the total solid content in the compositions except for the resin compositions of Examples 24 and 27. Examples 24 and 27 were prepared so that the pigment concentration with respect to the total solid content in the composition was 40% by mass.

The resin film 3 corresponds to the above-mentioned resin film 1 or a patterned resin film obtained by exposure-developing the resin film 2.

(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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 replaced with 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 replaced with 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 5320 Add 20.7 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 0.3 g of LS-2940, 55 g of pigment dispersion A in this order, and stir with a stirrer for 30 minutes to make a resin. The 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 replaced with 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 high solve BDM, IrgacureOXE02 (manufactured by BASF Japan) 1 g, Sururia 5320 (20% MIBK solution) 21 g, F-1 (1% PGMEA solution) 2 g, pigment dispersion A 55 g, in this order, and 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 replaced with 0.8 g of the polymerization initiator K-4 and 0.2 g of K-5.

(Example 30)
The same resin as in Example 23 except that the polymerization initiator K-1 was replaced with the polymerization initiator K-3 and the polymerizable compound M-1 4 g was replaced with the polymerizable compounds M-1 2 g and M-2 2 g. The composition was prepared.

(Example 31)
The polymerization initiator K-1 was replaced with the polymerization initiator K-3, 15 g of PGMEA was replaced with 7 g of PGMEA and 8 g of PGMEA, and 4 g of the polymerizable compound M-1 was replaced with 2 g of the polymerizable compounds M-12 and 2 g of M-3. Except for the above, a resin composition was prepared in the same manner as in Example 23.

(Example 32)
Examples except that the pigment dispersion A was replaced with the pigment dispersion D, the polymerization initiator K-1 was replaced with the polymerization initiator K-2, and the polymerizable compound M-1 was replaced with 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 with a stirrer for 30 minutes 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, and F-1 (1% PGMEA). 2 g of the solution), 6 g of Megafuck 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 (dispo 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, and F-1 (1). % PGMEA solution) (2 g), Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 0.5 g, and pigment dispersion A (55 g) in this order, and the resin composition is 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, and F-1 (1% PGMEA). 2 g of the solution), 15 g of Megafuck 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 ( Content of S-1 with respect to 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 replaced with the polymerization initiator K-3.

(Example 36)
In a 200 g container (dispo 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, and F-1 (1% PGMEA). Add 2 g of solution), 1 g of LS-2940, 55 g of pigment dispersion A, and 6 g of Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) in this order, and stir and mix with a stirrer for 30 minutes. To prepare a resin composition.

(Example 37)
A resin composition was prepared in the same manner as in Example 34 except that the polymerization initiator K-2 was replaced with the polymerization initiator K-1 and the polymerizable compound M-1 was replaced with 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 IrgacureOXE02 (manufactured by BASF Japan), Sururia 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 with a stirrer for 30 minutes to prepare a resin composition.

(Comparative Example 5)
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), 1 g of IrgacureOXE02 (manufactured by BASF Japan), 30 g of PGMEA, F-1 (1% PGMEA solution) (2 g) and pigment dispersion C (55 g) were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Comparative Example 6)
In the preparation of Example 34, the resin composition of Comparative Example 6 was prepared by the same method except that the pigment dispersion liquid A was replaced with the pigment dispersion liquid C.
(2) Preparation and evaluation of resin film <Evaluation of adhesion>
The resin compositions of each Example and Comparative Example were 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. The following evaluation was performed with a film thickness such that the OD value at this time was 2.
The substrate after prebaking was subjected to proxy exposure (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 1000 mJ / cm ² ) via a predetermined mask (150 μm □ type island pattern).
After that, the obtained substrate was paddle-developed for 10 to 60 seconds (time required for resolution when pattern exposure was performed) using a 2.38 wt% developer of TMAH (tetramethylammonium hydroxide). .. After washing with water and drying, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to prepare a substrate having a pattern.
The obtained island pattern was subjected to a tape pull test in accordance with JIS-K5400. The case where all the patterns remained was designated as A, the case where a part of the pattern was peeled off was designated as B, and the case where all the patterns were peeled off was designated as C.
The results are shown in Tables 7 and 8.

<Evaluation of resolution>
The resin compositions of each Example and Comparative Example were 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.
After that, proxy exposure (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 500 mJ / cm ² ) was applied to the prebaked substrate via predetermined masks having various line and space line widths. went.
After that, the obtained substrate was paddle-developed for 10 to 60 seconds (time required for resolution when pattern exposure was performed) using a 2.38 wt% developer of TMAH (tetramethylammonium hydroxide). .. After washing with water and drying, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to prepare a substrate having a pattern.
The obtained pattern was observed with an optical microscope, and the minimum line width (μm) in which the line-and-space pattern was not peeled off was taken as the numerical value of resolution.
For example, when a line and space of 100 μm is resolved and no peeling occurs, it is determined that the line and space has a resolution of 100 μm.
The results are shown in Tables 7 and 8.
It has been confirmed that the surface roughness (arithmetic mean Ra) of each of the resin films of Examples 23 to 33 is 100 to 2000 Å before the exposure treatment. The method for measuring the surface roughness (arithmetic mean Ra) is as described above. Further, 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% (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 moisture resistance, and good adhesion was also obtained. In particular, it was confirmed that the resin films of Examples 34 to 35 were also excellent in resolution.
On the other hand, from the results of Comparative Examples 4, 5 and 6, it was confirmed that the moisture resistance and adhesion were inferior when the titanium nitride-containing particles containing a metal atom other than the titanium atom were not contained. Further, for example, by comparing Example 34 and Comparative Example 6, it was found that the resolution was inferior when the titanium nitride-containing particles containing a metal atom other than the titanium atom were not contained. In Comparative Example 4, it is presumed that the addition of the filler causes unevenness on the side wall of the pattern, which also reduces the resolution.
Further, by comparison with Examples 34 to 37, it was found that the resolution can be further improved by using K-2 or K-3 as the polymerization initiator.
Further, by comparing Examples 34, 1D and 2D, by containing 1 to 15% by mass of a resin having at least one of a fluorine atom and a silicon atom with respect to the total solid content of the composition, moisture resistance and resolution are obtained. It was confirmed that the properties are compatible with each other.

[Preparation 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 (pre-baking) for 2 minutes using a hot plate at 100 ° C. Was done. Then, an exposure treatment (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 1000 mJ / cm ² ) was carried out on the coating film obtained above via a predetermined mask.
After that, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. to prepare a pigment layer Y1. The coating was performed with a film thickness having an OD value of 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 hot plate at 100 ° C. Then, an exposure treatment (exposure apparatus UX3100-SR (manufactured by Ushio, Inc.), exposure amount 1000 mJ / cm ² ) was carried out on the coating film obtained above via a predetermined mask.
After that, the substrate was heat-treated (post-baked) for 300 seconds using a hot plate at 220 ° C. 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. .. The coating was applied at a film thickness such that the OD of the pigment layer Y2 alone was 0.5.

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

Light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° to the prepared substrate with a resin film, and the reflectance was measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.
The reflectance at 400 nm at this time was 3.0.
Further, the substrate with the resin film was subjected to a high temperature and high humidity test for 750 hours under the conditions of a temperature of 85 ° C. and a humidity of 95% using a high acceleration life test device (EHS-221 manufactured by ESPEC).
When the transmittance of the substrate with the resin film at a wavelength of 400 nm before and after the moisture resistance test was measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation, the rate of change ΔT (%) was less than 1%.

(Example 39)
A substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced according to the method for producing a substrate with a resin film of Example 38. In Example 39, the pigment layer Y1 is coated and formed with a film thickness such that the OD value is 0.5, and then the pigment layer Y2 is coated on the upper layer with a film thickness such that the OD of the pigment layer Y2 alone is 1.0. Formed.
Light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° from the substrate surface side in the direction opposite to that of Example 38 with respect to the produced substrate with a resin film, and its reflectance was measured.
The reflectance at 400 nm at this time was 2.5%.
Further, the substrate with the resin film was subjected to a high temperature and high humidity test for 750 hours under the conditions of a temperature of 85 ° C. and a humidity of 95% using a high acceleration life test device (EHS-221 manufactured by ESPEC).
When the transmittance of the resin film-coated substrate before and after the moisture resistance test at a wavelength of 400 nm was measured, the rate of change ΔT (%) was less than 0.5%.

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

(Example 40)
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), 1 g of IrgacureOXE02 (manufactured by BASF Japan), 30 g of PGMEA, F-1 (1% PGMEA solution) (2 g) and pigment dispersion A (55 g) were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Preparation of laminated film)
A substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced according to the method for producing a substrate with a resin film of Example 38.
In this example, using the resin composition prepared above, a coating film was laminated on a glass substrate so as to have OD1.0 (pigment layer Y1) and OD0.5 (pigment layer Y2) in order.
Light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° to the prepared substrate with a resin film, and the reflectance was measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. The reflectance at 400 nm at this time was 4.0%.
Further, the substrate with the resin film was subjected to a high temperature and high humidity test for 750 hours under the conditions of a temperature of 85 ° C. and a humidity of 95% using a high acceleration life test device (EHS-221 manufactured by ESPEC). The rate of change ΔT (%) was less than 1%.

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

Claims (26)

Titanium nitride-containing particles containing at least one metal atom selected from copper, silver, gold, nickel, vanadium, iron and tungsten, and
Binder resin and
With filler
A resin composition containing a polymerization initiator .
A resin composition in which the binder resin is an alkali-soluble resin having a polymerizable group .
However, the titanium nitride-containing particles are not included in the filler. Titanium nitride-containing particles containing at least one metal atom selected from copper, silver, gold, nickel, vanadium, iron and tungsten, and
Binder resin and
With filler
Polymerization initiator and
A resin composition containing a polymerizable compound.
However, the titanium nitride-containing particles are not included in the filler. 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 any one of claims 1 to 3 , wherein the filler is hollow silica. The resin composition according to any one of claims 1 to 4 , wherein the maximum value in the particle size distribution of the filler is 50 to 500 nm. Titanium nitride-containing particles containing at least one metal atom selected from copper, silver, gold, nickel, vanadium, iron and tungsten, and
Binder resin and
A resin composition containing a polymer having a fluorine atom and a curable functional group. The resin composition according to claim 6 , wherein the content of the polymer is 1 to 15% by mass with respect to the total solid content in the resin composition. The resin composition according to claim 6 or 7 , wherein the polymer is a polymer compound containing a repeating unit containing a fluorine atom and a repeating unit having a polymerizable group. The resin composition according to any one of claims 6 to 8 , further comprising a polymerization initiator. The resin composition according to any one of claims 1 to 5 and 9 , wherein the polymerization initiator is an oxime compound. When the X-ray diffraction spectrum of the titanium nitride-containing particles is measured using CuKα-ray as an X-ray source, the diffraction angle 2θ of the peak derived from the TiN (200) plane of the titanium nitride-containing particles is 42.5 ° or more. The resin composition according to any one of claims 1 to 10 , which is in the range of 43.5 ° or less. The resin composition according to any one of claims 1 to 11 , wherein the titanium nitride-containing particles contain at least one metal atom selected from silver, nickel, vanadium, iron and tungsten. The resin composition according to any one of claims 1 to 12 , wherein the titanium nitride-containing particles contain at least one metal atom selected from vanadium, iron and tungsten. The resin composition according to any one of claims 1 to 13 , further comprising a dispersed resin. The resin composition according to any one of claims 1 to 14 , further comprising a silane coupling agent having an epoxy group. A polymerizable compound having a mosquito shield skeleton, the resin composition according to any one of claims 1 to 15. The resin composition according to claim 16 , 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 17 , 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. A resin film formed by using the resin composition according to any one of claims 1 to 5 .
A resin film having a surface roughness Ra of the outermost surface of the resin film of 100 to 2000 Å. The resin film is a resin film in which a pigment layer X1 and a pigment layer X2 each containing the titanium nitride-containing particles are laminated adjacent to each other.
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 claim 19 , wherein the surface roughness Ra of the surface of the resin film on the pigment layer X2 side is 100 to 2000 Å. A resin film formed by using the resin composition according to any one of claims 6 to 8 .
A pigment layer containing titanium nitride-containing particles containing at least one metal atom other than a titanium atom, and a pigment layer.
A resin film containing a surface layer formed by using the polymer. 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 selected from copper, silver, gold, nickel, vanadium, iron and tungsten are laminated adjacent to each other. ,
A resin film in which the concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other.
The pigment layer Y1 is formed by using the resin composition D, which is the resin composition according to any one of claims 1 to 5 .
The pigment layer Y2 is a resin film formed by using the resin composition E which is the resin composition according to any one of claims 1 to 5 . A color filter comprising a resin film formed from the resin composition according to any one of claims 1 to 18 and any one selected from the resin film according to any one of claims 19 to 22 . A light-shielding film comprising a resin film formed from the resin composition according to any one of claims 1 to 18 and any of the resin films according to any one of claims 19 to 22 . A solid-state image sensor comprising a resin film formed from the resin composition according to any one of claims 1 to 18 and any one selected from the resin film according to any one of claims 19 to 22 . An image display device comprising a resin film formed from the resin composition according to any one of claims 1 to 18 and any one selected from the resin film according to any one of claims 19 to 22 .