TW201800846A - Resin composition, resin film, color filter, light shielding film, solid-state imaging device, and image display device - Google Patents

Abstract

Provided are a resin composition capable of forming a resin film having excellent low reflectivity and excellent moisture resistance, and a resin film, color filter, light-shielding film, solid-state imaging element, and resin film having excellent low reflectivity and excellent moisture resistance. Image display device. The resin composition contains titanium nitride-containing particles containing at least one metal atom other than titanium atoms, a binder resin, and at least any one selected from a filler and a compound containing at least one of a fluorine atom and a silicon atom.

Description

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

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

The solid-state imaging device includes a photographing lens, a solid-state imaging element such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Film Semiconductor) disposed behind the photographing lens, and a circuit board on which the solid-state imaging element is mounted. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, and a smartphone. In a solid-state imaging device, noise may be generated due to reflection of visible light. Therefore, in Patent Document 1, a predetermined light-shielding film is provided in the solid-state imaging device, thereby suppressing the generation of noise. As a composition for forming a light-shielding film, a light-shielding composition containing a black pigment such as titanium black is used. [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Publication No. 2007-115921

On the other hand, in recent years, various characteristics are required for a light-shielding film. For example, with the reduction in size, thickness, and sensitivity of solid-state imaging devices, further reduction in reflection of light-shielding films is required. Further, the present inventors have found that if a light-shielding film containing titanium black is exposed to high temperature and high humidity, its spectral performance is reduced (that is, "humidity resistance" is poor). If the spectral performance of the light-shielding film is lowered, the desired light-shielding energy may not be developed, so improvement is desired.

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

The present inventors have conducted intensive studies in order to achieve the above-mentioned problems, and as a result, have found the following and have completed the present invention, that is, by using a combination of predetermined titanium nitride-containing particles, a binding resin, and a filler selected from A resin composition of at least one of a compound of at least one of a fluorine atom and a silicon atom can solve the above problems. That is, it was found that the above-mentioned object can be achieved by the following structure.

(1) A resin composition comprising: titanium nitride-containing particles containing at least one metal atom other than titanium atoms; a binder resin; and at least one selected from a filler and a compound containing at least one of a fluorine atom and a silicon atom Either. (2) The resin composition according to (1), wherein when the X-ray diffraction spectrum of the titanium nitride-containing particles is measured using CuKα rays as an X-ray source, the titanium nitride-containing particles are derived from TiN (200 The diffraction angle 2θ of the peak of the surface is in a range of 42.5 ° 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 a maximum value in a particle size distribution of the filler is 50 to 500 nm. (6) The resin composition according to any one of (1) to (5), which contains the compound containing at least one of the fluorine atom and the silicon atom, and the compound containing at least one of the fluorine atom and the silicon atom. The content of N is 1 to 15% by mass based on the total solid content in the resin composition. (7) The resin composition according to any one of (1) to (6), wherein the compound containing at least one of a fluorine atom and a silicon atom includes a repeating unit containing at least one of a fluorine atom and a silicon atom And polymer compounds having repeating units of polymerizable groups. (8) The resin composition according to any one of (1) to (6), wherein the compound containing at least one of a fluorine atom and a silicon atom is a reactive silicone. (9) The resin composition according to any one of (1) to (8), further comprising a dispersing resin. (10) The resin composition according to any one of (1) to (9), further comprising a polymerization initiator. (11) The resin composition according to (10), wherein the polymerization initiator is an oxime compound. (12) The resin composition according to any one of (1) to (11), further comprising a silane coupling agent having an epoxy group. (13) The resin composition according to any one of (1) to (12), further comprising a polymerizable compound having a Cardo skeleton. (14) The resin composition according to (13), wherein the polymerizable compound having a Cardo skeleton is a polymerizable compound having a 9,9-diarylfluorene 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 relative to the total solid content of the resin composition. . (16) A resin film comprising titanium nitride-containing particles and a binder resin containing at least one metal atom other than titanium atoms, and wherein the surface roughness Ra of the outermost surface of the resin film is 100 to 2000 Å. (17) The resin film according to (16), further comprising a filler. (18) The resin film according to (17), wherein a maximum value in a 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 according to any one of (16) to (19), wherein the resin film is a resin film in which an adjacent layer contains the pigment layer X1 and the pigment layer X2 containing the titanium nitride particles, respectively, The concentration of the titanium nitride-containing particles contained in the pigment layer X2 is lower than the concentration of the titanium nitride-containing particles contained in the pigment layer X1, and the surface roughness Ra of the surface of the pigment layer X2 side of the resin film is Ra. It is 100 ～ 2000Å. (21) A resin film comprising: a pigment layer containing titanium nitride-containing particles containing at least one metal atom other than titanium atoms; and a surface layer disposed adjacent to the pigment layer and containing fluorine atoms And at least one compound of silicon atom. (22) The resin film according to (21), wherein the compound containing at least one of a fluorine atom and a silicon atom includes a resin containing at least one of a fluorine atom and a silicon atom. (23) The resin film according to (22), wherein the resin containing at least one of a fluorine atom and a silicon atom includes a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group. (24) A resin film comprising a pigment layer Y1 and a pigment layer Y2 containing titanium nitride particles containing titanium nitride particles containing at least one metal atom other than at least one type of titanium atom, respectively, wherein the pigment layers Y1 and The concentrations of the titanium nitride-containing particles contained in the pigment layer Y2 are different from each other. (25) A color filter including a resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24) Either. (26) A light-shielding film comprising a resin film formed from the resin film according to any one of (1) to (15) and the resin film according to any one of (16) to (24) Either. (27) A solid-state imaging element comprising a resin film selected from the resin composition described in any one of (1) to (15) and the resin film described in any one of (16) to (24) Either. (28) An image display device including a resin film formed from the resin composition according to any one of (1) to (15) and the resin according to any one of (16) to (24) Any of the membranes. [Inventive effect]

According to the present invention, it is possible to provide a resin composition capable of forming a resin film having excellent low reflectivity and excellent moisture resistance. In addition, according to the present invention, it is possible to provide a resin film having excellent low reflectivity and excellent moisture resistance, a color filter including the resin film, a light-shielding film, a solid-state imaging element, and an image display device.

Hereinafter, the aspect for implementing this invention is demonstrated. In addition, in the description of the group (atomic group) in the present specification, the expressions that are not described as substituted and unsubstituted include those having substituents together with those having no substituents. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to acryl and methyl Acrylic acid. The "pigment" in the present invention means, for example, an insoluble pigment compound which is insoluble in a solvent. Here, the "solvent" includes the solvents exemplified in the solvent column described later. Therefore, these pigment compounds insoluble in the solvent correspond to the pigment in the present invention. In addition, "active light" or "radiation" in this specification means, for example, a bright line spectrum of a mercury lamp, an extreme ultraviolet (EUV light), an X-ray, an electron beam, and the like represented by an excimer laser. In the present invention, "light" means active light or radiation. Regarding "exposure" in this specification, unless otherwise specified, it is not limited to exposure based on far-ultraviolet rays, X-rays, and EUV light represented by a bright line spectrum of a mercury lamp, excimer laser, etc. The depiction of isoparticle beams is also included in the exposure. In this specification, "~" is used as a meaning which includes the numerical value described before and after it as a lower limit value and an upper limit value. In addition, in this specification, "1Å" has the same meaning as "0.1 nanometer (nm)".

[First Embodiment: Resin Film with Ra of 100 to 2000 Å] The resin film in the first embodiment is characterized in that it contains titanium nitride-containing particles and a binding resin containing at least one metal atom other than a titanium atom. The outermost surface roughness Ra is 100 to 2000 Å. This time, the present inventors have found that by setting the surface roughness of the outermost surface of a resin film containing titanium nitride particles containing metal atoms other than at least one type of titanium atom to the above numerical range, Excellent low reflectivity and moisture resistance. In particular, it was confirmed that when a resin film contains a filler (preferably silica particles) or a resin having a polysiloxane structure and a method of damaging the film surface is used (respectively, Embodiments 1A and 1B described later), The obtained film had further improved low-reflection properties and was significantly superior in moisture resistance. Regarding the surface roughness (arithmetic average roughness Ra) of the resin film, from the viewpoint that the effect of the present invention is more excellent, the surface roughness Ra is preferably 300 to 2000 Å (Angstroms), and more preferably 300 to 1500 Å. The surface roughness Ra was calculated using DektakXT manufactured by Bruker Corporation, and measuring a distance of 1 mm from the resin film at a resolution of 1 μm / point.

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

Hereinafter, various materials and a manufacturing method for the resin film constituting the first embodiment will be described. Hereinafter, as a method of damaging the surface of a film, a state in which a filler is contained in a resin film will be described.

[Embodiment 1A] Examples of the material constituting the resin film include titanium nitride-containing particles containing at least one metal atom other than titanium atoms, a binding resin, and a filler. A resin film can be formed by apply | coating the resin composition containing the said structural material or its precursor material on a board | substrate. Moreover, the said resin composition can also be set as the photosensitive resin composition which has exposure and developability. In this case, a polymerization initiator, a polymerizable compound, and the like may be blended in the resin composition. In addition, a binder resin, a polymerizable compound, a dispersion resin described later, and the like may be used as the alkali-soluble material. Hereinafter, various materials included in the resin composition (hereinafter, referred to as “resin composition A”) will be described in detail.

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

The titanium nitride-containing particles are composite particles containing titanium nitride particles and metal particles. "Composite microparticles" refer to particles in which titanium nitride particles and metal microparticles are composited or in a highly dispersed state. Among them, "compositing" means that particles are composed of two components of titanium nitride and metal, and "highly dispersed state" means that titanium nitride particles and metal particles exist separately, and particles with a small amount of components are not agglomerated and uniform. , The same dispersed. In addition, the "titanium nitride particles" include titanium nitride as a main component, and generally include low-order titanium oxide (low- titanium oxide) represented by titanium oxide TiO ₂ and Ti _n O _2n-1 (1≤n≤20) as a subcomponent. order titanium oxid) and titanium oxynitride represented by TiN _y O _z (y, z are respectively greater than 0 and less than 2).

The content of metal atoms and the content of titanium atoms can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectrometry, the content of nitrogen atoms can be analyzed by inert gas melting thermal conductivity method, and the content of oxygen atoms can be analyzed by Analysis was performed by 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 microparticles, atoms other than the above-mentioned titanium atom, nitrogen atom, oxygen atom, and metal atom may be contained as impurities. When the amount of impurities is small and it is difficult to determine, the calculation is performed without considering the impurities. From the viewpoint of dispersion stability and light-shielding properties, 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 particles) is not particularly limited, and examples thereof include copper, silver, gold, vanadium, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, and molybdenum. , Tungsten, niobium, tantalum, calcium, titanium, bismuth, antimony and lead, and at least one of these alloys. Among them, at least one selected from the group consisting of copper, silver, gold, iron, platinum, palladium, nickel, vanadium, tin, cobalt, rhodium and iridium, and these alloys is preferred, and is selected from copper, silver, gold, nickel Vanadium, platinum, tin, and iron, and at least one of these alloys are more preferred. From the viewpoint of more excellent moisture resistance, at least one selected from silver and iron is more preferred, and silver is particularly preferred. The content of the metal atoms (metal particles) in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 50% by mass relative to the total mass of the titanium nitride-containing particles, and 0.01% by mass to 30% by mass is More preferably, it is more preferably 0.2% by mass or more and 30% by mass or less. In addition, when plural kinds of metal atoms (metal particles) are included, the total content is included in the meaning of the above numerical range. When the content of the metal atom exceeds 0.001% by mass, the pattern formability of the cured film is excellent. When the content of the metal atom is less than 50% by mass, the moisture resistance and the abrasion resistance are excellent. The hardened film-based electrode is excellent in corrosion resistance. That is, the cured film can prevent electrode corrosion. The metal atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate. It is considered that titanium nitride in the titanium nitride-containing particles is attached to the electrode and the substrate via the metal atoms. Therefore, it is considered that after the patterning of the hardened film such as a development process, metal atoms remain on the electrode and the substrate, and it becomes easy to remove titanium nitride. Therefore, it can be estimated that by setting the content of the metal atoms in the titanium nitride-containing particles to a predetermined amount or more, the pattern formability of the cured film is improved.

When stored under 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 can be inferred that the content of the metal atoms in the titanium nitride-containing particles is less than 0.4% by mass, and the electrode has excellent corrosion resistance. When this effect is obtained, 0.01 to 0.2% by mass is more preferred, and 0.02 to 0.1% by mass is even more preferred.

The metal microparticles in the titanium nitride-containing particles are not subjected to a treatment such as surface coating, but exist in a stable state as microparticles. In order to obtain a higher light-shielding property as the metal fine particles, it is preferable that the particles are appropriately micronized. The grain size determined from the half-value width of the strongest main peak in the X-ray diffraction spectrum of the metal fine particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less. The grain size can be calculated using the Scherrer formula based on the half-value amplitude of the X-ray diffraction peak. For example, in the X-ray diffraction spectrum of silver, when CuKα rays are used as the X-ray source, as the strongest peak, the peak derived from the (111) plane appears near 2θ = 38.1 °. As the grain size obtained from the half-value width of the (111) plane, 50 nm or less is more preferable, and 20 nm or more and 50 nm or less is more preferable.

In order to improve the light-shielding property, it is preferable that the titanium nitride particles have the following characteristics. In the X-ray diffraction spectrum of titanium nitride, when CuKα ray is used as the X-ray source, it is the strongest peak. For TiN, the peak derived from the (200) plane appears near 2θ = 42.5 °, and for TiO, it is derived from ( 200) The peak of the plane appears around 2θ = 43.4 °. On the other hand, although not the strongest peak intensity, but on anatase type TiO _2, in the vicinity of 2θ = 48.1 ° derived from the observed (200) plane peak of _2, in the vicinity of 2θ = 39.2 ° observer on the rutile type TiO To the peak originating from the (200) plane. Therefore, among titanium compounds having a crystal structure of nitrogen and oxygen atoms, the diffraction peak 2θ also has the strongest peak in the range of 42.5 ° to 43.4 °. The more the crystal state containing a large number of oxygen atoms, the peak position is relatively Displace at 42.5 ° toward the high-angle side.

From the viewpoint of light-shielding properties, titanium nitride particles include TiN as a main component, and a diffraction angle 2θ derived from a peak of the (200) plane is preferably 42.5 ° or more and 43.5 ° or less, and more preferably 42.5 ° or more and 42.8 ° or less. It is more preferable that it is 42.5 ° or more and less than 42.7 °. Titanium nitride particles usually take the form of oxynitride by containing a part of oxygen atoms by oxidation of the particle surface or the like. In general, the incorporation of oxygen when synthesizing titanium nitride particles is particularly significant when the particle diameter is small. When the amount of oxygen contained is small, higher light-shielding properties can be obtained, and therefore it is particularly preferable that TiO ₂ is not contained as a secondary component. The content of the oxygen atom is preferably 10% by mass or less and more preferably 6.0% by mass or less with respect to the mass of the titanium nitride particles.

From the viewpoint of light-shielding properties, the grain size of the titanium nitride particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less. With a grain size of 20 nm or more, the ratio of the surface of the active particles to the volume of the particles becomes small, resulting in a good balance. As a result, titanium nitride-containing particles having excellent heat resistance and durability can be obtained.

Regarding the diffraction angle 2θ of the above-mentioned titanium nitride-containing particles originating from the peak of the TIN (200) plane, from the viewpoint of light-shielding properties, 42.5 ° or more and 43.5 ° or less are preferred. In order to improve light-shielding properties, 42.5 ° or more and 42.8 ° or less More preferably, it is more preferably 42.5 ° or more and less than 42.7 °. In addition, when titanium oxide TiO ₂ is contained as a subcomponent, the peak with the strongest intensity, the peak derived from anatase TiO ₂ (101) appears near 2θ = 25.3 °, and the peak derived from rutile TiO ₂ (110). Appears around 2θ = 27.4 °. However, since TiO ₂ is white, it is a factor that reduces the light-shielding property. Therefore, it is preferable to reduce it to such an extent that it is not observed as a peak.

The titanium nitride-containing particles are preferably produced by a process of mixing and condensing Ti and metal elements in a gas phase state, and more preferably by a thermal plasma method using a nitrogen-containing gas as a plasma gas.

As the titanium nitride-containing particles, those described in International Publication No. 2010/147098, Japanese Patent Application Laid-Open No. 2007-153662, and the like can also be 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 even more preferably 40 to 55% by mass relative to the total solids content in the resin composition.

As a method for producing titanium nitride-containing particles, those described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. In addition, the titanium nitride-containing particles are not exposed to the atmosphere immediately after the particles are produced, but are left in a sealed container for controlling the oxygen concentration for a predetermined time (preferably 12 to 72 hours, more preferably 12) 48 hours. More preferably, 12 to 24 hours). In this case, the content of water is more preferably controlled. As a result, the surface and grain boundaries of the titanium nitride-containing particles become stable, and it can be presumed that the performance optimizer of the composition. Specifically, pinholes in the cured film obtained by using the composition of the present invention can be suppressed. The oxygen (O ₂ ) concentration and the moisture content in the sealed container whose oxygen concentration is controlled are preferably 100 mass ppm or less, more preferably 10 mass ppm or less, and 1 mass ppm or less. The above oxygen (O ₂₎ concentration and adjusting the content of water, including the use of an oxygen (O ₂₎ content of the above range of the oxygen concentration and the water of (O ₂₎ and water of nitrogen or argon, an inert gas is preferred Among them, nitrogen is more preferred. As a result, the surface and grain boundaries of the titanium nitride-containing particles become stable, and it can be presumed that the performance optimizer of the composition. Specifically, titanium nitride-containing particles having a relatively high optical density can be obtained, and pinholes of a cured film obtained by using the composition of the present invention can be suppressed. In addition, the temperature for a predetermined period of time is preferably 300 ° C or lower, more preferably 200 ° C or lower, and even more preferably 100 ° C or lower. With this range, titanium nitride-containing particles having a high optical density can be obtained.

The titanium powder material used in the production of titanium nitride-containing particles is preferably one having a high purity. The titanium powder material is not particularly limited, and a titanium element having a purity of 99.99% by mass or more is preferred, and a 99.999% by mass or more is more preferred.

In addition, the content of silicon atoms in the titanium powder material is preferably less than 0.3% by mass, and more preferably less than 0.1% by mass, and it is particularly preferable not to include it. In addition, the content of water in the titanium powder material is preferably less than 1% by mass, and more preferably less than 0.1% by mass, and it is particularly preferable not to include it. By setting it as the said range, a desired effect can be acquired more notably.

Examples of the process for dispersing titanium nitride-containing particles include processes using compression, pressing, punching, cutting, or cavitation as a mechanical force for dispersing. Specific examples of these processes include bead mill, sand mill, roll mill, ball mill, high-speed impeller, sand mixing, jet flow mixing, high-pressure wet micronization, ultrasonic dispersion, and micro-jet. In addition, it is possible to appropriately use "Distribution Technology Encyclopedia, Issued by Information Corporation, July 15, 2005" or "Distribution technology centered on suspension (solid / liquid dispersion system) and practical comprehensive information on industrial applications Collecting, operation and development center publishing department, October 10, 1978 "process and disperser. Refinement of pigments by the salt milling process is also possible. The raw materials, equipment, and processing conditions used in the salt milling process can be, for example, those described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629. Among these, sand grinding (bead grinding) is preferred. In addition, in the pulverization of pigments in a sand mill (bead mill), it is preferable to perform the treatment under conditions that improve the pulverization efficiency by using micro-beads having a smaller diameter or increasing the filling rate of the micro-beads. After the treatment, it is preferable to remove the basic particles by filtration, centrifugation, or the like.

The titanium nitride-containing particles described above can also be preferably used in a process for dispersing pigments described later.

<Binder resin> The resin composition A contains a binder resin. It is preferable that the bonding resin does not include both fluorine atoms and silicon atoms. Among them, "excluding both fluorine atoms and silicon atoms" means that the resin does not actually contain fluorine atoms and silicon atoms, and each content is preferably 3% by mass or less, and more preferably 0.1% by mass or less relative to the total mass of the resin. .

The binder resin is not particularly limited, and a linear organic polymer is preferably used. As such a linear organic polymer, a known one can be arbitrarily used. The molecular weight of the binder resin is not particularly limited. As a polystyrene conversion value based on the GPC (gel permeation chromatography) method, a weight average molecular weight (Mw) of 5,000 to 100,000 is preferable. The number average molecular weight (Mn) is preferably 1,000 to 20,000. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6 mm ID × 15 cm) as columns, and using THF (eluent as Tetrahydrofuran).

As described above, the resin composition A can have exposure and developability. Therefore, when the resin composition A is a photosensitive resin composition, as the binding resin, a resin capable of water development or weak alkaline water development is preferred, and it is a linear organic that is soluble or swellable to water or weak alkaline water. Polymer is more preferred. Among them, alkali-soluble resins (resins having a group that promotes alkali-solubility) are particularly preferred as the binding resin.

The molecular weight of the alkali-soluble resin is not particularly limited, and a weight-average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000. The weight average molecular weight and the number average molecular weight can be measured by the method described above. As the alkali-soluble resin, it may be a linear organic high-molecular polymer, and it can have at least one base that promotes alkali-solubility from a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The group is appropriately selected from alkali-soluble resins.

As the alkali-soluble resin, from the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferred. From the viewpoint of performance control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are more preferred. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfonic acid group, a phenolic hydroxyl group, and the like, which are soluble in organic solvents and can be developed with a weakly alkaline aqueous solution Is better. The acid group may be only one kind, or two or more kinds.

In the production of the alkali-soluble resin, for example, a method based on a known radical polymerization method can be applied. Those skilled in the art can easily set polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when producing an alkali-soluble resin by a radical polymerization method, and can also set experimentally. condition.

As the alkali-soluble resin, a polymer having a carboxyl group in a 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 partially esterified maleic acid are preferable. Copolymers, alkali-soluble phenolic resins such as phenolic resins, etc., acidic cellulose derivatives having a carboxyl group in a side chain, and addition of an anhydride to a polymer having a hydroxyl group. 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 that can be copolymerized with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compounds, and N-substituted maleimide monomers. . Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (Meth) acrylate, isobutyl (meth) acrylate, 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. Examples of vinyl compounds include styrene , Α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate Methyl acrylate macromonomers, etc., as the N-substituted maleimide imide monomer described in Japanese Patent Application Laid-Open No. 10-300922, include N-phenylmaleimide and N-cyclohexyl Maleimidine and so on. In addition, these other monomers that can be copolymerized with (meth) acrylic acid may be only one kind, or may be two or more kinds.

In order to improve the crosslinking efficiency of the resin composition A, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acrylfluorenyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in a side chain is useful. Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (containing COOH, polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., and Viscoat R- 264, KS resist 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (made by Daicel Corporation.), Acrycure-RD -F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), Etc.

As the alkali-soluble resin, benzyl (meth) acrylate / (meth) acrylic copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (methyl) Base) acrylate copolymer, benzyl (meth) acrylate / (meth) acrylic acid / other monomer multi-component copolymer. In addition, a 2-hydroxyethyl (meth) acrylate copolymerized with 2-hydroxypropyl (meth) acrylate / polystyrene described in Japanese Patent Application Laid-Open No. 7-140654 can also be preferably used. Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methyl Acrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer Body / benzyl methacrylate / methacrylic acid copolymer and the like. In addition, as a commercially available product, for example, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.) Can be used.

The alkali-soluble resin includes compounds containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimers"). The polymer (a) obtained by polymerizing the monomer components is also preferable.

[Chemical Formula 1]

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

[Chemical Formula 2]

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), reference can be made to the description in Japanese Patent Application Laid-Open No. 2010-168539.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, Linear or branched alkyl such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl, 2-ethylhexyl; aryl such as phenyl; ring Hexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and other alicyclic groups; 1-methoxy Alkyl-substituted alkyl groups such as ethyl and 1-ethoxyethyl; alkyl groups such as benzyl substituted with aryl. Among these, from the viewpoint of heat resistance, substituents of primary or secondary carbons, such as methyl, ethyl, cyclohexyl, benzyl, etc., which are not easily separated by acid or heat, are particularly preferred.

As a specific example of the ether dimer, refer to, for example, paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-29760, which is incorporated into this specification. The ether dimer may be only one kind, or two or more kinds. The structure derived from the compound represented by the general formula (ED1) and / or the compound represented by the general formula (ED2) can be copolymerized with other monomers.

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

[Chemical Formula 3]

In the 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 an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15.

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

Specific examples of the alkali-soluble resin include the following. In addition, "Me" represents a methyl group.

[Chemical Formula 4]

The alkali-soluble resin can be referred to the descriptions after paragraph numbers 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to <0685> to <0700> of US Patent Application Publication No. 2012/0235099), and these contents are incorporated herein Application instructions. Further, the copolymer (B) described in paragraphs 0029 to 0063 of Japanese Patent Application Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, paragraph number 0088 to Japanese Patent Publication No. 2012-208474 can also be used. The adhesive resin described in 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of Japanese Patent Application Publication No. 2012-137531 and the adhesive resin used in the examples, Japanese Patent Application Laid-Open No. 2013-024934 The adhesive resins described in paragraphs 0132 to 0143 of the publication and the adhesive resins used in the examples, the paragraphs 092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and the adhesive resins used in the examples, Japanese Patent Laid-Open No. 2012-032770 The binder resin described in paragraphs 0030 to 0072 of the Japanese Patent Publication No. These contents are incorporated into the specification of this 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 more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, even more preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

In addition, as another resin, a 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 based on the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and most preferably 1.5% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. The resin composition A may contain only one kind of a binding resin, or may contain two or more kinds. When two or more kinds 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 provided to break the surface. The titanium nitride-containing particles are not included in the filler. In addition, particles for imparting colorability such as other pigments are not included in the filler. As the filler, non-colorability is preferable. The composition of the filler is not particularly limited, and either inorganic particles or organic particles can be used. The inorganic particles are not particularly limited, and examples thereof include oxides such as silicon, titanium, aluminum, tin, zinc, and antimony. The inorganic particles may have a porous or hollow (hollow) structure inside. The organic particles are not particularly limited, and examples of the material include cellulose derivatives, acrylic resins, polyolefins, polyamides, polycarbonates, polystyrene, vinyl acetate, vinyl alcohol, and vinyl chloride. Resins such as homopolymers or copolymers of vinyl butyral, ethylene polymers of copolymers, and homopolymers and copolymers of diene. From the viewpoint of low reflectivity, among them, silicon dioxide particles and acrylic particles are preferable, and hollow silicon dioxide (hollow silicon dioxide particles) having a hollow structure is more preferable.

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

When the resin composition A contains a filler, the content is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the total solids content in the composition. The resin composition A may contain only one kind of filler, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Dispersion resin> The resin composition A may contain a dispersion resin. The dispersing resin contributes to improving dispersibility of colored pigments such as other pigments used in addition to the titanium nitride-containing particles (hereinafter, also referred to as “black pigments” as appropriate) as needed. Examples of the dispersion resin include polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, ( (Meth) acrylic copolymers, formalin naphthalenesulfonic acid, and the like. Dispersing resins (hereinafter, also referred to as "polymer compounds") can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structure.

The polymer compound is adsorbed on the surface of the dispersion such as a black pigment and a pigment, if necessary, to prevent re-aggregation. Therefore, as a preferable structure, a terminal-modified polymer, a grafted polymer, and a block-type polymer which have a fixed part with respect to a pigment surface can be mentioned. On the other hand, by modifying the surface of the titanium nitride-containing particles, it is also possible to promote the adsorption of the polymer compounds to these.

The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, a "structural unit" has the same meaning as a "repeating unit." This kind of polymer compound having a structural unit having a graft chain has an affinity with a solvent due to the graft chain, and therefore, it is one having excellent dispersibility of a color pigment such as a black pigment and dispersion stability over time. In addition, in the composition, due to the presence of the graft chain, it has an affinity with a polymerizable compound or other resins that can be used, so that it is difficult to generate a residue during alkali development. When the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorption force to a colored pigment such as a black pigment decreases, and the dispersibility tends to decrease. Therefore, it is preferred that the number of atoms other than hydrogen atoms in the graft chain be in the range of 40 to 10,000. It is more preferable that the number of atoms other than hydrogen atoms is 50 to 2,000. The number of atoms other than hydrogen atoms is 60 to 500. Further preferred. Among them, "graft chain" means the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the main chain branched group.

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

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

Corresponding to the structural unit with a graft chain possessed by a polymer compound, AA-6 (trade name, TOAGOSEI CO., LTD ..), a commercially available macromonomer suitable for the synthesis of polymer compounds, 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 ..), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD ..), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD ..) , AY-707 (trade name, manufactured by TOAGOSEI CO., LTD ..), AY-714 (trade name, manufactured by TOAGOSEI CO., LTD ..), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD ..) ), AK-30 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD ..), ARONIX M-110 (trade name, TOAGOSEI CO., LTD. (Manufactured), ARONIX M-5300 (trade name, manufactured by TOAGOSEI CO., LTD.), ARONIX M-5400 (trade name, manufactured by TOAGOSEI CO., LTD.), ARONIX M-5700 (trade name, TOAGOSEI CO., LTD) .Manufactured), Blemmer PP-100 (trade name, NOF CORPORAT Manufactured by ION), Blemmer PP-500 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55- PET-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name, NOF Corporation.), Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION.), And the like. Among them, AA-6 (trade name, manufactured by Toagosei. Company, Limited.), AA-10 (trade name, TOAGOSEI CO., LTD ..), and AB-6 (trade name, manufactured by TOAGOSEI CO., LTD ..) are used. ), 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 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Etc. are preferred.

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

[Chemical Formula 5]

In Formulae (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In the formulae (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. As X ¹ , X ² , X ³ , X ^4, and X ⁵ , from the viewpoint of limitation in synthesis, it is preferable that they are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each is independently hydrogen Atoms or methyl groups are more preferred, and methyl groups are particularly preferred.

In the formulae (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. 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 each represent a bonding site with the left terminal group and the right terminal group in Formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of simplicity of synthesis.

[Chemical Formula 6]

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 specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. And amine groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has 5 to 6 carbon atoms. An alkyl or alkoxy group of 24 is preferred, wherein each is independently 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. Kew is better. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

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

In the formula (3), R ³ represents a branched or linear alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, a plurality of R ³ may be the same as each other or different from each other. In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. Examples of R ⁴ include a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and a hydrogen atom or an alkyl group is more preferable. 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 preferred, and a linear alkyl group having 1 to 6 carbon atoms is more preferred. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same as each other or different from each other.

In addition, the polymer compound may have two or more different structural units and a structural unit having a graft chain. That is, the molecules of the polymer compound may include structural units represented by formulas (1) to (4), which are different from each other. In formulas (1) to (4), n, m, p, and When q represents an integer of 2 or more, in the formulae (1) and (2), the side chains may include structures in which j and k are different from each other. In the formulae (3) and (4), there are plural numbers in the molecule Each of R ³ , R ⁴ and X ⁵ may be the same as each other or different from each other.

As the structural unit represented by the formula (1), a structural unit represented by the following formula (1A) is more preferable from the viewpoint of dispersion stability and developability. In addition, as the structural unit represented by the formula (2), a structural unit represented by the following formula (2A) is more preferable from the viewpoint of dispersion stability and developability.

[Chemical Formula 7]

In the formula ^{(1A), X 1, X} Y 1, Z 1 and n are as defined in the formula (1) is ^1, Y ^1, Z ¹ and n, respectively, preferred ranges are also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred range is also the same.

In addition, as the structural unit represented by the formula (3), a structural unit represented by the following formula (3A) or formula (3B) is more preferable from the viewpoint of dispersion stability and developability.

[Chemical Formula 8]

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

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

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

In addition, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, does not correspond to the structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phenolic hydroxyl group, and the like).

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

The ClogP value is a value calculated by a program "CLOGP" which can be obtained from Daylight Chemical Information System, Inc. This program provides a "calculated logP" value calculated by the fragmentapproach of Hansch, Leo (see below). Fragmentapproach divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and totals the logP contribution amount allocated to the fragment to estimate the logP value of the compound. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. AJ Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (partition coefficient). It is a quantitative value representing the physical property value of how an organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water. Expression. logP = log (Coil / Cwater) In the formula, Coil represents the Mohr concentration of the compound in the oil phase, and Cwater represents the Mohr concentration of the compound in the water phase. If the value of logP increases with a positive (plus) value between 0, it means that the oil solubility increases, and if the absolute value increases with minus (minus), it means an increase in water solubility, which has a negative correlation with the water solubility of organic compounds. Parameters for estimating the hydrophobicity of organic compounds are widely used.

The polymer compound, as the hydrophobic structural unit, preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulae (i) to (iii).

[Chemical Formula 9]

In the formulae (i) to (iii), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon number of 1 to 6 Alkyl (for example, methyl, ethyl, propyl, 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 more preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably hydrogen atoms. X represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, substituted alkynylene), and divalent Aromatic group (eg, arylene, substituted arylene), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted An amino 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 a saturated aliphatic group is preferred. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group or a heterocyclic group.

An L-based single bond, an alkylene group, or a divalent linking group containing an alkylene oxide structure is preferred. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may include a polyoxyalkylene structure containing two or more alkylene oxide structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferable, and an integer of 2 to 10 is more preferable.

Examples of Z include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and a substituted arylene group). Aryl), heterocyclyl, or a combination of these. These groups may include an oxygen atom (-O-), a sulfur atom (-S-), an imine group (-NH-), a substituted imine group (-NR ^31- , wherein R ³¹ is an aliphatic group , Aromatic or heterocyclic), carbonyl (-CO-).

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 also includes a ring group hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring group hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclic octane ring (bicyclic [2.2.2 ] Octane ring, bicyclic [3.2.1] octane ring, etc.) and other bicyclic hydrocarbon rings; homoblane (homobledane), adamantane, tricyclic [5.2.1.0 ^{2 , 6} ] decane, tricyclic [4.3 .1.1 ^{2 , 5} ] undecane ring and other 3-cyclic hydrocarbon rings; tetracyclic [4.4.0.1 ^{2 , 5} .. 1 ^{7 , 10} ] dodecane, perhydro-1 ^{, 4} -methylene-5, 8 -4-ring hydrocarbon rings such as a methylene naphthalene ring and the like. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused ring hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydrofluorene, perhydrofluorene, perhydroindene, perhydro Condensed rings such as fluorene rings are condensed with a plurality of 5 to 8-membered cycloalkane rings. Compared with an unsaturated aliphatic group, an aliphatic group is a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

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

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and the like), and an alkyl group having 1 to 6 carbon atoms ( For example, methyl, ethyl, propyl, etc.), Z or -LZ. Here, the meanings of L and Z are the same as those of L and Z described above. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ^2, and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group, or a divalent link including an alkylene oxide structure Compounds in which X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferred. Further, as the monomer represented by the general formula (ii), a compound in which 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 preferable. Further, as the monomer represented by the general formula (iii), a compound in which R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.

Examples of the representative compounds represented by the formulae (i) to (iii) include radical polymerizable compounds selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, as examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated herein.

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

The polymer compound can introduce a functional group that can interact with a colored pigment such as a black pigment. Among them, the polymer compound preferably further includes a structural unit having a functional group capable of interacting with a colored pigment such as a black pigment. Examples of the functional group that can interact with a color pigment such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. When a polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, it contains a structural unit having an acid group, a structural unit having a basic group, a structural unit having a coordination group, or A structural unit containing a reactive functional group is preferred. In particular, the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, in the resin composition A, the polymer compound serving as a dispersion resin that facilitates dispersion of a color pigment such as a black pigment has alkali-solubility. A composition containing such a polymer compound becomes an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. In addition, since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent and the coating property is also improved. It is speculated that this is because the acid group in the structural unit having an acid group easily interacts with a color pigment such as a black pigment, the polymer compound stably disperses the color pigment such as the black pigment, and the polymer compound that disperses the color pigment such as the black pigment. The viscosity becomes low, and the polymer compound itself is easily and stably dispersed.

Among them, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit having a graft chain, or may be a different structural unit, and a structural unit system having an alkali-soluble group as an acid group A structural unit different from the hydrophobic structural unit described above. That is, it does not correspond to the said hydrophobic structural unit.

As a functional group that can interact with a color pigment such as a black pigment, that is, an acid group, for example, there are a carboxylic acid group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group. One type is preferable, and a carboxylic acid group having a high adsorptive power to a colored pigment such as a black pigment and a high dispersibility is particularly preferable. That is, it is preferable that the polymer compound further has a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or two or more kinds of structural units having an acid group. The polymer compound may or may not contain a structural unit having an acid group. When it is contained, the content of the structural unit having an acid group is expressed in terms of mass. It is preferably 5 to 80% relative to the total mass of the polymer compound. From the viewpoint of damage to the image strength of alkali development, 10 to 60% is more preferable.

Basic groups that are functional groups that can interact with color pigments such as black pigments include primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic rings containing N atoms, and fluorenylamine groups. For example, a tertiary amine group having a high adsorptive power against a color pigment such as a black pigment and a high dispersibility is particularly preferred. The polymer compound may have one or more of these basic groups. The polymer compound may or may not contain a structural unit having a basic group. When contained, the content of the structural unit having a basic group is calculated in terms of mass, and is 0.01% or more and 50% or less with respect to the total mass of the polymer compound. Preferably, from the viewpoint of suppressing the development resistance, 0.01% or more and 30% or less are more preferable.

Examples of functional groups that can interact with colored pigments such as black pigments, that is, coordination groups and reactive functional groups include, for example, acetoacetoxy, trialkoxysilyl, isocyanate groups, Acid anhydride, trichloromethane, etc. Especially for black pigments, such as acetoacetoxyl, which has good adsorption and high dispersibility. The polymer compound may have one or two or more of these groups. The polymer compound may contain a structural unit having a coordinating group or a functional group having a reactivity, or it may not be contained. When contained, the content of these structural units is calculated by mass, and is 10% or more relative to the total mass of the polymer compound. It is more preferably 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing obstructing developability.

When the polymer compound in the present invention has a functional group capable of interacting with a coloring pigment such as a black pigment in addition to the graft chain, it may include various functional groups capable of interacting with a coloring pigment such as a black pigment as described above. It is not particularly limited how these functional groups are introduced, and the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulae (iv) to (vi).

[Chemical Formula 10]

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon number of 1 to 6 alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group The base is better. In the general formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred. In addition, Y in the general formula (v) represents a methine group or a nitrogen atom.

In addition, L ₁ in the general formulae (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imine bond (-NR ³¹ '-, wherein R ³¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. 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. It is preferable that the aliphatic group is a saturated aliphatic group compared with an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. In the heterocyclic ring, one or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

L ₁ is preferably a single bond, an alkylene group, or a divalent linking group containing an alkylene oxide structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure including two or more alkylene oxide structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferable, and an integer of 2 to 10 is more preferable.

In the general formulae (iv) to (vi), Z ₁ represents a functional group capable of interacting with a colored pigment such as a black pigment other than the graft chain. A carboxylic acid group and a tertiary amine group are preferred, and a carboxylic acid group For the better.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, , methyl, ethyl and propyl, etc.), - Z ₁ or -L ₁ -Z _1. Wherein, L ₁ and Z ₁ meaning the same as the above L ₁ and Z _1, preferred embodiments are also the same. R ¹⁴ , R ^15, and R ¹⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent link including an alkylene oxide structure. A compound in which X ₁ is an oxygen atom or an imine group, and Z ₁ is a carboxylic acid group is preferred. Further, as the monomer represented by the general formula (v), a compound in which 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 group is preferable. In addition, as the monomer represented by the general formula (vi), a compound in which R ¹⁴ , R ^15, and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z is a carboxylic acid group is Better.

Representative examples of the monomer (compound) represented by the general formulae (iv) to (vi) are shown below. Examples of the monomer include a reaction of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and phthalic anhydride, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and tetrahydroxyphthalic anhydride, Reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol, 4-hydroxybenzylpropene, and the like.

From the viewpoints of interaction with a coloring pigment such as a black pigment, dispersion stability, and permeability to a developing solution, the content of a structural unit having a functional group that can interact with the coloring pigment such as a black pigment is higher than that of a polymer compound. The total mass is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass.

In addition, in order to improve various properties such as image strength, the polymer compound may be added before the effects of the present invention are impaired, and further contain a structural unit having a graft chain, a hydrophobic structural unit, and a pigment having a coloring matter such as a black pigment. The structural units of the interacting functional group are different from each other and have various functions (for example, a structural unit having a functional group having an affinity with the dispersion medium used for the dispersion, etc.). Examples of such other structural units include structural units derived from a radical polymerizable compound selected from acrylonitrile and methacrylonitrile. The polymer compound can use one or two or more of these other structural units, and its content is expressed in terms of mass, and relative to the total mass of the polymer compound, 0% to 80% is preferred, and 10% to 60% is preferred. The following are particularly preferred. When the content is within the above range, sufficient pattern-formability can be maintained.

The range of the acid value of the polymer compound is from 0 mgKOH / g to 160 mgKOH / g, more preferably from 10 mgKOH / g to 140 mgKOH / g, and from 20 mgKOH / g to 120 mgKOH / g. good. When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling during development during the formation of the resin layer is more effectively suppressed. In addition, when the acid value of the polymer compound is 10 mgKOH / g or more, alkali developability is further improved. In addition, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored pigments such as black pigments can be more suppressed, the number of coarse particles can be reduced, and the stability of the composition over time can be further improved.

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. In addition, a resin having a desired acid value can be obtained by changing the content of a structural unit that is a component containing a polymer compound, that is, an acid group.

When forming a resin film, the weight average molecular weight of the polymer compound in the present invention is taken as a polystyrene conversion value by the GPC (gel permeation chromatography) method from the viewpoints of suppression of pattern peeling at the time of development and developability. 4,000 or more and 300,000 or less are preferable, 5,000 or more and 200,000 or less are more preferable, 6,000 or more and 100,000 or less are more preferable, and 10,000 or more and 50,000 or less are more preferable. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION.), Using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as the column, and using THF as the eluent (Tetrahydrofuran).

The polymer compound can be synthesized by a known method. Examples of the solvent used in the synthesis of the polymer compound include dichloroethane, 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-dimethyl Methylformamide, N, N-dimethylacetamide, dimethylmethylene, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. 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 Kusumoto Chemicals, Ltd., and "Disperbyk-101 (Polyamidamine Phosphate), 107 (Carboxylic Acid) manufactured by BYK Chemie. Acid ester), 110 (copolymers containing acid groups), 111 (phosphoric acid-based dispersant), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymers) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010-4165 (polyurethane), EFKA4330-4340 (block copolymer), 4400-4440 (modified Polyacrylic acid ester), 5010 (polyurethane), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Ajinomoto "AJISPER PB821, PB822, PB880, PB881" manufactured by Fine-Techno Co., Inc., "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300" manufactured by KYOEISHA CHEMICAL Co., LTD. (Acrylic Copolymer) "," Disparlon KS-86 "manufactured by Kusumoto Chemicals, Ltd. 0, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (naphthalenesulfonate) manufactured by Kao Corporation Acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymeric polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "," SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative) manufactured by The Lubrinzol corporatin, 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals Co., Ltd. Manufacture of "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals Co., Ltd., Hinoakuto T-8000E, etc., Shin-Etsu Chemical Co., Ltd. manufactures polyorganosiloxane polymer KP341, Yusho Co Ltd manufactures "W001: cationic surfactant , Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleene ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, poly Nonionic surfactants such as ethylene glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, manufactured by MORISHITA & CO., LTD. EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "manufactured by SAN NOPCO LIMITED And other polymer dispersants, manufactured by ADEKA CORPORATION "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" , And "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd. and the like. In addition, Acrylicbase FFS-6752, Acrylicbase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments. DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, AJISPER PB881, etc. manufactured by Ajinomoto Fine-Techno Co., Inc. These polymer compounds may be used alone or in combination of two or more kinds.

In addition, as examples of specific examples of the polymer compound, reference may be made to the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417, which are incorporated into this specification.

In addition, as the dispersion resin, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824) can be used. The contents can be referred to and incorporated into this specification. Furthermore, in addition to the above, paragraphs 0028 to 0084 of Japanese Patent Application Laid-Open No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) which include a side chain structure having an acidic group bonded via a linking group can be used The polymer compounds constituting the components may be referred to and incorporated into the present specification.

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

In addition, as a process for dispersing the pigment, a process using compression, extrusion, impact, shearing, or cavitation as a mechanical force for dispersing is mentioned. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a high-speed impeller, a sand grinder, a jet mixer, a high-pressure wet micronization, Ultrasonic dispersion or microjet machine. In addition, "Dispersion Technology Encyclopedia, Issued by Information Corporation, July 15, 2005" or "Dispersion Technology (Suspension (Solid / Liquid Dispersion System) Centered Dispersion Technology" and Industrial Applications Comprehensive data collection, issued by the Publishing Department of the Business Development Center, and the process and disperser described in "October 10, 1978". It is possible to carry out miniaturization of pigments based on the salt milling process. The raw materials, equipment, and processing conditions used in the salt milling process can be described in, for example, Japanese Patent Laid-Open No. 2015-194521 and Japanese Patent Laid-Open No. 2012-046629. Among these, a sand mill (bead mill) is preferred. In addition, in the pulverization of pigments in a sand mill (bead mill), it is preferable to perform the treatment under conditions that improve the pulverization efficiency by using small-diameter beads, increasing the bead filling rate, and the like, and further pulverizing It is preferable to remove coarse particles by filtration, centrifugation, or the like thereafter.

<Polymerization initiator> The resin composition A may contain a polymerization initiator. The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, those having a photosensitivity (so-called photopolymerization initiator) are preferred. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity from the ultraviolet region to visible light. In addition, the polymerization initiator may be an active agent that has some effect with a photo-excited photosensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer. In addition, the photopolymerization initiator preferably contains at least one compound having a Molar absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (more preferably, 330 vm to 500 nm.).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japanese special Compounds described in Japanese Patent Publication No. 53-133428, compounds described in German Patent No. 3337024, compounds based on J. Org. Chem. Of FC Schaefer, etc .; compounds described in 29, 1527 (1964), Japanese Patent Application Laid-Open No. 62-58241 Compounds described in the gazette, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, compounds described in the specification of US Patent No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a fluorenylphosphine compound, and a phosphine oxide compound. , Metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes A compound of the group of its salt, halomethyloxadiazole compound, and 3-aryl substituted coumarin compound is preferable.

Trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds are further Preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when a light-shielding film for a solid-state imaging element is produced using the resin film of the present invention, it is necessary to form a fine pattern in a sharp shape, and it is therefore preferable to develop the residue in the unexposed portion together with the curability. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, step exposure is used for hardening exposure, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Taking these aspects into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern such as a solid-state imaging element. In addition, by using an oxime compound, color transfer properties can be optimized. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into the specification of the present application.

As a photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be used suitably. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine-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 Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption wavelength matches a long-wave light source such as 365 nm or 405 nm. As a fluorenyl phosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name, both manufactured by BASF) can be used as a commercially available product.

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

[Chemical Formula 11]

In formula (I), R ^a represents an alkyl group, a fluorenyl group, an aryl group, or a heterocyclic group, R ^b represents an alkyl group, an aryl group, or a heterocyclic group, and a plurality of R ^c each independently represent a hydrogen atom, an alkyl group, or a -OR ^h represents a group. R ^h represents an electron-withdrawing group or an alkyl ether group. Here, at least any one of a plurality of R ^c represents a group represented by -OR ^h .

In the formula (I), R ^a represents an alkyl group, a fluorenyl group, an aryl group or a heterocyclic group, an aryl group or a heterocyclic group is preferred, and a heterocyclic group is more preferred. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 1 to 10, and even more preferably from 1 to 4. The alkyl group may be any of a straight chain, a branch, and a cyclic ring, and a straight chain or a branch is preferred. The fluorenyl group has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms. Examples of the fluorenyl group include an ethenyl group and a benzamyl group. The number of carbon atoms of the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. Aryl may be a single ring or a fused ring. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a fused ring. The number of condensation is preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 3 to 5, and even more preferably from 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 aforementioned group represented by R ^a may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1, and the like. 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. A fluorine atom is preferred. The number of carbon atoms of the alkyl group as the substituent and the alkyl group represented by R ^X1 and R ^X2 is preferably 1 to 20. The alkyl group may be any of a straight chain, a branch, and a cyclic ring, and a straight chain or a branch is preferred. In the alkyl group, a part or all of the hydrogen atom may be substituted with a halogen atom (preferably a fluorine atom). In addition, in the alkyl group, a part or all of the hydrogen atom may be substituted with the above-mentioned substituent. The number of carbon atoms of the aryl group as the substituent and the aryl group represented by R ^X1 and R ^X2 is preferably 6-20, more preferably 6-15, and still more preferably 6-10. Aryl may be a single ring or a fused ring. In addition, in the aryl group, a part or all of the hydrogen atom may be substituted with the above-mentioned substituent. The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a fused 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. In addition, in the heterocyclic group, a part or all of the hydrogen atom may be substituted with the aforementioned substituent.

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

[Chemical Formula 12]

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 bonding position. 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 single ring or a fused ring. The number of carbon atoms of the ring constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15 and even more preferably 6 to 10. It is preferable that the aromatic hydrocarbon ring is a benzene ring and a naphthalene ring. Among them, at least one of Ar ¹ and Ar ² is preferably a benzene ring, and Ar ¹ is more preferably a benzene ring. Ar ² is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Examples of the substituent that Ar ¹ and Ar ² may have include the substituents described for R ^a . Ar ¹ is preferably unsubstituted. Ar ² may be unsubstituted or may have a substituent. As a substituent, -COR ^X1 is preferred. R ^X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and 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 the formula (II), R ³ represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent R ^a group. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The alkyl group may be any of a straight chain, a branch, and a cyclic ring, and a straight chain or a branch is preferred. The number of carbon atoms of the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. Aryl may be a single ring or a fused ring.

In the formula (I), R ^b represents an alkyl group, an aryl group or a heterocyclic group, an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. Alkyl, aryl and heterocyclyl have the same meanings as those described for R ^a . These groups may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for R ^a .

In formula (I), a plurality of R ^c each independently represent a hydrogen atom, an alkyl group, or a group represented by -OR ^h . R ^h represents an electron-withdrawing group or an alkyl ether group. Here, at least any one of a plurality of R ^c represents a group represented by -OR ^h .

The number of carbon atoms of the alkyl group represented by R ^c is preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 1 to 10, and even more preferably from 1 to 4. The alkyl group may be any of a straight chain, a branch, and a cyclic ring, and a straight chain or a branch is preferred.

As -OR ^h, R ^h is represented by the electron-withdrawing group, for example, include a nitro group, a cyano group, a fluorine atom, at least one hydrogen atom is substituted with fluorine atom of alkyl group having 1 to 20 carbon atoms and the like. Among these, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom is preferred. The number of carbon atoms of the alkyl group is preferably from 1 to 15, more preferably from 1 to 10, and even more preferably from 1 to 4, and it may be any of linear, branched, and cyclic, and linear or branched is more preferred. .

-OR ^h, R ^h is represented by the ether group represents a substituted alkyl of an alkoxyalkyl group. The number of carbon atoms of the alkyl group in the alkyl ether group and the alkyl group in the alkoxy group in the alkyl ether group is preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 1 to 10, and from 1 to 4 Especially better. The alkyl group may be any of a straight chain, a branch, and a cyclic ring, and a straight chain or a branch is preferred. The total number of carbon atoms in the alkyl ether group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

Among the plurality of R ^c , one or two are preferably a group represented by -OR ^h . At this time, -OR ^h, R ^h-based electron-withdrawing group (e.g., at least one hydrogen atom is substituted with fluorine atoms, an alkyl group having a carbon number of 1 to 20 atoms), R ^c of the remaining hydrogen atom is preferred based. On the other hand, when the -OR ^h, R ^h based alkyl ether group, the remaining R ^c is an alkyl group and the other is a hydrogen atom is preferred. And, R ^c are bonded in the benzene ring, with respect to the R ^c group is not bonded to the carbon 1, represented by the R ^c or a group represented by -OR ^h located in the ortho or para position is preferred.

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

[Chemical Formula 13]

[Chemical Formula 14]

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

[Chemical Formula 15]

In formula (III), R ¹ and R ² each independently represent 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 a carbon number An aralkyl group of 7 to 30. When R ¹ and R ² are phenyl groups, the phenyl groups can be bonded to each other to form a fluorenyl group. R ³ and R ⁴ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

In formula (III), R ⁵ represents -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ ,- OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydroxyl group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aromatic group having 7 to 30 carbon atoms An alkyl group or a heterocyclic group having 4 to 20 carbon atoms, a represents an integer of 0 to 5.

In the above formula (III), it is preferable that R ¹ and R ² are independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably directly bonded. Specific examples of the compound represented by the formula (III) include compounds described in paragraphs 0076 to 079 of Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this manual.

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

[Chemical Formula 16]

In addition, the commercially available polymerization initiator is not particularly limited, and examples thereof include IRGACURE OXE 01 (1,2-octanedione 1- [4- (phenylthio) -2--2- (manufactured by BASF JAPAN LTD.). 0-benzylidene oxime)]), IRGACURE OXE 02 (ethyl ketone 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (0-Ethyl oxime)), 2- (Ethyloxyiminomethyl) thioxan-9-acetone, O-fluorenyl oxime (for example, Adekaoptomer N-1919, Adeka Arkles NCI manufactured by ADEKA CORPORATION) -831), Adeka Arkles NCI-930, etc., which are incorporated into this manual.

The content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 7% by mass relative to the total solid content of the composition. . The resin composition A may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more kinds 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 bonded to a silicon atom and can form a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a fluorenyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyl group having 4 or less carbon atoms is particularly preferred. In addition, in order to improve the adhesion between the substrate and the cured film, it is preferable that the silane coupling agent does not include fluorine atoms and silicon atoms (except for silicon atoms bonded by hydrolyzable groups), and does not include fluorine atoms and silicon atoms. (Among them, the silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms are preferred.

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

The silane coupling agent preferably has one or more hardenable functional groups selected from the group consisting of a (meth) acrylic fluorenyloxy group, an epoxy group, and an oxetanyl group. The hardening functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom through a linking group. Among them, epoxy groups are preferred from the viewpoint of improving the adhesion, development resistance, and solvent resistance. Moreover, as a preferable aspect of the curable functional group contained in the said silane coupling agent, a radical polymerizable group is mentioned.

The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, there are many cases of 100 to 1,000. From the standpoint of more excellent effects of the present invention, 270 or more is preferable, and 270 to 1,000 is more preferable.

As one of the preferable aspects of a silane coupling agent, the silane coupling agent X represented by Formula (W) is mentioned. The formula (W) R _Z2 -Lz-Si- (R _Z1 ) ₃ R _z1 represents a hydrolyzable group, and is defined as described above. R _z2 represents a hardenable functional group, as defined above, and the preferred range is also as described above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group which may be substituted by a halogen atom, an arylene group which may be substituted by a halogen atom, -NR ^12- , -CONR ^12- , -CO- , -CO _2- , SO ₂ NR ^12- , -O-, -S-, -SO ₂ -or a combination of these. Among them, at least one selected from the group consisting of a halogen atom-substitutable alkylene group having 2 to 10 carbon atoms and a aryl group substituting a halogen atom having 6 to 12 carbon atoms, or containing these groups and A combination of at least one group selected from the group consisting of -NR ^12- , -CONR ^12- , -CO-, -CO _2- , SO ₂ NR ^12- , -O-, -S-, and SO _2- The group is preferably a group containing a substituted alkylene group having 2 to 10 carbon atoms, -CO _2- , -O-, -CO-, -CONR ¹² -or a combination of these groups Mission is better. Here, the above 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 Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl- Triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) Γ-aminopropyl-triethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) ., Ltd. trade name KBM-503), 3-glycidyl ether propylmethyldimethoxysilane (trade name KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidyl ether propyl Trimethoxysilane (trade name LS-2940 manufactured by Shin-Etsu Chemical Co., Ltd.), glycidyl ether octyltrimethoxysilane (trade name KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.), etc. .

Other preferable aspects of the silane coupling agent include a silane coupling agent Y having at least a silicon atom, a nitrogen atom, a hardenable functional group in the molecule, and a hydrolyzable group bonded to the silicon atom. The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. These may be the same atom or substituent, or may be different. Examples of the bondable atom and substituent include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, and an amine substituted with an alkyl group and / or an aryl group. Group, silyl group, alkoxy group having 1 to 20 carbon atoms, aryloxy group, and the like. These substituents may be further substituted by a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amine group which may be substituted with an alkyl group and / or an aryl group, and a halogen atom. , Sulfonamido, alkoxycarbonyl, amido, urea, ammonium, alkylammonium, carboxyl or its salt, sulfo or its salt, and the like. In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above. The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and it is preferable that the nitrogen atom exists in the form of a secondary amine group or a tertiary amine group, that is, the nitrogen atom has at least one organic group as a substituent. Is better. The structure of the amine group may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amine group such as aniline. Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine, and halogen. Atom, sulfonylamino, alkoxycarbonyl, carbonyloxy, sulfonylamino, urea, alkyleneoxyammonium, alkylammonium, carboxyl or its salt, sulfo, and the like. In addition, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred examples of the organic linking group include the above-mentioned nitrogen atom and a substituent which can be introduced into an organic group bonded thereto.

The definition of the hardenable 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 only needs to have at least one hardenable functional group in one molecule, and may also have two or more hardenable functional groups. From the viewpoint of sensitivity and stability, it has 2 to 20 hardeners. Sexual functional groups are more preferred, 4 to 15 are more preferred, and 6 to 10 are more preferred 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 range (270 or more is preferred).

The content of the silane coupling agent in the resin composition A is more preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass relative to the total solids content in the composition. The resin composition A may contain one kind of silane coupling agent alone, or may contain two or more kinds. 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 containing one or more ethylenically unsaturated groups, more preferably two or more compounds, more preferably three or more compounds, and even more preferably five or more compounds. 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, a (meth) acrylfluorenyl group, and the like.

The polymerizable compound may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, or a mixture of these and a polymer of these. A monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amidines. And these polymers, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amidines of unsaturated carboxylic acids and aliphatic polyamine compounds, and these polymers are preferred. Further, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or the above may be appropriately used. Dehydration condensation reactants of unsaturated carboxylic acid esters or amidoamines with monofunctional or polyfunctional carboxylic acids, and the like. In addition, unsaturated carboxylic acid esters having an electrophilic substituent such as isocyanate group and epoxy group, or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups or toluene Unsaturated carboxylic acid esters such as sulfonyl groups and the like or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Further, instead of the unsaturated carboxylic acid, a styrene derivative such as an unsaturated phosphonic acid or styrene, or a compound group substituted with a vinyl ether, an allyl ether, or the like can be used. As these specific compounds, the compounds described in paragraphs [0095] to [0108] of Japanese Patent Application Laid-Open No. 2009-288705 can also be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound containing 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 examples thereof, the compounds described in paragraphs 0227 of Japanese Patent Application Laid-Open No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 can be referred to, and the contents are incorporated into the specification of the present application.

As the polymerizable compound, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) can also be used. Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product) Sale product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acrylfluorenyl groups are passed through ethylene glycol and propylene glycol residues The structure (for example, SR454, SR499 marketed by Sartomer company Inc.) is preferable. These oligomer types can also be used. Furthermore, 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 following is a description of the state of a preferable polymerizable compound.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphate group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride and an unreacted hydroxyl group of the aliphatic polyhydroxy compound are reacted to have an acid group. The polymerizable compound is more preferable. Among the esters, 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 development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in terms of production and operation. In addition, the photopolymerization performance is good and the curability is excellent.

As for the polymerizable compound, a compound having a caprolactone structure is also preferable. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, and trihydroxymethyl. Polyols such as methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerin, and trimethylol melamine are obtained by esterification with (meth) acrylic acid and ε-caprolactone Ε-caprolactone modified polyfunctional (meth) acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 17]

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 represented by the following general formula (Z-2) The remainder is a group represented by the following general formula (Z-3).

[Chemical Formula 18]

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

[Chemical Formula 19]

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

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

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

[Chemical Formula 20]

In the general formulae (Z-4) and (Z-5), E each independently represents-((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) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In the general formula (Z-4), the total number of (meth) acrylfluorenyl groups is three or four, m each 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) acrylfluorenyl groups is five or six, n each 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), an integer of 0 to 6 is preferable, and an integer of 0 to 4 is more preferable. In addition, an integer of 2 to 40 in total for each m is preferable, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is more preferable. In the general formula (Z-5), an integer of 0 to 6 is more preferable, and an integer of 0 to 4 is more preferable. In addition, an integer of 3 to 60 in total of each n is preferable, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is more preferable. And-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (Z-4) or (Z-5) is an oxygen atom The form of the side end and the X bond is more preferable.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used singly or in combination of two or more kinds. In particular, at least one of the six X's in the general formula (Z-5) is a propylene fluorenyl group, and the six X's in the general formula (Z-5) are all acryl fluorinyl groups. The state of a mixture of compounds which are hydrogen atoms is preferred. With such a structure, 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, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a process known as a conventionally known process: through ring-opening addition reaction, ethylene oxide or propylene oxide is mixed with pentaerythritol Or a process of dipentaerythritol bonding; and, for example, a process of introducing a (meth) acrylfluorenyl group by reacting (meth) acrylfluorene chloride with a terminal hydroxyl group of a ring-opening skeleton. Each process is a well-known process, 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 include compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)"). Among them, exemplary compounds (a) and (b) ), (E), (f) are preferred.

[Chemical Formula 21]

[Chemical Formula 22]

Examples of commercially available polymerizable compounds represented by the general formulae (Z-4) and (Z-5) include SR-, which is a four-functional acrylic ester having four ethylene oxide chains manufactured by Sartomer company Inc. 494. DPCA-60, a 6-functional acrylate with 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., and TPA-330, a 3-functional acrylate with 3 isobutylene oxide chains, etc. .

Examples of the polymerizable compound include urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Other than these, amines having an ethylene oxide system 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. Carbamate compounds are also preferred. In addition, it is also possible to use an amine structure or a thioether structure in the molecule by using those described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. The addition of a polymerizable compound results in a resin composition A having a very high speed of light. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), and DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL Co., LTD), and the like.

In addition, the SP (solubility parameter) value of the polymerizable compound used in the present invention is preferably 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more. In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HLHoy Journal of Painting, 1970, Vol. 42, 76-118). In addition, the SP value is shown by omitting the unit, but the unit is cal ^1/2 cm ^-3/2 .

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

Formula (Q3) [Chemical Formula 23]

In the general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group including a benzene ring surrounded by a dotted 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 limits of e, f, g, and h are respectively from Ar ¹¹ to Ar ¹⁴ The number of substituents minus the value of a, b, c or d. Here, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ and R ¹ to R ⁴ may be independently substituted with The benzene ring surrounded by a dotted line may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), the aryl group represented by Ar ¹¹ to Ar ¹⁴ containing a benzene ring surrounded by a dotted line is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms ( For example, phenyl, naphthyl) is more preferred, and phenyl (limited to a benzene ring surrounded by a dotted line) is more preferred.

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, and an aliphatic group having a polymerizable group is preferred. The aliphatic group having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, and an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 to An alkylene group of 10 is more preferable, and an alkylene group of 2 to 5 carbon atoms is more preferable. 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. Jia, the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom or a sulfur atom is more preferably the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom is further preferred. With X ¹ ~ X ⁴ represents an aliphatic group of the polymerizable group at the 1 to 2 hetero atoms is substituted are preferred, substituted heteroatom is more preferably 1, and Ar ¹¹ ~ Ar ¹⁴ is represented to include It is further preferred that the aryl group of the benzene ring surrounded by a dashed line is substituted with a hetero atom next to it. As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable property, respectively) And a cationic polymerizable group) are preferred. As the radically polymerizable group, a generally known radically polymerizable group can be used, and a preferable one includes a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, and specifically, Examples include vinyl, (meth) acryloxy, and the like. Among them, (meth) acrylic fluorenyloxy is more preferable, and propylene fluorenyloxy is more preferable. As the cationically polymerizable group, generally known cationically polymerizable groups can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spiro Cyclic orthoester, vinyloxy, etc. Among them, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferable. It is preferable that the polymerizable group included in the substituents included in Ar ¹ to Ar ⁴ is a radical polymerizable group. Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, two to four of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, and Ar ¹ to Ar ⁴ More preferably, 2 or 3 of the substituents having a polymerizable group are included, and 2 of Ar ¹ to Ar ⁴ further include a substituent of a polymerizable group. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ may be independently replaced by a benzene ring surrounded by a dotted line, or may be substituted. It is a ring other than a benzene ring surrounded by a dotted line.

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

In the general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited, and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, a fluorenyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, and an aromatic group. Group, heteroaryl group, alicyclic group and the like. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group, or an aryl group, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group is more preferable. Of these, methyl, methoxy or phenyl is further preferred. In the general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, R ¹ to R ⁴ may be independently substituted by dotted lines. The surrounding benzene ring may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are the numbers of substituents that can be included from Ar ¹¹ to Ar ¹⁴ respectively. Subtract the value of a, b, c, or d. e, f, g, and h are each independently 0 to 4, which is preferably, 0 to 2, which is more preferable, and 0, which is further preferable. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, e, f, g, and h are preferably 0 or 1, and 0 is more preferable.

Examples of the compound represented by the formula (Q3) include 9,9'-di [4- (2-propenyloxyethoxy) phenyl] fluorene and the like. As the polymerizable compound having a 9,9-diarylfluorene skeleton, the compounds described in Japanese Patent Application Laid-Open No. 2010-254732 can also be preferably used.

The commercially available polymerizable compound having a Cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD), Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.), and the like.

The content of the polymerizable compound in the resin composition A is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 2% by mass or more. The upper limit is, for example, more preferably 35% by mass or less, and more preferably 30% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

In addition, 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 dispersing resin and the binder resin described above is preferably 0.3 to 2.0. From the viewpoint of more excellent rubbing properties, 0.45 to 1.5 are more preferable.

<Organic solvent> The resin composition A may contain an organic solvent. The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the resin composition A. In consideration of the solubility, coatability, and safety of polymerizable compounds and adhesive resins, it is selected as Better.

As the organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and butyl acetate. Isopropyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g., methyl oxyacetate, ethyl ethoxylate, butyl oxyacetate (e.g. , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters ( For example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Methyl ester, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionates (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxo Propyl propionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2-oxy-2-methyl Ethyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, acetone Propyl ester, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers, for example, diethylene glycol di Methyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, and the like, and as ketones, for example, may be preferred Examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene.

About these organic solvents, it is also preferable to mix 2 or more types from a viewpoint of the solubility of a polymerizable compound, a binder resin, etc., and improvement of a coating surface shape. At this time, it is selected from the group consisting of the aforementioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diglyme, and butyl acetate. , 3-methoxypropanoic acid methyl ester, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate 2 A mixed solution of the above types is particularly preferred. In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains no peroxide.

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

<Other additives> The resin composition A may contain various additives as needed, for example, fillers, adhesion promoters, antioxidants, polymerization inhibitors, antiflocculants, surfactants, infrared absorbers, ultraviolet absorbers, and the like. As these additives, for example, those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116 can be referred to, and these contents are incorporated into the specification of the present application. The resin composition A may contain, for example, a sensitizer or a light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same publication, and the like. In addition, pigments or dyes other than the titanium nitride-containing particles can be blended. Examples of other pigments include the following.

<Other pigments> Examples of the pigment include various conventionally known inorganic pigments and organic pigments. Examples of the inorganic pigment include metal oxides such as iron, zirconium, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and tungsten, and composite oxides of the above-mentioned metals. Examples of the organic pigment include the following. However, the present invention is not limited to these. Dye 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., CI 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., CI 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 CI pigments Green 7, 10, 36, 37, 58, 59 CI Pigment Violet 1, 19, 23, 27, 32, 37, 42 CI 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, CI pigment black 27

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

As the dye, for example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent No. 2592207, U.S. Patent No. 4,885,001, U.S. Patent No. 5,667,920, U.S. Patent No. 5,505,920, U.S. Patent No. 5,667,920, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application No. 6-35183, Japanese Patent Application No. 6-51115 And the pigment disclosed in Japanese Patent Application Laid-Open No. 6-194828. When distinguished as a chemical structure, a pyrazole azo compound, a pyrrole methylene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, and pyridine can be used. Zolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazomethine compounds, and the like. As the dye, a pigment multimer can be used. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097.

These organic pigments or dyes can be used alone or in combination to improve color purity. You can also use more than two kinds.

For example, from the viewpoint of adjusting the color tone, a red pigment for use with the titanium nitride-containing particles is preferable. Although not particularly limited, as a red pigment, pigment red 254 is preferable. In addition, from the viewpoint of improving light-shielding properties, yellow pigments for concrete and the above-mentioned titanium nitride-containing particles are preferred. Although not particularly limited, pigment yellow 150 is preferred as a yellow pigment.

<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 surfactant can be used.

By containing a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (especially, fluidity) when the coating liquid is prepared can be further improved, and the uniformity of coating thickness and liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a composition containing a fluorine-based surfactant, the surface tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved. The applicability to the surface to be coated is improved. Therefore, it is possible to form a film having a uniform thickness with less variation in thickness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac F475, Megafac F475479, Megafac F475479 , Megafac F482, Megafac F554, Megafac F780 (above, manufactured by DIC Corporation), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.). As the fluorine-based surfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylic acid ester compound having a fluorine atom and derived from a repeating unit having 2 or more (preferably 5 or more) can be preferably used. The repeating unit of the (meth) acrylate compound of an alkyleneoxy group (ethyleneoxy group and propyleneoxy group is preferred). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[Chemical Formula 24]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, 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 herein.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate) , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylen Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, 150R1, SOLSPERSE 20000 (manufactured by The Lubrizol Corporatin), etc. In addition, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), And an organosiloxane polymer KP341 (Shin-Etsu Chemical Co. , Ltd.), (meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD), W001 (manufactured by Yusho Co Ltd), and the like.

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

Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Additives & Instruments), etc. In addition, resins and reactive silicones having a polysiloxane as described below are not included in the silicone-based surfactants described herein.

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, and most preferably 0.005 to 0.98% by mass relative to the total solids content of the composition of the present invention.

[Embodiment 1B] Next, as a method of damaging the surface of a film, a state in which a resin film contains a resin having a polysiloxane is described. Examples of the material constituting the resin film include resins having at least the above-mentioned titanium nitride-containing particles, a binding resin, and further 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 coating this on a substrate. Moreover, the said resin composition can also be used as a photosensitive resin composition which has exposure and developability. In this case, a polymerization initiator, a polymerizable compound, and the like may be further added to the resin composition. Moreover, an alkali-soluble material can also be used as a binder resin, a polymerizable compound, a dispersion resin mentioned later, and the like. Hereinafter, various materials included in the resin composition (hereinafter, referred to as "resin composition B") will be described in detail. The materials in the resin composition B are the same except that the filler in the resin composition A is a reactive silicone, and the preferred embodiments are also the same.

[Resin composition B] <Resin having a polysiloxane structure and reactive silicone> In the present invention, as another method of damaging the surface of the resin film, the resin film can also contain a resin having a polysiloxane structure . The resin having a polysiloxane structure mentioned herein is preferably a resin formed from a reactive silicone described later. Reactive silicone is an organic-inorganic hybrid material with low surface free energy. Therefore, if a resin composition containing a reactive silicone and a binding resin (further containing the aforementioned polymerizable compound) is coated on a substrate, the reactive silicone will not react with the bonding resin (and the polymerizable compound described later) It may exist locally on the surface and form an uneven shape. The resin having a polysiloxane structure corresponds to a compound containing at least one of a fluorine atom and a silicon atom.

As a reactive silicone resin, it is a reaction in which a polysiloxane has a side chain, a single end, or both ends, and is substituted with an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a methacrylic group, a mercapto group, or a phenol group. Modified silicone resin. Specific examples of the amine-modified silicone resin include KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, manufactured by Chisso Corporation). Examples of the epoxy-modified silicone resin include KF-105, X-22-163A, X-22-163B, KF-101, and KF-1001. (Above, manufactured by Shin-Etsu Chemical Co., Ltd.) Examples of the polyether-modified silicone resin include X-22-4272 and X-22-4952, and examples of the carboxyl-modified silicone resin include X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of the methanol-modified silicone resin include KF-6001 and KF-6003 (above, Shin-Etsu Chemical Co., Ltd.), as the methacrylic modified silicone resin, X-22-164C (above, manufactured by Shin-Etsu Chemical Co., Ltd.), as the mercapto-modified silicone resin, Examples include KF-2001 (above, 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.) )Wait. Examples of the hydroxy-modified silicone resin include FM-4411, FM-4421, FM-DA21, and FM-DA26 (above, manufactured by Chisso Corporation).

In addition, X-22-170DX, X-22-2426, X-22-176F (above, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. of the single-end reactive silicone resin can also be used as the reactive silicone Resin.

In addition, from the viewpoint of stably and better showing the uneven shape and the stability of the coating liquid, the content ratio of the reactive silicone to the adhesive resin (adhesive resin: reactive silicone) is 100: 1 to 100 : 30 is more preferable, and 100: 5 to 100: 30 is more preferable.

When the resin composition B contains reactive silicone, its content is preferably 0.2 to 20% by mass, more preferably 0.5 to 15% by mass, and 1 to 15% by mass relative to the total solids content of the composition. 1 to 10% by mass is particularly preferred. The resin composition B may contain only one kind of reactive silicone, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

[Production Method of Resin Compositions A and B] The resin compositions A and B may be prepared by mixing the aforementioned components, respectively. When the resin compositions A and B are prepared, the components constituting the resin compositions A and B may be uniformly blended, or the components may be dissolved or dispersed in a solvent and then blended in sequence. In addition, the input sequence and working conditions at the time of cooperation are not particularly limited. For example, all components can be dissolved or dispersed in a solvent at the same time to prepare a composition. If necessary, each component can be appropriately set to two or more solutions or dispersions, and these can be mixed during use (during coating). Prepared into a composition. In order to remove foreign substances or reduce defects, it is preferable to filter the resin compositions A and B with a filter. The filter can be used without particular limitation as long as it has been conventionally used for filtering purposes and the like. Examples include fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, Ultra high molecular weight) and other filters. Among these raw materials, polypropylene (including high-density polypropylene) is preferred. The pore diameter of the filter is preferably about 0.01 to 7.0 μm, more preferably about 0.01 to 3.0 μm, and even more preferably about 0.05 to 0.5 μm. By setting it as this range, the fine foreign material which hinders preparation of a uniform and smooth resin composition in a post process can be reliably removed.

When using filters, different filters can be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. In addition, the first filters having different pore diameters within the above range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by NIHON PALL LTD. (DFA4201NXEY, etc.), Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corpration), or KITZ MICROFILTER CORPORATION can be selected. The second filter can be formed using the same material as the first filter. For example, the filtration by the first filter may be performed only by the dispersion liquid, or the second filtration may be performed after mixing with other components.

[Manufacturing Method of Resin Film] Next, a manufacturing method of the resin film will be described. The resin film of the first embodiment is preferably produced using a resin composition A or a resin composition B. When using the resin composition A or B to manufacture the resin film of the first embodiment, as a method for manufacturing the resin film, it is preferable to have at least a process (resin film formation process) in which the resin composition A or B is provided to the substrate to form a resin film. good. 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, as a method for producing a resin film, the resin composition A or B is provided to a substrate to form a coating film. The process (coating film formation process) and the process for exposing the coating film (exposure process) are preferred. In addition, 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, a patterned resin film can be formed. As specific steps, it is preferable to have the above-mentioned coating film forming process, a process for exposing the coating film to a pattern (pattern exposure process), and a process for developing and removing unexposed portions to form a patterned resin film (development process). . Hereinafter, in the above steps, as a representative example, a method for manufacturing a resin film having a coating film formation process, a pattern exposure process, and a development process will be described in detail. In addition, as described in detail in the subsequent paragraph, the steps of the resin film forming process itself are the same as the steps of the coating film forming process. In addition, the exposure process and the pattern exposure process are the same steps except that the exposure is performed in a pattern in the pattern exposure process.

<Coating film formation process> In this process, a resin film A or B is used to form a coating film on a substrate. 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 active-wire-curable materials such as the titanium nitride-containing particles, the binding resin, the filler, the polymerization initiator, and the polymerizable compound is formed. In addition, when the resin composition B is used, a resin having a polysiloxane structure formed of the titanium nitride-containing particles, a binding resin, a reactive silicone, and the like, and a polymerization initiator and a polymerizable compound are formed. Coating film of linear hardening material. Examples of the substrate include transparent substrates made of glass, silicon, polycarbonate, polyester, aromatic polyamine, polyimide, polyimide, and the like. A thin film transistor for driving an organic electroluminescence (organic EL) element may be formed on the transparent substrates. In addition, a substrate for a solid-state imaging element in which a solid-state imaging element (light-receiving element) such as a CCD (Charge Coupled Element) or CMOS (Complementary Metal Oxide Film Semiconductor) is provided on a substrate can be used. As a method for applying the resin composition A or B to a substrate, a slit coating method, an inkjet method, a spin coating method, a spray coating method, a cast coating method, a roll coating method, or a screen printing method can be used. Various methods. From the viewpoint of obtaining a uniform film thickness of the coating film, a spin coating method and a spray coating method are preferred. When the substrate surface is uneven, a spray coating method and an inkjet method are preferred from the viewpoint of obtaining a uniform film thickness.

In addition, the coating film formed on the substrate may be subjected to heat treatment (pre-baking). At this time, the temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and 100 ° C or lower. The pre-baking time is preferably 10 to 300 seconds, and more preferably 40 to 250 seconds. Heating can be performed by a hot plate, an oven, or the like.

In addition, as described above, when the resin composition A or B does not include the active-ray-curable material, a resin film can be formed on the substrate by performing the steps described in the coating film forming process described above.

<Pattern exposure process> This process is a process of exposing the coating film obtained in the coating film formation process to a pattern. As an exposure method, for example, pattern exposure can be performed by using an exposure device such as a stepper, and performing exposure through a mask having a predetermined mask pattern. Thereby, the exposed part can be hardened. As radiation (light) that can be used at the time of exposure, ultraviolet rays such as g-rays and i-rays can be preferably used (i-rays are particularly preferred). Regarding the irradiation amount (exposure amount), for example, 30 to 1500 mJ / cm ² is preferable, 50 to 1000 mJ / cm ² is more preferable, and 80 to 500 mJ / cm ² is more preferable. In addition, hardening of the active-ray-curable material is performed in the exposure portion.

<Developing process> This process is a process of developing and removing an unexposed part to form a patterned resin film. The development and removal of the unexposed portion can be performed using a developing solution. Thereby, the coating film of the unexposed part in the exposure process is melt | dissolved in a developing solution, and only the light-hardened part (resin film) remains. As the developing solution, an organic alkali developing solution that does not damage the solid-state imaging element and circuit of the substrate is preferred. 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 developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and Organic basic compounds such as butylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene. Examples include dissolving these alkaline agents into an aqueous solution having a concentration of 0.001 to 10% by mass, a concentration of 0.005 to 6% by mass is preferable, and a concentration of 0.01 to 5% by mass is particularly preferable. Moreover, as a developing solution, an inorganic base can be used. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate is preferable. As the developing solution, a surfactant can be used. As an example of a surfactant, a nonionic surfactant is preferable. In addition, when using a developing solution containing such an alkaline aqueous solution, it is usually preferable to wash (rinse) with pure water after development.

[Layer Structure of Resin Film] The resin film may have a single-layer structure including a pigment layer containing titanium nitride 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 adjacent layers contain a structure in which a pigment layer X1 and a pigment layer X2 containing titanium nitride particles are contained, respectively. 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 Ra of the surface on the pigment layer X2 side of the resin film is set to 100Å Above 2000Å is preferred. That is, the outermost surface side of the resin film containing the pigment layer (pigment layer X2) containing the smallest concentration of titanium nitride particles (the layer position farthest from the substrate) appears with respect to the light incident from the surface of the pigment layer X2 side. Excellent light scattering can be made more excellent in low reflectivity. Among them, 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" correspond to the titanium nitride-containing particles with respect to the total solid content of each pigment layer Content.

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

[Second Embodiment: A resin film in which at least one of fluorine atom and silicon atom exists locally on the surface] The resin film in the second embodiment is characterized in that it has the following structure: a pigment layer (hereinafter, simply referred to as "pigment" Layer ".), Containing titanium nitride-containing particles containing one or more metal atoms other than the above-mentioned titanium atom; and a surface layer (hereinafter, simply referred to as a" surface layer ") disposed adjacent to the pigment layer and containing fluorine A compound of at least one of atoms and silicon atoms. The thickness of the resin film is not particularly limited, but is preferably 0.2 to 25 μm, and more preferably 1.0 to 10 μm. The above thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the resin film, and arithmetically averaging these values. The thickness of the surface layer in the resin layer is preferably 0.050 to 0.200 μm.

The resin film can be formed by preparing a compound resin composition containing titanium nitride-containing particles containing at least the above-mentioned metal atoms other than one or more titanium atoms, a binding resin, and at least one of fluorine atoms and silicon atoms. (Hereinafter referred to as "resin composition C"), and apply this to 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), and this compound shows a low surface free energy. Therefore, for example, in a coating film formed by coating the resin composition C on a substrate, the compound is easily concentrated and exists near the surface of the coating film on the opposite side of the substrate. This local surface presence 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 obtained coating film has a pigment layer (lower layer) containing titanium nitride particles as a black pigment and a surface layer (upper layer) formed of a compound containing at least one of a fluorine atom and a silicon atom. 2-layer structure. If such a two-layer structure is formed, the light reflected on the surface of the surface layer and the light reflected at the interface between the surface layer and the pigment layer are eliminated by interference, and can be made low-reflective. In addition, the resin film contains titanium nitride-containing particles as a black pigment in the pigment layer. It has been confirmed that the titanium nitride-containing particles and the compound containing at least one of a fluorine atom and a silicon atom exhibit excellent resistance. Wet. Trace amounts of free radical initiators and unreacted monomers are present in resins such as (meth) acrylic polymers. In a hot and humid environment, heat, oxygen, and moisture produce haze and transparency that accompany the yellowing of the resin. Deterioration of the scutellaria baicalensis is caused by cutting of the polymer, and chain decomposition caused by free radicals generated during cutting (see Japanese Patent Application Laid-Open No. 2011-65146, paragraph [0017]). Since a compound containing at least one of a hydrophobic fluorine atom and a silicon atom is locally present on the surface, it is possible to prevent water from being mixed into the film and prevent the resin from being deteriorated. In addition, although the mechanism is not clear, even if moisture is mixed into the film, it is thought that the titanium nitride-containing particles containing one or more metal atoms other than titanium atoms will capture the generated free radicals.

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 blended in the resin composition C. Furthermore, an alkali-soluble material can be used as a binder resin, a polymerizable compound, a dispersion resin, and the like. Hereinafter, various materials and production methods of the resin composition C will be described.

[Resin Composition C] <A compound containing at least one of a fluorine atom and a silicon atom> The resin composition C contains a compound containing at least one of a fluorine atom and a silicon atom. The compound (hereinafter, also referred to as a “specific compound”) containing at least one of a fluorine atom and a silicon atom is not particularly limited, and preferably has at least one of a fluorine atom and a silicon atom, and a hardenable functional group. In addition, from the viewpoints that the reflectance of the resin film is lower, the pattern linearity of the resin film is more excellent, and defects of the resin film are less likely to occur, the specific compound preferably has a fluorine atom. The specific compound may be a monomer, a polymer, or a polymer. When the specific compound is a polymer, a (meth) acrylate polymer is preferable, and a (meth) acrylate polymer having a fluorine atom is more preferable. Moreover, as one of the preferable aspects of a specific compound, the compound which does not have a benzene ring structure is mentioned, The compound which has a fluorine atom and does not have a benzene ring structure is more preferable. The silane coupling agent is not included in a specific compound.

When the specific compound contains a fluorine atom, the specific compound preferably has 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. The alkylene group substituted with a fluorine atom is preferably a linear, branched or cyclic alkylene group having at least one hydrogen atom substituted with a fluorine atom. The alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group substituted with at least one hydrogen atom 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 even more preferably 1 to 5. 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 a fluorine atom. As examples of an alkyl group substituted with a fluorine atom and an aryl group substituted with a fluorine atom, for example, paragraphs 0266 to 0272 of Japanese Patent Application Laid-Open No. 2011-100089 can be referred to, and the contents are incorporated into this specification.

Among these, from the viewpoints of lower reflectance of the resin film, more excellent linearity of the pattern of the resin film, and difficulty in generating defects of the resin film, the specific compound includes a group X in which an alkylene group substituted with a fluorine atom is bonded to an oxygen atom A group (repeating unit) represented by the formula (X) is more preferable, and a perfluoroalkylene ether group is more preferable. Formula (X)-(L _A -O)-The above L _A represents an alkylene group substituted with a fluorine atom. The number of carbon atoms in the alkylene group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 5. The alkylene group substituted with a fluorine atom may contain an oxygen atom. In addition, the alkylene group substituted with a fluorine atom may be linear or branched. "Perfluoroalkylene ether group" means the above-mentioned L _A- based perfluoroalkylene group. "Perfluoroalkylene" means a group in which all hydrogen atoms in the alkylene group are replaced with fluorine atoms. The group (repeating unit) represented by the formula (X) can be repeatedly connected, and the number of repeating units is not particularly limited. From the viewpoint of more excellent effects of the present invention, 1 to 50 is preferable, and 1 to 20 is more preferable . That is, a group represented by the formula (X-1) is preferable. Formula (X-1)-(L _A -O) _r -In formula (X-1), L _{A is} as described above, and r represents the number of repeating units, and a preferred range thereof is as described above. Further, a plurality of - (L _A -O) - in L _A may be identical or different.

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

[Chemical Formula 25]

The total number of carbon atoms in the alkyl chain of the alkylsilyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Alkylsilyl and trialkylsilyl are preferred. Examples of the aryl group in the arylsilyl group include a phenyl group. When the partial structure (S) is included, the partial structure (S) may be included to form a ring structure. As part of the structure (S) which can be preferably used in the present invention, -Si (R) ₂ -O-Si (R) _2- (R is an alkyl group having 1 to 3 carbon atoms), alkoxysilane Basis is better. As an example of the structure including the partial structure (S), for example, paragraphs 0277 to 0279 of Japanese Patent Application Laid-Open No. 2011-100089 can be referred to, and the contents are incorporated into this specification.

The specific compound may have at least one fluorine atom and silicon atom, and may have two or more. 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 also have two or more curable functional groups. The curable functional group may be only one type, or may be two or more types. The curable functional group may be a thermosetting functional group or a photocurable functional group. The hardenable functional group is selected from the group consisting of (meth) acryloxy, epoxy, oxetanyl, isocyanate, hydroxyl, amine, carboxyl, thiol, alkoxysilyl, and methylol. One or more of the group of vinyl, vinyl, (meth) acrylamido, styryl, and maleimido is preferred, and is selected from the group consisting of (meth) acrylamido, epoxy, And one or more oxetanyl groups are more preferred. 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 more preferably 0.01 to 5.00 mmol / g.

When the specific compound is a monomer, the number of one or more types of groups selected from fluorine atom and silicon atom in one molecule is preferably 1-20, and more preferably 3-15. In addition, the number of hardenable functional groups in one molecule is not particularly limited, and from the viewpoint that the effect of the present invention is more excellent, two or more are preferable, and four or more are more preferable. The upper limit is not particularly limited, and there are many cases where the number is less than ten and more cases where the number is less than six.

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

[Chemical Formula 26]

In the formulae (B1) to (B3), R ¹ to R ¹¹ each 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) acryloxy, epoxy or oxetanyl group, X ² represents an alkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, an alkylsilyl group, an arylmethyl group A silane group or a group containing the above partial structure (S), X ³ represents a repeating unit represented by the formula (X-1).

In formulae (B1) to (B3), it is preferable that R ¹ to R ¹¹ are each independently a hydrogen atom or an alkyl group. When R ¹ to R ¹¹ represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. When R ¹ to R ¹¹ represent a halogen atom, a fluorine atom is preferred. In the formulae (B1) to (B3), when L ¹ to L ⁴ represent a divalent linking group, examples of the divalent linking group include a halogen atom-substituted alkylene group and a halogen atom-substituted terylene. Base, -NR ^12- , -CONR ^12- , -CO-, -CO _2- , SO ₂ NR ^12- , -O-, -S-, -SO ₂ -or a combination of these. Among them, at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms which can be substituted by a halogen atom and an arylene group having 6 to 12 carbon atoms which can be substituted by a halogen atom, or these groups and A combination of at least one group selected from the group consisting of -NR ^12- , -CONR ^12- , -CO-, -CO _2- , SO ₂ NR ^12- , -O-, -S-, and SO _2- The group is preferably a group containing a halogen atom-substituted alkylene group having 2 to 10 carbon atoms, -CO _2- , -O-, -CO-, -CONR ¹² -or a combination of these groups Mission is better. Here, the above R ¹² represents a hydrogen atom or a methyl group.

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

[Chemical Formula 27]

In addition, specific examples of the repeating unit represented by the formula (B2) include the following, but the present invention is not limited to these. In a 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.

[Chemical Formula 28]

[Chemical Formula 29]

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

[Chemical Formula 30]

[Chemical Formula 31]

The content of the repeating unit represented by the above formula (B1) is more preferably 5 to 98 mol%, and more preferably 30 to 95 mol% relative to all 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 mole%, and 5 to 60 mole% relative to all the repeating units in the specific compound. Better. In addition, when the repeating unit represented by the formula (B2) is not included and the repeating unit contained in the formula (B3) is included, the content of the repeating unit represented by the formula (B2) is set to 0 mol% and expressed by the formula (B3) The content of the repeating unit is preferably in the above range.

The specific compound may have a repeating unit other than the repeating units represented by the formulae (B1) to (B3). The content of other repeating units is preferably 50 mol% or less, and more preferably 30 mol% or less, relative to all repeating units in a specific compound.

When the specific compound is a polymer, the weight average molecular weight (Mw: polystyrene conversion) is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. When the specific compound is a polymer, the degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90. The GPC (gel permeation chromatography) method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION) and using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as columns, As eluent, THF (tetrahydrofuran) was used.

As a commercial product of a specific compound, for example, as a specific compound having a fluorine atom, Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, manufactured by DIC Corporation can be used, Megafac RS-77, as a specific compound with a silicon atom, can use BYK-UV 3500, BYK-UV 3530, BYK-UV3570 manufactured by BYK ADDITIVES & INSTRUMENTS, TEGO Rad 2010, TEGO Rad manufactured by EVONIK JAPAN CO., LTD. 2011, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, TEGO Rad 2600, TEGO Rad 2650, TEGO Rad 2700, etc.

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

In addition, as the compound containing at least one of a fluorine atom and a silicon atom, a reactive silicone contained in the resin composition B can also be used. The preferable aspect 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, still more preferably 1 to 15% by mass, and 1 to 10% of the total solids content in the resin composition. Mass% is particularly preferred. The composition may include one specific compound alone or two or more. When the composition contains two or more specific compounds, the total amount may be within the above range.

<Other materials> Among the materials in the resin composition C, the fillers in the resin composition A are the same except that they are compounds containing at least one of a fluorine atom and a silicon atom, and they are the same in a preferred aspect.

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

The resin composition of the present invention preferably does not contain metals other than those contained in the titanium nitride-containing particles, metal salts containing halogens, impurities such as acids and alkalis, and the like. As the content of impurities contained in these materials, 1 ppm or less is preferable, 1 ppb or less is more preferable, 100 ppt or less is more preferable, 10 ppt or less is more preferable, and it is most preferable that it is not substantially contained (below the detection limit of the measuring device). Examples of the method for removing impurities such as metals from various materials include filtration using a filter or a purification process based on distillation (especially thin-film distillation and molecular distillation). Examples of distillation-based purification processes include "<Factory Operation Series> Supplement and Distillation, Issued on July 31, 1992, Chemical Industry Corporation" or "Chemical Industry Manual, Issued on September 30, 2004, Asakura Bookstore, 95 pages" ~ 102 pages. " The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and 3 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. The filter may be a composite material combining these materials and an ion exchange medium. As the filter, an organic solvent may be used. In the filtration process, multiple filters can be used in series or in parallel. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, or the process of filtering multiple times can be a cyclic filtering process. In addition, as a method for reducing impurities such as metals contained in various materials, there can be mentioned a method in which, as a raw material constituting each material, a raw material having a small metal content is selected, and the raw material constituting each material is filtered by a filter, Or, distillation is performed under conditions that minimize contamination by lining the inside of the device with Teflon (registered trademark). The preferable conditions for filter filtration of the raw materials constituting various materials are the same as those described above. In addition to filter filtration, it is possible to remove impurities based on the adsorbent, or to use a combination of filter filtration and adsorbent. 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 manufacturing method of the resin film will be described. The resin film of the second embodiment is preferably produced using a resin composition C. In addition, it does not prevent a method of forming a surface layer 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 using the resin composition C to manufacture the resin film of the second embodiment, it is preferable to have at least a process (resin layer forming process) in which the resin composition C is provided on the substrate to form a resin film including a pigment layer and a surface layer. When the resin composition C is a curable composition containing an active-ray-curable material such as a polymerization initiator and a polymerizable compound, as a method for manufacturing a resin film, a method of forming a coating film by applying the resin composition C to a substrate ( A coating film forming process) and a process for exposing the coating film (exposure process) are preferred. In addition, when the resin composition C is a curable composition containing an active-ray-curable material such as a polymerization initiator and a polymerizable compound, a patterned resin film can be formed. As specific steps, it is preferable to have the above-mentioned coating film forming process, a pattern-exposed coating film process (pattern exposure process), and a process of developing and removing unexposed parts to form a pattern-like resin film (development process). The specific steps of the above-mentioned processes are the same as those of the processes in the first embodiment, and their preferred aspects are also the same.

[Third Embodiment: A resin film having a Ra of 100 to 2000 Å and a compound containing at least one of a fluorine atom and a silicon atom existing locally on the surface] Further, as a modification of the first embodiment (third embodiment), The resin film of the first embodiment has a two-layer structure including a pigment layer including the above-mentioned titanium nitride-containing particles containing at least one metal atom other than titanium atoms, and a surface layer disposed adjacent to the pigment layer. And contains a compound containing at least one of a fluorine atom and a silicon atom, and sets the surface roughness Ra of the surface layer that becomes the outermost surface of the resin film to 100 to 2000 Å. The resin film having the above-mentioned structure shows excellent moisture resistance and more excellent low reflectivity.

When it is set to the state 様, the resin composition A may be further compounded with a compound containing at least one of a fluorine atom and a silicon atom. In addition, 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 preferable aspect (including the compounding amount) is also the same. In addition, the manufacturing method of the resin film of the third embodiment is also the same as that of the first embodiment, and the preferred aspects thereof are also the same.

[Fourth Embodiment: Resin Film Laminated with Pigment Layers of Different Optical Concentrations] The resin film in the fourth embodiment is an adjacent laminated layer containing titanium nitride containing the above-mentioned metal atoms containing at least one or more titanium atoms, respectively. The resin film of the pigment layer Y1 and the pigment layer Y2 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. Among them, 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" correspond to the titanium nitride-containing particles with respect to the total solid content of each pigment layer Content.

The method for manufacturing the resin film in the fourth embodiment is not particularly limited, and it includes at least a resin composition (hereinafter, also referred to as “resin composition D”) for forming a pigment layer Y1 to form a pigment on a substrate. A process of forming a layer Y1 (a process of forming a pigment layer Y1); and a process of forming a pigment layer Y2 on a pigment layer Y1 using a resin composition (hereinafter, also referred to as "resin composition E") forming a pigment layer Y2 (a pigment Layer Y2 forms a process). 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 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, if the pigment layer Y2 is used as a pigment layer having a smaller concentration of titanium nitride particles and light is incident from the pigment layer Y2 side, the light reflected on the surface of the pigment layer Y1 and between the pigment layer Y1 and the pigment layer Y2 The light reflected by the interface is eliminated by interference, and can be made low-reflective. On the other hand, the same effect can be obtained when the pigment layer Y1 on the substrate side is used as a pigment layer having a smaller concentration of titanium nitride 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, and more preferably 30 to 55% by mass. The concentration of the titanium nitride-containing particles in the pigment layer having a low concentration is preferably 1 to 45% by mass, and more preferably 1 to 40% by mass. (Concentration of titanium nitride-containing particles contained in pigment layer Y1)-(Concentration of titanium nitride-containing particles contained in pigment layer Y2) The absolute value 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. In addition, the total thickness of the two layers is preferably 0.5 to 2.0 μm, and more preferably 1.0 to 1.5 μm. The above thickness is an average thickness, and the thickness of any five or more points of the film is measured, and the values are arithmetically averaged.

The optical density (optical density, hereinafter, "OD value") of the resin film is preferably 3 or more in the visible light region with a wavelength of 380 to 700 nm, and more preferably 4 to 5. When the overall OD value is less than 3, a part of the light of the backlight is transmitted, which causes a decrease in contrast. On the other hand, if it exceeds 5, there is a tendency that the amount of black pigment added increases and the reflectance becomes relatively high.

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

Examples of the material included in the resin compositions D and E include the material included in the resin composition A of the first embodiment, and the preferred ranges are 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, a process for exposing the pigment layer (exposure process) may be further provided. When the exposure process is a process for exposing the pigment layer in a pattern, after the exposure process, a process for developing and removing unexposed portions to form a colored pattern (development process) may be further provided. About the preferable aspect of the said coating-film formation process, exposure process, and development process, it is the same as the pigment layer formation process, exposure process, and development process in 1st Embodiment, respectively, and the preferable aspect is also the same.

[Color filter and light-shielding film] The resin films according to the first to fourth embodiments of the present invention can be preferably used as a color filter or a light-shielding film. In particular, it is possible to preferably use a film in which the resin film is cured by exposure. In addition, as described later, the light-shielding film is appropriately arranged on each member, and for example, it can be arranged in a frame shape.

The color filter can be preferably used for a solid-state imaging element such as a CCD (Charge Coupled Element) or a CMOS (Complementary Metal Oxide Film Semiconductor), and is particularly suitable for a high-resolution CCD or CMOS with more than 1 million pixels. The color filter can be used, for example, by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a micro lens for condensing light.

In addition, the color filter can be preferably used as an organic EL element. As the organic EL element, a white organic EL element is preferred. The organic EL element preferably has a tandem structure. The tandem structure of organic EL elements is described in Japanese Patent Application Laid-Open No. 2003-45676, supervised by Miyoshi Akira, "Forefront of Organic EL Technology Development-High Brightness, High Precision, Long Life, Experience Collection-", Technical Information Association, pages 326-328, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided on one surface of the substrate between a lower electrode having light reflectivity and an upper electrode having light transmittance. The lower electrode is preferably made of a material having sufficient reflectance in the wavelength region of visible light. The organic EL layer preferably includes a plurality of light-emitting layers and has a multilayer structure (tandem structure) in which the plurality of light-emitting layers are laminated. In the organic EL layer, for example, the plurality of light emitting layers may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer. In addition, it is preferable to include a plurality of light-emitting auxiliary layers for emitting light from the light-emitting layer together with the plurality of light-emitting layers. The organic EL layer can have a laminated structure in which a light emitting layer and a light emitting auxiliary layer are alternately laminated, for example. The organic EL element having the organic EL layer having such a structure can emit white light. At this time, it is preferable that the spectrum of the white light emitted by the organic EL element has a strong maximum emission peak in the blue region (430nm-485nm), the green region (530nm-580nm), and the yellow region (580nm-620nm). . In addition to this kind of emission peak, it is more preferable to have a maximum emission peak in the red region (650nm-700nm). By combining an organic EL element (white organic EL element) that emits white light with the color filter of the present invention, it is possible to obtain a spectroscopic beam having excellent color reproducibility, and it is possible to display a sharper image or image.

The light-shielding film can be formed in various components in the image display device or the sensor module (for example, an infrared cut-off filter, a peripheral portion of a solid-state imaging element, a peripheral portion of a wafer-level lens, a back surface of a solid-state imaging element, etc.) use. In addition, a light-shielding film may be formed on at least a part of the surface of the infrared-light-cut filter, and the infrared-light-cut filter with a light-shielding film may be used. The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 25 μm, and more preferably 1.0 to 10 μm. The above thickness is an average thickness, which is a value obtained by measuring an arbitrary 5 or more points of the light-shielding film and arithmetically averaging these. The reflectance of the light-shielding film is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and even more preferably 4% or less. In addition, the reflectance of the light-shielding film is a value measured by injecting light of 400 to 700 nm into the light-shielding film at an incident angle of 5 ° and measuring the light with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. Reflectivity.

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

It has a structure in which a plurality of photodiodes, polycrystalline silicon, and other transmission electrodes are included on a substrate and have a light-receiving area constituting a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.). And the transmission electrode has a light-shielding film having only a light-receiving portion opening of the photodiode, and the light-shielding film has a device protection film including silicon nitride and the like formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. There are color filters on it. Furthermore, it may be a structure having a light-condensing mechanism (for example, a micro lens, etc.) on the device protective layer and under the color filter (close to one side of the substrate), a structure having a light-concentrating mechanism on the color filter, and the like. In addition, the color filter may have a structure in which a hardened film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid shape. It is preferable that the partition wall has a low refractive index with respect to each color pixel. Examples of the imaging element having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577.

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

Definitions of display devices or details of each display device are described, for example, in "Electronic Display Devices (by Sasaki Akio, Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display Devices (Ibuki Shunshu, Industrial Books) Co., Ltd. issued in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Second-generation liquid crystal display technology (edited by Ryuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "second generation liquid crystal display technology".

The color filter of the present invention can be used for a liquid crystal display device of a color TFT (Thin Film Transistor) system. A color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD. 1996)". Furthermore, the present invention can also be applied to liquid crystal display devices with enlarged viewing angles such as lateral electric field driving methods such as IPS (In Plane Switching), pixel division methods such as MVA (Multi-domain Vertical Alignment), STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend). In addition, the color filter in the present invention can also be used in a bright and high-definition COA (Color-filter On Array) method. For a liquid crystal display device of the COA system, the required characteristics for a color filter may be the required characteristics for an interlayer insulation film, that is, low dielectric constant and peeling liquid resistance, in addition to the usual required characteristics as described above. The color filter of the present invention is excellent in light resistance and the like, and therefore can provide a liquid crystal display device of the COA type with high resolution and excellent long-term durability. In addition, in order to meet the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer. These image display methods are described in, for example, page 43 of "EL, PDP, and LCD Display-Latest Trends in Technology and Market-(TORAY Research Center, Inc. Survey and 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 protective film. The color filter of the present invention can be applied to a liquid crystal display device including these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima CMC-Group. 1994)", "Current Status and Future Outlook of the Liquid Crystal Related Market in 2003 (Volume II) (Table Ryoji Fuji Chimera Research Institute, Inc., 2003). " Regarding the backlight, in addition to SID meeting Digest 1380 (2005) (A. Konno et.al), it is described in the monthly display December, 2005, pages 18 to 24 (Island Kangyu), and in SID meeting Digest 1380 (2005) 25 ~ 30 pages (Yaki Taki).

In addition, the cured film obtained by curing the hardening composition can be used in portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers or scanners; surveillance cameras , Barcode readers, ATMs, high-speed cameras, or personal authentication using face image authentication; automotive camera equipment; medical cameras such as endoscopes, capsule endoscopes, or catheters Equipment; biosensors, biosensors, cameras for military reconnaissance, cameras for stereo maps, meteorology, marine observation cameras, land resource surveillance cameras or space astronomy, deep space target exploration cameras and other space equipment The light-shielding member, light-shielding layer, anti-reflection member, or anti-reflection layer of the optical filter or module used in the above.

In addition, the cured film obtained by curing the curable composition can also be applied to applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). Although it is not particularly limited, in addition to an optical filter or an optical film used in a micro LED or a micro OLED, it can be preferably used for a component that imparts a light-shielding function or an anti-reflection function. Examples of the micro LED or the micro OLED include a micro LED or a micro OLED of Japanese Patent Application Publication No. 2015-500562 or Japanese Patent Application Publication No. 2014-533890.

The cured film obtained by curing the curable composition can also be used in applications such as quantum dot displays. Although it is not particularly limited, in addition to an optical filter or an optical film used in a quantum dot display, it is also preferably used for a component that provides a light-shielding function or an anti-reflection function. Examples of quantum dot displays include those disclosed in U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, or U.S. Patent Application Publication No. 2014/0035960 . [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed in a limited manner by the embodiments shown below. In addition, unless otherwise specified, "parts" and "%" are mass standards.

Hereinafter, each component used in an Example and a comparative example is demonstrated in detail.

(Pigment) (Black Pigment Pig-1) A black pigment Pig-1 was produced under the following conditions. High-frequency power 5.5kW Plasma gas flow 5L / min argon 5L / min Nitrogen spray flow 20L / min Nitrogen powder supply JEOL Ltd. powder supply device TP-99010FDR Supply gas nitrogen 15L / min Supply amount 15g / min Powder Ti Powder TOHO TITANIUM CO., LTD TC-200 Ag powder Mitsui Mining & Smelting Co., Ltd. SPQ03R Fe powder JFE Steel Corporation JIP 270M

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 30 ℃, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ gas introduced into the Ar gas atmosphere In the state, it was left to stand at 30 ° C for 24 hours.

With respect to the obtained titanium nitride-containing particles (Pig-1 black pigment), the content of titanium (Ti) atoms and metal atoms was measured by ICP emission spectrometry. With respect to the total amount (100% by mass) of the black pigment Pig-1, the content of Ti atoms is 60% by mass, the content of Ag atoms is 15% by mass, and the content of Fe atoms is 1% by mass. In the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. The content of nitrogen and oxygen atoms was measured using an oxygen and nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by HORIBA, Ltd., and calculated by an inert gas thermal conductivity method. As a result, the content of nitrogen atoms was 19% by mass with respect to the total amount (100% by mass) of the black pigment Pig-1, and the content of oxygen atoms was 5 with respect to the total amount (100% by mass) of the black pigment Pig-1. quality%.

In addition, 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 put into an aluminum standard sample holder, and measurement was performed by a wide-angle X-ray diffraction method (RU-200R, manufactured by Rigaku Corporation). As the measurement conditions, the X-ray source was set to CuKα rays, the output was set to 50kV / 200mA, the slit system was set to 1 ° -1 ° -0.15mm-0.45mm, the measurement step (2θ) was set to 0.02 °, and the scanning speed was set to 2 ° / min. The diffraction angle of the peak originating from the TiN (200) plane, which can be observed around 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 was determined as follows, that is, a high-precision full-automatic gas adsorption device ("BELSORP" 36) manufactured by MicrotracBEL Corp. was subjected to vacuum degassing at 100 ° C, and the liquid of N ₂ gas was measured The adsorption isotherm at nitrogen temperature (77K) was analyzed by the BET method. As a result, the specific surface area of the black pigment Pig-1 obtained by the BET method was 29 m ² / g.

(Black pigment Pig-2) A black pigment Pig-2 was produced under the following conditions. High-frequency power 5.5kW Plasma gas flow 5L / min argon 5L / min Nitrogen spray flow 20L / min Nitrogen powder supply JEOL Ltd. powder supply device TP-99010FDR Supply gas nitrogen 15L / min Supply amount 15g / min Powder Ti TC-200 Ag powder made by TOHO TITANIUM CO., LTD SP-03 Ag powder made by Mitsui Mining & Smelting Co., Ltd. SPQ03R Ni powder made by TOHO TITANIUM CO., LTD

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 30 ℃, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ gas introduced into the Ar gas atmosphere In the state, it was left to stand at 30 ° C for 24 hours.

With respect to the obtained titanium nitride-containing particles (Pig-2 black pigment), the content of titanium (Ti) atoms and metal atoms was measured by ICP emission spectrometry. With respect to the total amount (100% by mass) of the black pigment Pig-2, the content of Ti atoms is 65% by mass, the content of Ag atoms is 8% by mass, and the content of Ni atoms is 2% by mass. In the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. The content of nitrogen and oxygen atoms was measured using an oxygen and nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by HORIBA, Ltd., and calculated by an inert gas thermal conductivity method. As a result, the content of nitrogen atoms was 20% by mass with respect to the total amount (100% by mass) of the black pigment Pig-2, and the content of oxygen atoms was 5 with respect to the total amount (100% by mass) of the black pigment Pig-2. quality%.

In addition, an X-ray diffraction test was performed on the black pigment Pig-2 by the following method. X-ray diffraction was performed as follows. That is, a powder sample was put into an aluminum standard sample holder, and measurement was performed by a wide-angle X-ray diffraction method (RU-200R, manufactured by Rigaku Corporation). As a measurement condition, an X-ray source was set to CuKα rays, an output was set to 50 kV / 200 mA, a slit system was set to 1 ° -1 ° -0.15mm-0.45mm, a measurement step (2θ) was set to 0.02 °, and a scanning speed Set to 2 ° / minute. The diffraction angle of the peak originating from the TiN (200) plane, which can be observed around 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 was determined as follows, that is, a high-precision fully automatic gas adsorption device ("BELSORP" 36) manufactured by MicrotracBEL Corp. was subjected to vacuum degassing at 100 ° C, and the N ₂ gas was measured. Adsorption isotherms at liquid nitrogen temperature (77K), and the isotherms were analyzed by the BET method. As a result, the specific surface area of the black pigment Pig-2 obtained by the BET method was 33 m ² / g.

(Black pigment Pig-3) A black pigment Pig-3 was produced by the same method as the black pigment Pig-2 except that the following powders were used. The V powder refers to vanadium powder. Powder Ti powder TC-200 Ag powder manufactured by TOHO TITANIUM CO., LTD Mitsui Mining & Smelting Co., Ltd. SPQ03R V powder TAIYO KOKO Co., LTD. VN200

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 100 ℃ for, and concentration of O ₂ in the embodiment becomes 100ppm O ₂ gas introduced into the Ar gas atmosphere Under the shape, it was left to stand at 100 ° C for 24 hours.

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

The diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2. As a result, the diffraction angle of the peak derived from the TiN (200) plane of the black pigment Pig-3 was evaluated. 2θ is 42.8 °.

The specific surface area of the black pigment Pig-3 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 25 m ² / g.

(Black Pigment Pig-4) A black pigment Pig-4 was produced by the same method as the black pigment Pig-2 except that the following powders were used. The W powder refers to a tungsten powder. Powder Ti powder TC-200 W by TOHO TITANIUM CO., LTD powder W-H Fe powder by JAPAN NEW METALS CO., LTD. JIP 270M by JFE Steel Corporation

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 200 ℃, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ gas introduced into the Ar gas atmosphere In a state, it was left to stand at 200 ° C for 24 hours.

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

The diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2. As a result, the diffraction angle of the peak derived from the TiN (200) plane of the black pigment Pig-4 was evaluated. 2θ is 43.0 °.

The specific surface area of the black pigment Pig-4 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 27 m ² / g.

(Black Pigment Pig-5) A black pigment Pig-5 was produced in the same manner as the black pigment Pig-2 except that the following powders were used. Powder Ti powder TC-200 made by TOHO TITANIUM CO., LTD Ni powder made by TOHO TITANIUM CO., LTD Fe powder JFE Steel Corporation made JIP 270M

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 200 ℃, the concentration of O ₂ in the embodiment become 1000ppm O ₂ gas introduced into the Ar gas atmosphere In a state, it was left to stand at 200 ° C for 24 hours.

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

The diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2. As a result, the diffraction angle of the peak derived from the TiN (200) plane of the black pigment Pig-5 was evaluated. 2θ is 43.5 °.

The specific surface area of the black pigment Pig-5 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 34 m ² / g.

(Black pigment Pig-6) A black pigment Pig-6 was produced in the same manner as the black pigment Pig-2 except that the following powders were used. Powder Ti powder TC-200 Ag manufactured by TOHO TITANIUM CO., LTD SPQ03R W manufactured by MITSUI MINING & SMILTING CO., LTD W-H V powder manufactured by JAPAN NEW METALS CO., LTD. VN200 manufactured by TAIYO KOKO Co., LTD.

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, for 24 hours at 30 ℃, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ gas introduced into the Ar gas atmosphere In the state, it was left to stand at a temperature of 30 ° C for 24 hours.

In the same manner as the black pigment Pig-2, the content of titanium (Ti) atoms and metal atoms of the obtained titanium nitride-containing particles (black pigment Pig-6) was measured. As a result, with respect to the total amount (100% by mass) of the black pigment Pig-6, the content of Ti atoms was 57% by mass, the content of Ag atoms was 10% by mass, the content of W atoms was 7.99% by mass, and the content of V atoms 0.01 mass%. Moreover, the content of nitrogen atom and oxygen atom was also measured by the same method as the black pigment Pig-2. As a result, the content of nitrogen atoms was 18% by mass with respect to the total amount (100% by mass) of the black pigment Pig-6, and the content of oxygen atoms was 7 with respect to the total amount (100% by mass) of the black pigment Pig-6. quality%.

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

The specific surface area of the black pigment Pig-6 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 32 m ² / g.

(Black Pigment Pig-7) A black pigment Pig-7 was produced in the same manner as the black pigment Pig-2 except that the following powders were used. Powder Ti powder TC-200 Ag made by TOHO TITANIUM CO., LTD MITSUI MINING & SMILTING CO., LTD made SPQ03R Fe powder JFE Steel Corporation made JIP 270M

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, allowed to stand for 24 hours at (300 ℃), the concentration of O ₂ in the embodiment become 1000ppm O ₂ gas introduced into the Ar gas atmosphere In the state, it was left to stand at a temperature of 300 ° C for 24 hours.

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

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

The specific surface area of the black pigment Pig-7 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 30 m ² / g.

(Black Pigment Pig-8) A black pigment Pig-8 was produced in the same manner as the black pigment Pig-2 except that the following powders were used. Powder Ti powder TC-200 made by TOHO TITANIUM CO., LTD Ni powder made by TOHO TITANIUM CO., LTD V powder TAIYO KOKO Co., Ltd. made VN200

After the particles after plasma treatment under an Ar gas atmosphere, the O ₂ concentration of 50ppm or less, allowed to stand for 24 hours at (300 ℃), the concentration of O ₂ in the embodiment become 1000ppm O ₂ gas introduced into the Ar gas atmosphere In the state, it was left to stand at a temperature of 300 ° C for 24 hours.

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

The diffraction angle 2θ of the peak derived from the TiN (200) plane was evaluated in the same manner as the black pigment Pig-2. As a result, the diffraction angle of the peak derived from the TiN (200) plane of the black pigment Pig-8 was evaluated. 2θ is 43.7 °.

The specific surface area of the black pigment Pig-8 was determined by the same method as the black pigment Pig-2. As a result, the specific surface area was 26 m ² / g.

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

[Table 1]

(Manufacturing method of pigment dispersion liquid A) The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR made by IKA COMPANY), and dispersion A was obtained. In addition, referring to the description of Japanese Patent Application Laid-Open No. 2013-249417, a resin (X-1) described below was synthesized. 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 of the graft chain (excluding hydrogen atoms) was 117.

[Chemical Formula 32]

-Composition 1-・ Pig-1 black pigment: 25 parts by mass ・ 30% by mass of propylene glycol monomethyl ether acetate resin (X-1) Solution: 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 dispersion treatment under the following conditions using NPM Pilot manufactured by Shinmaru Enterprises Corporation to obtain a pigment dispersion liquid A. (Dispersion conditions) ・ Bead diameter: φ0.05mm ・ Bead filling rate: 65% by volume ・ Grinding peripheral speed: 10m / sec ・ Separator peripheral speed: 11m / s ・ Mixed liquid amount for dispersion treatment: 15.0g ・Circulating flow (supply amount of pump): 60kg / hour ・ Temperature of treatment liquid: 20 ～ 25 ℃ ・ Cooling water: Tap water 5 ℃ ・ Bead mill ring channel internal volume: 2.2L ・ Number of channels: 84 channels

(Production method of pigment dispersion liquid B) A pigment dispersion liquid B was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with Pig-2.

(Production Method of Pigment Dispersion Liquid C) The black pigment Pig-1 was replaced with "13M-T (trade name)" manufactured by Mitsubishi Materials Corporation, and was produced in the same manner as the method for producing the pigment dispersion liquid A described above. Pigment dispersion liquid C. The pigment particles included in "13M-T (trade name)" manufactured by Mitsubishi Materials Corporation are titanium oxynitride.

(Production method of pigment dispersion liquid D) A pigment dispersion was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the resin (X-1) was replaced with a resin (X-2) having the following structure.液 D。 Liquid D.

(Resin (X-2)) [Chemical Formula 33]

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 (excluding hydrogen atoms) of the graft chain was 72.

(Production method of pigment dispersion liquid E) A pigment dispersion liquid E was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-3.

(Production method of pigment dispersion liquid F) A pigment dispersion liquid F was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-4.

(Production method of pigment dispersion liquid G) A pigment dispersion liquid G was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-5.

(Production method of pigment dispersion liquid H) A pigment dispersion liquid H was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-6.

(Production Method of Pigment Dispersion Liquid I) A pigment dispersion liquid I was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-7.

(Production method of pigment dispersion liquid J) A pigment dispersion liquid J was produced in the same manner as in the method for producing the pigment dispersion liquid A except that the black pigment Pig-1 was replaced with the black pigment Pig-8.

(Red Pigment Dispersion Liquid) Next, a paragraph (0409) of the document (International Publication No. 2015/029643) was referred to to prepare a red pigment dispersion liquid.

(Adhesive resin) ・ P-1: Acrylicbase FF-187 (manufactured by FUJIKURA KASEI CO., LTD.) ・ P-2: Acrycure RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.)

・ P-3: Mixed 4,4'-diaminophenyl ether (0.30 mol equivalent), p-phenylenediamine (0.65 mol equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.5 mol equivalent), 850 g of γ-butyrolactone, and 850 g of N-methyl-2-pyrrolidone to obtain a mixture, 3,3 ', 4,4'-oxodiphthalic acid was further added to the mixture After acid dianhydride (0.9975 mole equivalents), the mixture was reacted at 80 ° C for 3 hours. Maleic anhydride (0.02 mol equivalent) was further added to the obtained reactant, and it was made to react at 80 degreeC for 1 hour, and the polyamic acid (polymer concentration 20 mass%) solution was obtained as the polymer 3.

・ P-4: After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Patent No. 3120476; Example 1), add It became 40 mass parts of glycidyl methacrylate. Thereafter, after reprecipitation with distilled water, the solid content was recovered by filtration, and the solid content was dried. As a result of Polymer 4, acrylic acid having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g) was obtained. Polymer powder.

・ P-5: Acrylicbase FF-426 (FUJIKURA KASEI CO., LTD.)

(Filler) ・ Hollow silica: Sururia 5320, maximum particle size distribution: 75nm, manufactured by JGC Catalysts and Chemicals Ltd. (20wt% MIBK (methyl isobutyl ketone) solution) ・ Silica dioxide 1: FF-D- B1. Maximum particle distribution: 300nm, manufactured by KOHSHIN CHEMICAL (72wt% PGME solution) • Silicon dioxide 2: FF-B-B1, maximum particle distribution: 30nm, manufactured by KOHSHIN CHEMICAL (60wt% PGME solution) • Acrylic particles 1 : MX-80H3wT, particle maximum value: 800nm, manufactured by Soken Chemical & Engineering Co., Ltd. (powder) ・ Acrylic particle 2: MP-300, particle maximum value: 100nm, Soken Chemical & Engineering Co., Ltd Manufacturing

(A compound containing at least one of fluorine atom and silicon atom) ・ S-1: Megafac RS-72-K (manufactured by DIC Corporation) ・ S-2: Megafac RS-55 (containing fluorine atom and silicon atom, manufactured by DIC Corporation)・ S-3: KF-6001 (containing hydroxy silicone, manufactured by Shin-Etsu Chemical Co., Ltd.) In addition, the above S-1 and S-2 are repeating units containing at least one containing a fluorine atom and a silicon atom And a polymer compound having a repeating unit of a polymerizable group in a side chain.

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

[Chemical Formula 34]

(Solvent) • PGMEA: propylene glycol monomethyl ether acetate • PGME: 1-methoxy-2-propanol • High boiling solvent: Haisorubu BDM (diethylene glycol butyl methyl ether, boiling point 212 ° C, TOHO Chemical Industry Co. , Ltd.)

(Polymerization 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 (made by BASF) ・ K-5: KAYACURE DETX-S (made by Shojisangyo KK)

[Chemical Formula 35]

(Polymerizable compound) ・ M-1: Compound of the following structure (manufactured by Nippon Kayaku Co., Ltd.) [Chemical Formula 36]

・ M-2: OGSOL EA-0200 (manufactured by Osaka Gas Chemicals Co., Ltd.) ・ M-3: ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.) In addition, the above M-2 has a Cardo structure and is equivalent In a polymerizable compound with a 9,9-diarylfluorene skeleton.

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

[Production and Evaluation of Resin Film 1] (1) Preparation of Resin Composition A resin composition was prepared by stirring and mixing the components shown in Tables 2 and 3 described later. In addition, all the resin compositions of Examples 1 to 16 were prepared such that the solid content in the composition was 27.5% by mass. In addition, in the resin compositions of Examples 1 to 16, except for Example 7, the pigment concentration with respect to the total solid content in the composition was 50% by mass, and Example 7 was prepared to be 30% by mass. In addition, the resin compositions of Examples 8 to 14 and Examples 1A and 2A were prepared so that the content (M) of the polymerizable compound relative to the total content (B) of the dispersing resin and the binding resin was approximately (M / B). It became 0.9, and Examples 15 and 16 were prepared as 0.39 and 1.1, respectively.

(Example 1) To a 200 g container (disposable cup), 14 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 10 g of PGMEA, and 21 g of Sururia 5320 (20% MIBK) were sequentially added. (Solution), 55 g of the pigment dispersion liquid A, and stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 2) Sururia 5320 (20% MIBK solution) was replaced with silicon dioxide 1 (FF-D-B1, maximum particle distribution: 300 nm, manufactured by KOHSHIN CHEMICAL) (72 wt% PGME solution), and In Example 1, a resin composition was prepared in the same manner. The desired solid content concentration was adjusted by adjusting PGMEA.

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

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

(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) To a 200 g container (disposable cup), 6 g of P-4, 28 g of PGMEA, 7 g of ethyl lactate, 4 g of KF-6001 (S-3), and 55 g of pigment dispersion liquid A were sequentially added. The resin composition was prepared by stirring for 30 minutes with a stirrer.

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

(Comparative Example 2) To a 200 g container (disposable cup), 24 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 21 g of PGMEA, and 55 g of pigment dispersion liquid A were sequentially added. The resin composition was prepared by stirring with a stirrer for 30 minutes.

(Example 7) To a 200 g container (disposable cup), 30 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 13 g of NMP (N-methylpyrrolidone), and 7 g P-3 (20% PGMEA (propylene glycol monomethyl ether acetate) solution), 17 g of Sururia 5320 (20% MIBK solution), 33 g of pigment dispersion A (black pigment: 8.2 g, resin X-1: 2.5 g, PGMEA: 13 g, butyl acetate: 9.1 g), and the resin composition was prepared by stirring with a stirrer for 30 minutes.

(Example 8) To a 200 g container (disposable cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 22 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 14 g of Sururia 5320 (20% MIBK solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 9) To a 200 g container (disposable cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 32 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 4 g of silicon dioxide 1 (FF-D-B1, maximum particle distribution: 300 nm, manufactured by KOHSHIN CHEMICAL, 72 wt% PGME solution, 42 wt% of silicon dioxide in solid content), 55 g The pigment dispersion liquid A was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 10) Sururia 5320 (20% MIBK solution) was replaced with acrylic particles 1 (MX-80H3wT, maximum particle distribution: 800 nm, manufactured by Soken Chemical & Engineering Co., Ltd.) (powder), and others A resin composition was prepared in the same manner as in Example 8. The desired solid content concentration was adjusted by adjusting PGMEA.

(Example 11) To a 200 g container (disposable cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 33 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 3 g of KF-6001 (S-3), and 55 g of pigment dispersion liquid A were 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) To a 200 g container (disposable cup), 5 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 17 g of PGMEA, and 1 g of K-2, 13g of Sururia 5320 (20% MIBK solution), 12g of red dispersion (prepared according to the method of paragraph 0409 of International Publication No. 2015/029643), 50g of pigment dispersion A (black pigment: 12g (Resin X-1: 3.7 g, PGMEA: 21.3 g, butyl acetate: 13 g), and the resin composition was prepared by stirring with a stirrer for 30 minutes.

(Example 14) To a 200 g container (disposable cup), 5 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), and 1 g of P-5 ( 40% PGMEA (propylene glycol monomethyl ether acetate) solution), 34 g of PGMEA, 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 3 g of KF-6001, 55 g of pigment dispersion liquid A, and stirred with a stirrer for 30 minutes To prepare a resin composition.

(Example 15) To a 200 g container (disposable cup), 3 g of M-1, 9 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 18 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 14 g of Sururia 5320 (20% MIBK solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 16) To a 200 g container (disposable cup), 5 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 24 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 14 g of Sururia 5320 (20% MIBK solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 1A) To a 200 g container (disposable cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 32 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF Japan Co., Ltd.), 7 g of silicon dioxide 2 (FF-B-B1, maximum particle distribution: 30nm, manufactured by KOHSHIN CHEMICAL, 60wt% PGME solution, 10wt% of silicon dioxide in solid content), 55 g of the pigment dispersion liquid A was stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 2A) To a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 31.7 g of PGMEA, and 1 g were sequentially added. IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 0.3 g of silicon dioxide 1 (FF-D-B1, maximum particle distribution: 300 nm, manufactured by KOHSHIN CHEMICAL, 72wt% PGME solution, 42% by weight of silicon dioxide in solid content ), 55g of Pigment Dispersion A, and stirred for 30 minutes with a stirrer to prepare a resin composition.

(2) Production of resin film After the resin composition of each example and comparative example was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning Incorporated), it was heated on a heating plate at 100 ° C for 2 minutes. Handling (pre-baking). Thereafter, the coating film obtained above was subjected to an exposure process (exposure device UX3100-SR (manufactured by USHIO INC.), And the exposure amount was 1000 mJ / cm ² ) through a predetermined mask. Thereafter, the substrate was subjected to a heat treatment (post-baking) for 300 seconds using a 220 ° C. hot plate to produce a substrate with a resin film.

(3) Evaluation <Evaluation of contact angle> The contact angle was evaluated using the produced substrate with a resin film. Specifically, after adding one drop of pure water to a resin film on a substrate, an automatic contact angle meter (Kyowa Interface Science Co., Ltd. Drop Master 500 [trade name]) was used for the static contact angle at the elapse of 5 seconds. ), An automatic measurement was performed according to the θ / 2 method (measurement temperature: 25 ° C). The same measurement was performed 5 times, and the average value was made into the static contact angle with respect to pure water. The results are shown in Tables 2 and 3.

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

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

<Evaluation of Moisture Resistance> Using the produced substrate with a resin film, the moisture resistance was evaluated. Specifically, a high-acceleration life tester (EHS-221 manufactured by ESPEC CORP.) Was used to perform a high-temperature and high-humidity test for 750 hours at a temperature of 85 ° C and a humidity of 95%. For a substrate with a resin film before and after the moisture resistance test, the reflectance at a wavelength of 400 nm (the reflectance was measured using a spectroscope "UV4100 (trade name)" manufactured by Hitachi High-Technologies Corporation.). Those with an absolute value of 3% or more are designated as "D", those with a change rate of 1% or more and less than 3% are designated as "C", and those with a change rate of 0.5% or more and less than 1% are designated as "B" The evaluation was performed with a change rate of less than 0.5% as "A". In addition, a decrease in the reflectance based on the humidity resistance test causes a phenomenon such as film surface damage on the surface, so a decrease in the reflectance based on the humidity resistance test is not preferable. The results are shown in Tables 2 and 3.

<Friction test evaluation> The friction test evaluation was performed using the produced substrate with a resin film. Specifically, the friction cloth was rubbed 10 times with a force of 1 kgf, and the defects adhering to the surface of the resin film were visually observed. The same evaluation was performed three times, and the defect was confirmed in all the evaluations as C, and the defect was confirmed in any of the three evaluations as B, and the defect was not confirmed in all the evaluations. Set to A. The results are shown in Tables 2 and 3.

[Table 2]

[table 3]

Moreover, regarding 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 friction test was "A".

Based on the above results, it was confirmed that a resin film containing titanium nitride-containing particles and a binder resin containing metal atoms other than titanium atoms and having a surface roughness (arithmetic average roughness Ra) of 100 to 2000Å was excellent in low reflectivity and resistant to Wetness is also excellent. It was confirmed that especially when hollow silica is used as a filler (Examples 1, 5, 7, 8, 12, 13, 15, and 16), low reflectance is more excellent. In addition, according to a comparison between Examples 1 and 5, it was confirmed that when titanium nitride-containing particles containing metal atoms other than titanium atoms are used, particles containing silver and iron as metal atoms have more excellent moisture resistance. In addition, if the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersing resin and the binding resin is different, Example 8 (M / B: about 0.9) and Example 15 (M / B: 0.39) and Example 16 (M / B: 1.1), it was confirmed that in Example 8 and Example 16 with M / B in the range of 0.45 to 1.5, more excellent abrasion resistance was confirmed. Sex.

In Example 16, the photosensitive resin composition was prepared in the same manner except that the amounts of the adhesive resin and the polymerizable compound were adjusted so that M / B became 1.6 without changing the total amount of the adhesive resin and the polymerizable compound. . The same evaluation as in Example 16 was performed. As a result, the same result as in Example 16 was obtained except that the result of the friction test was "B".

In addition, when Examples 9 and 1A were compared, it was confirmed that in Example 1A, the maximum value in the maximum distribution of the added filler was 30 nm, and the moisture resistance was low. In addition, when Examples 9 and 10 are compared, in Example 10, the maximum value in the maximum distribution of the added fillers is 800 nm, and the results based on the friction test are low.

In addition, when Example 9 is compared with Example 2A, in Example 2A in which the filler content is less than 1.0% by mass, the moisture resistance is lowered.

On the other hand, since the resin film of Comparative Example 1 does not include titanium nitride-containing particles containing metal atoms other than titanium atoms, the resin film has lower moisture resistance than the resin film of Examples. As described above, there are trace amounts of radical initiators and unreacted monomers in resin films such as (meth) acrylic polymers. In a hot and humid environment, heat, oxygen, and moisture may generate free radicals. In addition, free radicals are generated during the severing and cutting of the polymer, which may cause chain decomposition. The resin film of the example contains titanium nitride-containing particles containing metal atoms other than titanium atoms. The metal atoms trap free radicals generated in the film, and it is inferred that the deterioration of the film is unlikely to occur and the moisture resistance is excellent. By. On the other hand, in the resin film of Comparative Example 1, surface deterioration occurred due to free radicals, resulting in poor moisture resistance.

In addition, since the resin film of Comparative Example 2 did not have a predetermined uneven structure on the surface, neither the low reflectivity nor the moisture resistance reached the desired level. In addition, it is estimated that the filler (especially, silicon dioxide particles) contained as the formation component of the unevenness is locally present on the surface of the resin film, and also has a function of suppressing contact between the titanium nitride-containing particles and moisture. It is considered that in Comparative Example 2, the absence of the filler also decreases the moisture resistance.

According to the comparison between Comparative Example 1 and Comparative Example 2 and Examples, it can be seen that the low reflectivity and moisture resistance of the resin film of Examples are significantly improved.

[Production and Evaluation of Resin Film 2] (1) Preparation of Resin Composition A resin composition was prepared by mixing the components shown in Tables 4 and 5 described later (Examples 17 to 22, Examples 1B to 3B, and Comparison Example 2, 3). In addition, the resin compositions of Examples 17 to 22 were prepared such that the solid content in the composition was 27.5% by mass, and the pigment concentration relative to the total solid content in the composition was 50% by mass. In addition, the mass ratio (M / B) of the content (M) of the polymerizable compounds prepared in the resin compositions of Examples 20 to 22 to the total content (B) of the dispersion resin and the binder resin was approximately 0.9. In addition, the resin compositions of Examples 1B and 2B in Table 5 have the same composition as that of Example 20 except that (M / B) of the resin compositions is 0.37 and 1.2, respectively.

And each component shown in Table 6 mentioned later was mixed, and the resin composition was prepared (Examples 1C-6C). In addition, the compositions of Examples 1C to 6C were different in the dispersion liquid type, and the composition was the same as that of Example 20 except that the dispersion liquids were different.

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

(Example 18) 5 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution) was replaced with 1.7 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution) and 1 g of Except for Megafac RS-55 (S-2) (100 wt% solution), a resin composition was prepared in the same manner as in Example 17. The desired solid content concentration was adjusted by adjusting PGMEA.

(Example 19) 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), except Except for the above, a resin composition was prepared in the same manner as in Example 17. The desired solid content concentration was adjusted by adjusting PGMEA.

(Example 20) To a 200 g container (disposable cup), 5 g of M-1, 4 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 29 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 6 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition.

(Example 21) Megafac RS-72-K (S-1) (30 wt% PGMEA solution) was replaced with Megafac RS-55 (S-2) (100 wt% solution), and the polymerization initiator was further changed from IrgacureOXE02 (BASF A resin composition was prepared in the same manner as in Example 20, except that the product was replaced by K-2. The desired solid content concentration was adjusted 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-2.

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

Comparative Example 3 A resin composition of Comparative Example 3 was prepared in the same manner as in Example 17 except that the pigment dispersion liquid A was replaced with the pigment dispersion liquid C.

(Example 1B) To a 200 g container (disposable cup), 3 g of M-1, 10 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 25 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 6 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition ( M / B = 0.37).

(Example 2B) To a 200 g container (disposable cup), 6 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 30 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 6 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution), and 55 g of pigment dispersion liquid A were stirred with a stirrer for 30 minutes to prepare a resin composition ( M / B = 1.2).

(Example 3B) A resin composition of Example 3B was prepared in the same manner as in Example 20 except that the dispersion 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) Production of resin film After the resin composition of each example and comparative example was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning Incorporated), the resin composition was subjected to a hot plate at 100 ° C for 2 minutes. Heat treatment (pre-baking). Thereafter, the coating film obtained above was subjected to an exposure process (exposure device UX3100-SR (manufactured by USHIO INC.), And the exposure amount was 1000 mJ / cm ² ) through a predetermined mask. Thereafter, the substrate was subjected to a heat treatment (post-baking) for 300 seconds using a 220 ° C. hot plate to produce a substrate with a resin film.

(3) Evaluation Using the produced substrate with a resin film, the resin film 2 was also subjected to various evaluations for the contact angle, reflectance, moisture resistance, and friction test by the same method as the resin film 1 described above. The results are shown in Tables 4, 5, and 6.

[Table 4]

[table 5]

The resin films of the above-mentioned examples each have 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. It was confirmed that the resin film was excellent in low reflectivity and excellent in moisture resistance.

In addition, if the mass ratio (M / B) of the content (M) of the polymerizable compound with respect to the total content (B) of the dispersing resin and the binding resin is different, Example 20 (M / B: about 0.9) and Example Comparing 1B (M / B: 0.37) and Example 2B (M / B: 1.2), Example 20 and Example 2B with M / B in the range of 0.45 to 1.5 were confirmed to have better abrasion resistance .

Except that the total amount of the adhesive resin and the polymerizable compound was not changed in Example 2B, the amounts of the adhesive resin and the polymerizable compound were adjusted so that M / B became 1.6, and a photosensitive resin composition was prepared in the same manner. The same evaluation as in Example 2B was performed. As a result, the same result as in Example 2B was obtained except that the result of the friction test was B. Further, according to a comparison between Example 20 and Example 3B, it was confirmed that when titanium nitride-containing particles containing metal atoms other than titanium atoms were used, particles containing silver and iron as metal atoms were more excellent in moisture resistance.

In the resin film of Comparative Example 2, since a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom was not formed, both the low reflectance and the moisture resistance did not reach desired levels. On the other hand, the resin film of Comparative Example 3 also 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 the substrate, but the titanium nitride-containing particles do not contain titanium. Metal atoms other than atoms have poor moisture resistance. In addition, according to the comparison between Comparative Example 2 and Comparative Example 3 and the Examples, it can be seen that the low reflectance and moisture resistance of the resin film of the Examples are significantly improved.

[TABLE 6]

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

[Production and Evaluation of Resin Film 3] (1) Preparation of Resin Composition A resin composition was prepared by mixing the components shown in Tables 7 and 8 described later (Examples 23 to 37, Examples 1D, 2D, and Comparison Example 4, 5, 6). In addition, all the resin compositions of Examples 23 to 37 and Comparative Examples 4, 5, and 6 were prepared so that the solid content of the composition was 27.5% by mass, and the content (M) of the polymerizable compound was relative to the total of the dispersion resin and the binder resin. The mass ratio (M / B) of the content (B) becomes approximately 0.9. In addition, in the resin compositions of Examples 23 to 37, in addition to the resin compositions of Examples 24 and 27, the pigment concentration with respect to the total solid content in the composition was set to 50% by mass. In Examples 24 and 27, the pigment concentration with respect to the total solid content in the composition was prepared to be 40% by mass.

The resin film 3 corresponds to a patterned resin film that is exposed and developed on the resin film 1 or the resin film 2.

(Example 23) To a 200 g container (disposable cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 21 g of Sururia 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 55 g of pigment dispersion liquid A, and the resin was prepared by stirring for 30 minutes with a stirrer组合 物。 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) To a 200 g container (disposable cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 16 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 20.7 g of Sururia 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 0.3 g of LS-2940, and 55 g of pigment dispersion liquid A, with stirring The device was stirred for 30 minutes to prepare a resin composition.

(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) To a 200 g container (disposable cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, and 2 g of Haisorubu BDM, 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 21 g of Sururia 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 55 g of pigment dispersion liquid A, and stir by agitator 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 polymerization initiator K-1 was replaced with the polymerization initiator K-3, and 4 g of the polymerizable compound M-1 was further replaced with 2 g of the polymerizable compound M-1 and 2 g of M-2. Except for the above, a resin composition was prepared in the same manner as in Example 23.

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

(Example 32) The pigment dispersion liquid A was replaced with the pigment dispersion liquid D, the polymerization initiator K-1 was replaced with the polymerization initiator K-2, and the polymerizable compound M-1 was further replaced with the polymerizable compound M- Except for the above, a resin composition was prepared in the same manner as in Example 23.

(Example 33) To a 200 g container (disposable cup), 5 g of M-1, 7 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 20 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 21 g of Sururia 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 44 g of pigment dispersion liquid A, and the resin was prepared by stirring for 30 minutes with a stirrer组合 物。 Composition.

(Example 34) To a 200 g container (disposable 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, 2 g of F-1 (1% PGMEA solution), 6 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution), 55 g of pigment dispersion liquid A, and stir with a stirrer for 30 minutes To prepare a resin composition.

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

(Example 2D) To a 200 g container (disposable 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, 2 g of F-1 (1% PGMEA solution), 15 g of Megafac RS-72-K (S-1) (30 wt% PGMEA solution), 55 g of pigment dispersion A, and stir for 30 minutes with a stirrer A resin composition was prepared (content of S-1 with respect to the total solid content of the composition: 17% by mass).

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

(Example 36) To a 200 g container (disposable cup), 4 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 27g of PGMEA, 2g of F-1 (1% PGMEA solution), 1g of LS-2940, 55g of pigment dispersion A, Megafac RS-72-K (S-1) (30wt% PGMEA solution): 6g, borrow The resin composition was prepared by stirring and mixing for 30 minutes with a stirrer.

(Example 37) Except having replaced the polymerization initiator K-2 with the polymerization initiator K-1 and further replacing the polymerizable compound M-1 with the polymerizable compound M-2, the same procedure as in Example 34 was performed. A resin composition was prepared.

(Comparative Example 4) To a 200 g container (disposable cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 16 g of PGMEA, and 1 g of IrgacureOXE02 (manufactured by BASF JAPAN LTD.), 21 g of Sururia 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 55 g of pigment dispersion liquid C, and the resin was prepared by stirring for 30 minutes with a stirrer组合 物。 Composition.

(Comparative Example 5) To a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), and 1 g of IrgacureOXE02 (BASF JAPAN) LTD.), 30 g of PGMEA, 2 g of F-1 (1% PGMEA solution), and 55 g of pigment dispersion liquid C, and stirred for 30 minutes with a stirrer to prepare a resin composition.

(Comparative example 6) Except having replaced the pigment dispersion liquid A with the pigment dispersion liquid C in the preparation of Example 34, the resin composition of the comparative example 6 was prepared by the same method. (2) Production and Evaluation of Resin Films <Evaluation of Adhesiveness> After the resin compositions of each Example and Comparative Example were spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning Incorporated), 100 ° C was used. The heating plate was heated (pre-baked) for 2 minutes. The following evaluation was performed with a film thickness at which the OD value was 2 at this time. The pre-baking substrate was subjected to proximity exposure (exposure device UX3100-SR (manufactured by USHIO INC.) And exposure amount 1000 mJ / cm ² ) through a predetermined mask (150 μm □ -type island pattern). Thereafter, the obtained substrate was subjected to spin-on immersion development using a 2.38 wt% developer solution of TMAH (tetramethylammonium hydroxide) for 10 to 60 seconds (the time required for discrimination when pattern exposure has been performed). After washing with water and drying, the substrate was subjected to a heat treatment (post-baking) for 300 seconds using a hot plate at 220 ° C to produce a substrate having a pattern. The obtained island-like pattern was subjected to a tape pull test in accordance with JIS-K5400. A case where all the patterns are left is A, a case where peeling occurs in part of the patterns is B, and a case where all the patterns are peeled is C. The results are shown in Tables 7 and 8.

<Evaluation of resolution> After the resin compositions of each Example and Comparative Example were spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning Incorporated), they were heated for 2 minutes using a 100 ° C hot plate. Handling (pre-baking). Thereafter, the pre-baking substrate was subjected to proximity exposure (exposure device UX3100-SR (manufactured by USHIO INC.) And exposure amount 500 mJ / cm ² ) through a predetermined mask having various line and gap line widths. Thereafter, the obtained substrate was subjected to spin-on immersion development using a 2.38 wt% developer solution of TMAH (tetramethylammonium hydroxide) for 10 to 60 seconds (the time required for discrimination when pattern exposure has been performed). After washing with water and drying, the substrate was subjected to a heat treatment (post-baking) for 300 seconds using a hot plate at 220 ° C. to produce a substrate having a pattern. The obtained pattern was observed by an optical micromirror, and the maximum line width (μm) in which the line and the gap pattern were not peeled was taken as the value of resolution. For example, when a line and a gap of 100 μm are resolved and no peeling occurs, it is determined to have a resolution of 100 μm. The results are shown in Tables 7 and 8. In addition, for each of the resin films of Examples 23 to 33, it was confirmed that the surface roughness (arithmetic average Ra) before the exposure treatment was 100 to 2000 Å. The method for measuring the surface roughness (arithmetic average Ra) is as described above. In addition, it was confirmed that in Examples 34 to 35, 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 adjacently on the substrate.

[TABLE 7]

[TABLE 8]

Moreover, regarding Example 33, the reflectance was 2% (reflectance at 400 nm), the moisture resistance was "A", and the adhesion was "A".

In the resin films of the examples, all were excellent in low reflectivity and excellent in moisture resistance, and good results were also obtained with respect to adhesion. 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 when titanium nitride-containing particles containing no metal atoms other than titanium atoms were included, the moisture resistance and the adhesion were poor. Further, for example, by comparing Example 34 with Comparative Example 6, it is known that when titanium nitride-containing particles containing no metal atoms other than titanium atoms are included, the resolution is poor. In Comparative Example 4, it is presumed that, by adding a filler, unevenness also appears on the side wall of the pattern, thereby reducing the resolution. In addition, according to the comparison of Examples 34 to 37, it was found that by using K-2 or K-3 as a polymerization initiator, the resolution can be further improved. In addition, according to the comparison between Example 34 and Examples 1D and 2D, it was confirmed that the resin containing at least one of fluorine atom and silicon atom in an amount of 1 to 15% by mass relative to the total solid content of the composition can satisfactorily take into account Moisture resistance and resolution.

[Production and Evaluation of Resin Film 4] (Example 38) After the resin composition (pigment concentration 50%) of Example 34 was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning Incorporated), 100 was used. The heating plate at a temperature of 2 ° C was subjected to a heat treatment (pre-baking) for 2 minutes. Thereafter, the coating film obtained above was subjected to an exposure process (exposure device UX3100-SR (manufactured by USHIO INC.), And the exposure amount was 1000 mJ / cm ² ) through a predetermined mask. Thereafter, the substrate was subjected to a heat treatment (post-baking) for 300 seconds using a 220 ° C. hot plate to prepare a pigment layer Y1. Coating was performed with a film thickness at an OD value of 1.0. The resin composition of Example 33 (pigment concentration: 40%) was spin-coated on the obtained pigment layer Y1, and then subjected to a heat treatment (prebaking) using a hot plate at 100 ° C for 2 minutes. Thereafter, the coating film obtained above was subjected to an exposure process (exposure device UX3100-SR (manufactured by USHIO INC.), And the exposure amount was 1000 mJ / cm ² ) through a predetermined mask. Thereafter, the substrate was subjected to a heating treatment (post-baking) on the substrate for 300 seconds using a 220 ° C. hot plate to form a pigment layer Y2, and a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was obtained. In addition, the pigment layer Y2 was applied with a film thickness of 0.5 alone.

The OD value is a value obtained by the following method. A pigment layer having a desired film thickness was formed on an alkali-free glass having a thickness of 0.7 mm, and the intensity of incident light and transmitted light were measured with a rubidium spectrometer (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.). Formula calculation. OD value = log ₁₀ (I ₀ / I) I ₀ : intensity of incident light I: intensity of transmitted light

With respect to the produced substrate with a resin film, light having a wavelength of 400 to 700 nm was incident on the resin film at an incident angle of 5 °, 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. The substrate with a resin film was subjected to a high-temperature and high-humidity test for 750 hours under conditions of a temperature of 85 ° C. and a humidity of 95% by using a high-acceleration life tester (EHS-221 manufactured by ESPEC CORP.). The transmittance of the substrate with a resin film before and after the moisture resistance test at a wavelength of 400 nm was measured with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. As a result, the change rate ΔT (%) was less than 1%.

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

As shown in Examples 38 and 39, when a pigment layer containing pigments having different pigment concentrations in a layer containing titanium nitride-containing particles containing two or more kinds of metal atoms was used, it was also confirmed that excellent low reflection was exhibited. And moisture resistance.

(Example 40) To a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), and 1 g of IrgacureOXE02 (BASF JAPAN LTD) were sequentially added. Manufactured), 30 g of PGMEA, 2 g of F-1 (1% PGMEA solution), and 55 g of pigment dispersion liquid A, and the resin composition was prepared by stirring for 30 minutes with a stirrer.

(Production of Laminated Film) According to the method for producing a substrate with a resin film in Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced. In this embodiment, a coating film is laminated on the glass substrate in the order of OD1.0 (pigment layer Y1) and OD0.5 (pigment layer Y2) on the glass substrate using the resin composition prepared as described above. With respect to the produced substrate with a resin film, light having a wavelength of 400 to 700 nm was incident on the resin film at an incident angle of 5 °, 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%. The substrate with a resin film was subjected to a high-temperature and high-humidity test for 750 hours at a temperature of 85 ° C and a humidity of 95% using a high-acceleration life tester (EHS-221 manufactured by ESPEC CORP.). , Its rate of change ΔT (%) is less than 1%.

(Example 41) According to the method for manufacturing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was manufactured. In this example, the resin composition prepared in Example 40 was used to laminate a coating film on a glass substrate so as to become OD0.5 (pigment layer Y1) and OD1.0 (pigment layer Y2) in this order. With respect to the produced substrate with a resin film, as in Example 39, light of 400 to 700 nm was incident from the substrate surface side toward the resin film at an incident angle of 5 °, and the reflectance was measured. The reflectance at 400 nm at this time was 4.0. The substrate with a resin film was subjected to a high-temperature and high-humidity test for 750 hours at a temperature of 85 ° C and a humidity of 95% using a high-acceleration life tester (EHS-221 manufactured by ESPEC CORP.). , Its rate of change ΔT (%) is less than 1%.

no

no

Claims (28)

A resin composition comprising: titanium nitride-containing particles containing at least one metal atom other than titanium atoms; a binder resin; and at least one selected from a filler and a compound containing at least one of a fluorine atom and a silicon atom. The resin composition according to item 1 of the scope of patent application, wherein when CuKα rays are used as X-ray sources to measure the X-ray diffraction spectrum of the titanium nitride-containing particles, the titanium nitride-containing particles are derived from TiN (200) The diffraction angle 2θ of the surface peak is in a range of 42.5 ° or more and 43.5 ° or less. The resin composition according to claim 1 or claim 2, wherein the filler is at least one of silica particles and acrylic particles. The resin composition according to item 3 of the patent application range, wherein the aforementioned filler is hollow silica. The resin composition according to claim 1 or claim 2, wherein the maximum value in the particle size distribution of the filler is 50 to 500 nm. The resin composition according to item 1 or 2 of the scope of the patent application, which contains the aforementioned compound containing at least one of a fluorine atom and a silicon atom, and the content of the aforementioned compound containing at least one of a fluorine atom and a silicon atom is relative to The total solid content in the resin composition is 1 to 15% by mass. The resin composition according to claim 1 or claim 2, wherein the compound containing at least one of a fluorine atom and a silicon atom includes a repeating unit containing at least one of a fluorine atom and a silicon atom, and a polymerizable group. Polymer compound of the repeating unit of the group. The resin composition according to claim 1 or claim 2, wherein the compound containing at least one of a fluorine atom and a silicon atom is a reactive silicone. The resin composition according to item 1 or 2 of the scope of patent application, further comprising a dispersing resin. The resin composition according to item 1 or item 2 of the scope of patent application, further comprising a polymerization initiator. The resin composition according to claim 10, wherein the polymerization initiator is an oxime compound. The resin composition according to item 1 or item 2 of the scope of patent application, further comprising a silane coupling agent having an epoxy group. The resin composition according to claim 1 or claim 2, further comprising a polymerizable compound having a cardo skeleton. The resin composition according to item 13 of the scope of application, wherein the polymerizable compound having a cardo skeleton is a polymerizable compound having a 9,9-diarylfluorene skeleton. The resin composition according to claim 1 or claim 2, wherein the content of the titanium nitride-containing particles is 30 to 60% by mass relative to the total solid content of the resin composition. A resin film comprising: titanium nitride-containing particles containing at least one or more metal atoms other than titanium atoms; and a bonding resin, wherein a surface roughness Ra of an outermost surface of the resin film is 100 to 2000 Å. The resin film according to item 16 of the patent application scope, further comprising a filler. The resin film according to claim 17 in which the maximum value in the particle size distribution of the filler is 50 to 500 nm. The resin film according to any one of claims 16 to 18 of the scope of patent application, further comprising a resin having a polysiloxane structure. The resin film according to any one of items 16 to 18 of the scope of application for a patent, wherein the resin film is a resin film in which adjacent layers contain the pigment layer X1 and pigment layer X2 containing the titanium nitride particles, respectively, 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 Ra of the surface on the pigment layer X2 side of the resin film is 100 to 2000Å. A resin film comprising: a pigment layer containing titanium nitride-containing particles containing at least one or more metal atoms other than titanium atoms; and a surface layer disposed adjacent to the pigment layer and containing fluorine atoms and silicon atoms At least one of the compounds. The resin film according to claim 21, wherein the compound containing at least one of a fluorine atom and a silicon atom includes a resin containing at least one of a fluorine atom and a silicon atom. The resin film according to item 22 of the scope of patent application, wherein the resin containing at least one of a fluorine atom and a silicon atom includes: a repeating unit containing at least one of a fluorine atom and a silicon atom; and a repeating unit having a polymerizable group . A resin film is a resin film in which a neighboring layer includes a pigment layer Y1 and a pigment layer Y2 containing titanium nitride particles containing at least one metal atom other than titanium atoms, wherein the pigment layer Y1 and the pigment layer Y2 are The aforementioned titanium nitride-containing particles are contained at different concentrations. A color filter comprising a resin film formed from the resin composition described in any one of claims 1 to 15 in the scope of patent application, and a color filter selected from any one of claims 16 to 24 in the scope of patent application Any one of the resin films. A light-shielding film comprising a resin film formed from the resin composition described in any one of claims 1 to 15 in the scope of patent application, and a resin film formed in any one of claims 16 to 24 in the scope of patent application Any of the resin films. A solid-state photographic element comprising a resin film formed from the resin composition described in any one of claims 1 to 15 in the scope of patent application and any one of claims 16 to 24 in the scope of patent application Any of the resin films. An image display device comprising a resin film formed from the resin composition described in any one of claims 1 to 15 in the scope of patent application and any one of claims 16 to 24 in the scope of patent application Any of the resin films described.