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WO2017150069A1 - Composition de résine, film de résine, filtre coloré, film de protection contre la lumière, dispositif d'imagerie à semi-conducteur, et dispositif d'affichage d'image - Google Patents

Composition de résine, film de résine, filtre coloré, film de protection contre la lumière, dispositif d'imagerie à semi-conducteur, et dispositif d'affichage d'image Download PDF

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Publication number
WO2017150069A1
WO2017150069A1 PCT/JP2017/003918 JP2017003918W WO2017150069A1 WO 2017150069 A1 WO2017150069 A1 WO 2017150069A1 JP 2017003918 W JP2017003918 W JP 2017003918W WO 2017150069 A1 WO2017150069 A1 WO 2017150069A1
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Prior art keywords
group
resin
resin composition
atom
resin film
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Ceased
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PCT/JP2017/003918
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English (en)
Japanese (ja)
Inventor
恒光 留場
久保田　誠
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2018502964A priority Critical patent/JP6800949B2/ja
Publication of WO2017150069A1 publication Critical patent/WO2017150069A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F99/00—Subject matter not provided for in other groups of this subclass

Definitions

  • 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 device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographing lens, and a circuit on which the solid-state imaging device is mounted.
  • a substrate This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smartphone, and the like.
  • noise due to reflection of visible light may occur. Therefore, in Patent Document 1, the generation of noise is suppressed by providing a predetermined light shielding film in the solid-state imaging device.
  • a light shielding composition containing a black pigment such as titanium black is used.
  • the present inventors have come to know that when a light-shielding film containing titanium black is exposed to high temperature and high humidity, its spectral performance deteriorates (that is, it is inferior to “moisture resistance”). Since the desired light-shielding ability may not be exhibited when the spectral performance of the light-shielding film deteriorates, improvement is desired.
  • the present inventors have at least selected from compounds containing predetermined titanium nitride-containing particles, a binder resin, a filler, and at least one of a fluorine atom and a silicon atom.
  • the present inventors have found that the above problems can be solved by using a resin composition in combination with any of the above, and thus completed the present invention. That is, it has been found that the above object can be achieved by the following configuration.
  • the peak diffraction angle 2 ⁇ derived from the TiN (200) plane of the titanium nitride-containing particles is 42.
  • the resin composition as described in (1) which exists in the range of 5 degrees or more and 43.5 degrees or less.
  • the compound containing at least one of the fluorine atom and the silicon atom is a polymer compound containing a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group.
  • the resin composition according to any one of (1) to (6), wherein the compound containing at least one of a fluorine atom and a silicon atom is a reactive silicone.
  • the resin composition according to (10), wherein the polymerization initiator is an oxime compound.
  • the resin composition according to (13), wherein the polymerizable compound having a cardo skeleton is a polymerizable compound having a 9,9-bisarylfluorene skeleton.
  • the resin composition according to any one of (1) to (14), wherein the content of the titanium nitride-containing particles is 30 to 60% by mass with respect to the total solid content in the resin composition. object.
  • the resin film is a resin film in which the pigment layer X1 and the pigment layer X2 each containing the titanium nitride-containing particles are laminated adjacently,
  • the concentration of the titanium nitride-containing particles contained in the pigment layer X2 is smaller than the concentration of the titanium nitride-containing particles contained in the pigment layer X1,
  • the resin containing at least one of the fluorine atom and the silicon atom includes a repeating unit containing at least one of a fluorine atom and a silicon atom, and a repeating unit having a polymerizable group.
  • Resin film A resin film in which a pigment layer Y1 and a pigment layer Y2 each containing titanium nitride-containing particles containing at least one metal atom other than a titanium atom are laminated adjacently, Resin films having different concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2.
  • a light shielding film comprising any one selected from the resin film formed from the resin composition according to any one of (1) to (15) and the resin film according to any one of (16) to (24). film.
  • the resin composition which can form the resin film excellent in low reflectivity and excellent in moisture resistance can be provided.
  • a resin film excellent in low reflectivity and excellent in moisture resistance a color filter including the resin film, a light shielding film, a solid-state imaging device, and an image display device.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “(meth) acrylate” represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • the “pigment” in the present invention means, for example, an insoluble coloring compound that does not dissolve in a solvent.
  • examples of the “solvent” include the solvents exemplified in the solvent column described later. Therefore, a coloring compound that does not dissolve in these solvents corresponds to the pigment in the present invention.
  • active light or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure in this specification is not limited to exposure with a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
  • to is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value. Further, in the present invention, “1 ⁇ ” is synonymous with “0.1 nanometer (nm)”.
  • the resin film according to the first embodiment includes titanium nitride-containing particles containing at least one metal atom other than titanium atoms and a binder resin, and has an outermost surface roughness Ra of 100 to 2000 mm. It is characterized by.
  • the present inventors have obtained a film obtained by setting the surface roughness of the outermost surface of a resin film containing titanium nitride-containing particles containing at least one metal atom other than titanium atoms within the above numerical range. Has been found to be excellent in low reflectivity and moisture resistance.
  • the surface roughness (arithmetic mean roughness Ra) of the resin film is preferably from 300 to 2,000 (angstrom), more preferably from 300 to 1,500 in view of more excellent effects of the present invention.
  • the surface roughness Ra is calculated by measuring the distance of 1 mm of the resin film with a resolution of 1 ⁇ m / point using DektakXT manufactured by BRUKER.
  • the thickness of the resin film is not particularly limited, and is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, from the viewpoint that the effect of the present invention is more excellent.
  • the above thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the resin film and arithmetically averaging them.
  • the material constituting the resin film examples include titanium nitride-containing particles containing at least one metal atom other than titanium atoms, a binder resin, and a filler.
  • the resin film can be formed by applying a resin composition containing the above-described constituent materials or precursor materials thereof onto a substrate.
  • the said resin composition can also be used as the photosensitive resin composition which has exposure and developability.
  • a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition.
  • a binder resin, a polymerizable compound, a dispersion resin described later, and the like may be used as the alkali-soluble material.
  • resin composition A various materials contained in the above-described resin composition (hereinafter referred to as “resin composition A”) will be described in detail.
  • Resin composition A contains, as a black pigment, titanium nitride-containing particles (hereinafter also referred to as “titanium nitride-containing particles”) containing at least one metal atom other than titanium atoms. Titanium nitride-containing particles contain titanium atoms and at least one metal atom other than titanium atoms. In the following description, “metal atom” means “metal atom other than titanium atom”.
  • the titanium nitride-containing particles described above are composite fine particles composed of titanium nitride particles and metal fine particles.
  • “Composite fine particles” refers to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state.
  • composite means that the particles are composed of both titanium nitride and metal components, and “highly dispersed” means that the titanium nitride particles and metal particles are It means that the particles exist individually and the small amount of particles are not aggregated and are uniformly and uniformly dispersed.
  • titanium nitride particles include titanium nitride as a main component, and are usually low-order titanium oxides represented by titanium oxide TiO 2 and Ti n O 2n-1 (1 ⁇ n ⁇ 20) as subcomponents. And TiN y O z (y and z are each greater than 0 and less than 2).
  • the metal atom content and titanium atom content are analyzed by ICP (radio frequency inductively coupled plasma) emission spectroscopy, and the nitrogen atom content is analyzed by inert gas melting-thermal conductivity method.
  • the amount can be analyzed by an inert gas melting-thermal conductivity method. Based on these analysis results, the amount of elements contained in the particles is calculated.
  • atoms other than the titanium atom, nitrogen atom, oxygen atom, and metal atom may be contained as impurities. However, if the amount of impurities is small and difficult to specify, the impurities are considered.
  • the specific surface area is preferably 5 m 2 / g or more 100 m 2 / g or less of titanium nitride-containing particles, 10 m 2 / g or more 60 m 2 / g or less is more preferable.
  • the specific surface area can be determined by the BET method.
  • the metal atom is not particularly limited.
  • At least one selected from copper, silver, gold, iron, platinum, palladium, nickel, vanadium, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, copper, silver, gold, nickel, More preferably, it is at least one selected from vanadium, platinum, tin and iron, and alloys thereof. From the viewpoint of better moisture resistance, at least one selected from silver and iron is more preferable, and silver is particularly preferable.
  • the content of metal atoms (metal fine particles) is preferably more than 0.001% by mass and less than 50% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01% by mass.
  • the total content is included in the above numerical range.
  • the content of the metal atom is more than 0.001% by mass, the patterning property of the cured film is excellent.
  • the metal atom content is less than 50% by mass, the moisture resistance and rubbing resistance are excellent.
  • the corrosion resistance of the electrode by the cured film is excellent. That is, it can suppress that a cured film corrodes an electrode.
  • the metal atom contained in the titanium nitride-containing particle has excellent adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particle was attached to the electrode and the substrate via the metal atom. Conceivable. For this reason, it is considered that metal atoms remain on the electrode and the substrate after the patterning of the cured film such as development processing, and the titanium nitride is easily removed. Therefore, it is presumed that the patterning property of the cured film is improved by setting the content of metal atoms in the titanium nitride-containing particles to a predetermined amount or more.
  • the content of metal atoms is preferably 0.001% by mass or more and less than 0.4% by mass. It is presumed that the anticorrosion property of the electrode became excellent by setting the content of metal atoms in the titanium nitride-containing particles to less than 0.4% by mass. In order to obtain this effect, the content is more preferably 0.01 to 0.2% by mass, and further preferably 0.02 to 0.1% by mass.
  • the metal fine particles in the titanium nitride-containing particles exist in a stable state as fine particles without performing surface coating or the like. In order to obtain higher light-shielding properties as metal fine particles, it is preferable that the fine particles be appropriately formed.
  • the crystallite size determined from the half-width of the strongest main peak in the X-ray diffraction spectrum of the metal fine particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less.
  • the crystallite size can be calculated from the full width at half maximum of the X-ray diffraction peak using Scherrer's equation.
  • the crystallite size obtained from the half width of the (111) plane is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less.
  • the titanium nitride particles preferably have the following characteristics in order to improve light shielding properties.
  • the titanium nitride particles preferably contain TiN as a main component, and the peak diffraction angle 2 ⁇ derived from the (200) plane is preferably 42.5 ° or more and 43.5 ° or less, 42 The angle is more preferably from 5 ° to 42.8 °, still more preferably from 42.5 ° to less than 42.7 °.
  • Titanium nitride particles are usually partially in the form of oxynitrides containing oxygen atoms due to oxidation of the particle surface. Usually, the mixing of oxygen during the synthesis of titanium nitride particles becomes particularly noticeable when the particle size is small.
  • a smaller amount of oxygen is preferable because higher light shielding properties can be obtained, and it is particularly preferable not to contain TiO 2 as a subcomponent.
  • the oxygen atom content is preferably 10% by mass or less, and more preferably 6.0% by mass or less, based on the mass of the titanium nitride particles.
  • the crystallite size of the titanium nitride particles is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less.
  • the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the particle volume becomes small and a good balance is obtained.
  • titanium nitride-containing particles that are remarkably excellent in heat resistance or durability can be obtained.
  • the diffraction angle 2 ⁇ of the peak derived from the TIN (200) plane of the titanium nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less from the viewpoint of light shielding properties, in order to improve the light shielding properties. Is more preferably 42.5 ° or more and 42.8 ° or less, and further preferably 42.5 ° or more and less than 42.7 °.
  • TiO 2 is white and causes light-shielding properties to decrease, it is preferably reduced to such an extent that it is not observed as a peak.
  • the titanium nitride-containing particles are preferably produced through a process of mixing and condensing Ti and a metal element in a gas phase, and produced by a thermal plasma method using a nitrogen-containing gas as a plasma gas. It is more preferable that
  • titanium nitride-containing particles those described in International Publication No. 2010/147098, Japanese Patent Application Laid-Open No. 2007-153662, and the like can be further referred to.
  • the content of titanium nitride-containing particles is preferably 30 to 60% by mass, more preferably 35 to 60% by mass, and more preferably 40 to 55% by mass with respect to the total solid content in the resin composition. More preferably.
  • the method for producing titanium nitride-containing particles the ones described in paragraphs ⁇ 0037> to ⁇ 0089> of WO2010 / 147098 can be referred to.
  • the titanium nitride-containing particles are produced for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours) in a closed container in which the oxygen concentration is controlled without immediately exposing them to the atmosphere after the particles are produced. And more preferably 12 to 24 hours). At that time, it is more preferable that the water content is controlled. Thereby, the surface and crystal grain boundary of the titanium nitride-containing particles are stabilized, and it is estimated that the performance of the composition is improved.
  • the oxygen (O 2 ) concentration and the moisture content in the closed container in which the oxygen concentration is controlled are each preferably 100 mass ppm or less, more preferably 10 mass ppm or less, and more preferably 1 mass ppm or less. More preferably.
  • Nitrogen above oxygen (O 2) concentration, and the adjustment of the water content, the above oxygen (O 2) concentration, and oxygen (O 2) in the above range of the content of water, and a water-containing It is preferable to use an inert gas such as gas or argon gas, and among these, it is more preferable to use nitrogen gas.
  • the surface and crystal grain boundary of the titanium nitride-containing particles are stabilized, and it is estimated that the performance of the composition is improved.
  • titanium nitride-containing particles having a high optical density can be obtained, and generation of pinholes in a cured film obtained using the composition of the present invention can be suppressed.
  • the temperature for standing for a predetermined time is preferably 300 ° C. or less, more preferably 200 ° C. or less, and particularly preferably 100 ° C. or less. Within this range, titanium nitride-containing particles having a higher optical density can be obtained.
  • the titanium powder material used for the production of titanium nitride-containing particles is preferably highly pure.
  • the titanium powder material is not particularly limited, and a titanium element having a purity of 99.99% by mass or more is preferable, and a material having 99.999% by mass or more is more preferably used.
  • the content of silicon atoms in the titanium powder material is preferably less than 0.3% by mass, more preferably less than 0.1% by mass, substantially including the total amount of the titanium powder material. It is particularly preferred not to.
  • the water content in the titanium powder material is preferably less than 1% by mass, more preferably less than 0.1% by mass with respect to the total amount of the titanium powder material, and substantially no inclusion. Particularly preferred. A desired effect can be acquired more notably that it is said range.
  • Examples of the process for dispersing the titanium nitride-containing particles include a process using compression, squeezing, impact, shearing, cavitation or the like as a mechanical force used for dispersion.
  • Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, ultrasonic dispersion, and a microfluidizer.
  • beads having a small diameter or to process under conditions where the grinding efficiency has been increased by increasing the filling rate of beads it is preferable to remove the elementary particles by centrifugation or the like.
  • the above titanium nitride-containing particles are also suitably used in a process for dispersing a pigment described later.
  • Resin composition A contains a binder resin.
  • the binder resin preferably contains neither fluorine atoms nor silicon atoms.
  • “containing neither fluorine atom nor silicon atom” means that the resin does not substantially contain fluorine atom and silicon atom, and each content is 3 to the total resin mass. It is preferable that it is mass% or less, and it is more preferable that it is 0.1 mass% or less.
  • binder resin It does not specifically limit as binder resin, It is preferable to use a linear organic polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily.
  • the molecular weight of the binder resin is not particularly defined, and it is preferable that the weight average molecular weight (Mw) is 5000 to 100,000 as a polystyrene-converted value by GPC (gel permeation chromatography) method.
  • Mn number average molecular weight
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the resin composition A can have exposure / developability. Therefore, when the resin composition A is a photosensitive resin composition, the binder resin is preferably a resin that can be developed with water or weakly alkaline water, and is soluble or swellable in water or weakly alkaline water. More preferably, it is a linear organic polymer.
  • the binder resin an alkali-soluble resin (a resin having a group that promotes alkali-solubility) is particularly preferable.
  • the molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably 5000 to 100,000.
  • the number average molecular weight (Mn) is preferably 1000 to 20,000.
  • a weight average molecular weight and a number average molecular weight can be measured by the above-mentioned method.
  • the alkali-soluble resin may be a linear organic polymer, and promotes at least one alkali-solubility in the molecule (preferably a molecule having an acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
  • Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are more preferred.
  • Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What is possible is preferred. Only one type of acid group may be used, or two or more types may be used.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • the alkali-soluble resin a polymer having a carboxyl group in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • examples include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable with (meth) acrylic acid is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and N-substituted maleimide monomers.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • the alkali-soluble resin which has a polymeric group examples include a (meth) allyl group and a (meth) acryloyl group.
  • the alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in the side chain is useful.
  • the alkali-soluble resin having a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing, polyurethane acrylic oligomer. Diamond Shammock Co. Ltd., biscort R-264, KS resist).
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate A multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used.
  • the alkali-soluble resin includes a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing monomer components.
  • 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.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • ED2 general formula (ED2)
  • JP 2010-168539 A the description in JP 2010-168539 A can be referred to.
  • the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include a methyl group, an ethyl group, linear or branched alkyl group such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, tert-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; phenyl group Aryl groups such as cyclohexyl group, tert-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group and the like; 1- Alkyl groups substituted with alkoxy such as methoxyethyl group and 1-ethoxyethyl group; alkyl groups substituted with alk
  • a primary or secondary carbon substituent which is difficult to be removed by an acid or heat such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, is particularly preferable in terms of heat resistance.
  • ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • the compound represented by the general formula (ED1) and / or the structure derived from the compound represented by the general formula (ED2) may be copolymerized with other monomers.
  • the alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or 1 to 20 carbon atoms that may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms. Further, the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • alkali-soluble resin examples include the following. “Me” means a methyl group.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
  • polyimide resins described in International Publication No. 2008/123097 are also useful.
  • the content of the binder resin in the resin composition A is preferably 0.01 to 40% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and most preferably 1.5% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • only one type of binder resin may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • composition A contains a filler.
  • the “filler” is a particle provided for the purpose of roughening the surface.
  • the above-mentioned titanium nitride-containing particles are not included in the filler.
  • grains used for coloring property provision, such as another pigment, are not contained in a filler, and a non-coloring thing is preferable as a filler.
  • the composition of the filler is not particularly limited, and either inorganic particles or organic particles may be used.
  • the inorganic particles are not particularly limited, and examples thereof include oxides such as silicon, titanium, aluminum, tin, zinc, and antimony.
  • the inorganic particles may have a porous or hollow (hollow) structure inside.
  • the organic particles are not particularly limited, and examples of the material include cellulose derivatives, acrylic resins, polyolefins, polyamides, polycarbonates, polystyrene, vinyl acetate, vinyl alcohol, vinyl chloride or vinyl butyral homopolymer or copolymer. Resins such as vinyl polymers such as coalescence, diene homopolymers and copolymers, and the like. Among these, silica particles and acrylic particles are preferable from the viewpoint of low reflectivity, and hollow silica having a hollow structure (hollow silica particles) is more preferable.
  • the maximum value in the particle size distribution of the filler is preferably 50 to 1000 nm, and more preferably 50 to 500 nm from the viewpoint of more excellent moisture resistance and rubbing resistance.
  • the maximum value in the particle size distribution of the filler can be measured by Nanotrac UPA-EX manufactured by Microtrac Bell.
  • the content thereof is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on the total solid content in the composition, More preferably, it is 3 to 15% by mass.
  • the resin composition A only one type of filler may be included, or two or more types of fillers may be included. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition A may contain a dispersion resin.
  • the dispersion resin contributes to the improvement of the dispersibility of the above-described titanium nitride-containing particles (hereinafter, also referred to as “black pigment” as appropriate) and other pigments such as other pigments used in combination as desired.
  • the dispersion resin include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene. Examples include sulfonic acid formalin condensate.
  • Dispersion resins (hereinafter also referred to as “polymer compounds”) can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers, based on their structures.
  • the polymer compound is adsorbed on the surface of a dispersion such as a black pigment and, if desired, a pigment used together, and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorptivity of the polymer compound to these can be promoted.
  • the polymer compound preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of a colored pigment such as a black pigment and dispersion stability after a lapse of time because it has an affinity for a solvent by the graft chain. It is.
  • the composition since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development. When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the “graft chain” means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain. .
  • the graft chain preferably has a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
  • the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure.
  • the graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
  • the structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be preferably used.
  • AA-6 trade name, Toa Gosei Co., Ltd.
  • AA-10 Product name, manufactured by Toa Gosei Co., Ltd.
  • AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • AS-6 trade name, produced by Toa Gosei Co., Ltd.
  • AN-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • Co., Ltd. AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-110 (trade name, manufactured by Toa Gosei Co., Ltd.), Aronix M-5300 (Trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) and the like are used.
  • the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoints of dispersion stability and developability.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
  • X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoints of dispersion stability and developability.
  • X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
  • the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a range of 5 to 30%.
  • the structural unit having a graft chain is contained within this range, the dispersibility of a colored pigment such as a black pigment is high, and the developability when forming a colored layer is good.
  • the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into partial structures (fragments) and estimates the log P value of the compound by summing the log P contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J.M. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom number 1 to 6 alkyl groups (for example, methyl group, ethyl group, propyl group, etc.) are represented.
  • R 1 , R 2 , and R 3 are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are particularly preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), or combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still 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 or 6-membered ring as the heterocycle.
  • Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included.
  • bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [4 .4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still 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. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl having 1 to 6 carbon atoms.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • an alkyl having 1 to 6 carbon atoms Represents a group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming an interaction with a colored pigment such as a black pigment.
  • the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment.
  • the functional group capable of forming an interaction with the colored pigment such as the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, in the resin composition A, the polymer compound as a dispersion resin that contributes to the dispersion of a colored pigment such as a black pigment has alkali solubility.
  • a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound has a structural unit which has an acid group
  • the acid group in the structural unit having an acid group easily interacts with a color pigment such as a black pigment, and the polymer compound stably disperses the color pigment such as a black pigment, This is presumably because the viscosity of the polymer compound to be dispersed is low and the polymer compound itself is easily dispersed stably.
  • the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit.
  • the structural unit possessed is a structural unit different from the hydrophobic structural unit described above. That is, it does not correspond to the hydrophobic structural unit described above.
  • Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and particularly preferred is a carboxylic acid group that has good adsorptive power to colored pigments such as black pigments and has high dispersibility.
  • the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units having an acid group.
  • the polymer compound may or may not contain a structural unit having an acid group, and when it is contained, the content of the structural unit having an acid group is, in terms of mass, with respect to the total mass of the polymer compound,
  • the content is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom, There are amide groups and the like, and particularly preferred is a tertiary amino group which has a good adsorptive power to colored pigments such as black pigments and has high dispersibility.
  • the polymer compound can have one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit having a basic group. When it is contained, the content of the structural unit having a basic group is based on the total mass of the polymer compound in terms of mass. The content is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing the development inhibition.
  • a coordinating group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment, and a functional group having reactivity
  • a functional group capable of forming an interaction with a colored pigment such as a black pigment
  • a functional group having reactivity for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride
  • examples include acid chlorides.
  • an acetylacetoxy group which has a good adsorptive power to colored pigments such as black pigments and high dispersibility.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, and if included, the content of these structural units is In terms of conversion, it is preferably 10% or more and 80% or less with respect to the total mass of the polymer compound, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developability inhibition.
  • the polymer compound in the present invention has a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, it forms an interaction with various colored pigments such as the black pigment as described above. It is only necessary to contain functional groups that can be used, and how these functional groups are introduced is not particularly limited, and the polymer compound is represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from monomers.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 11 , R 12 , and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably Are each independently a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
  • R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group is preferably a saturated aliphatic group rather than 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 number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still 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 or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable that it is a carboxylic acid group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, propyl group, etc.), - represents a Z 1, or -L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is methine. Compounds that are groups are preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and L 1 is a single bond or an alkylene group, A compound in which Z is a carboxylic acid group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenol Such as Le methacrylamide.
  • the content of the structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment is from the viewpoint of interaction with a colored pigment such as a black pigment, dispersion stability, and permeability to a developer.
  • the amount is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass based on the total mass of the polymer compound.
  • the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and a colored pigment such as a black pigment, as long as the effects of the present invention are not impaired.
  • Other structural units having various functions different from structural units having a functional group capable of forming an interaction for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g.
  • the range is as follows. When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming the resin layer is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored pigments such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a resin film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • dispersion resin in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding paragraphs 0075 to 0133 of US2011 / 0124824) can be used. The contents can be incorporated and incorporated herein.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the content of the dispersed resin in the resin composition A is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 1 to 30% by mass with respect to the total solid content of the composition.
  • Examples of the process for dispersing the pigment include a process using compression, squeezing, impact, shearing, cavitation or the like as the mechanical force used for dispersion.
  • Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, ultrasonic dispersion, or a microfluidizer.
  • beads In the grinding of pigments in sand mills (bead mills), it is preferable to use beads with small diameters and to treat them under conditions that increase the grinding efficiency by increasing the filling rate of beads. It is preferable to remove the elementary particles by separation or the like.
  • the resin composition A may contain a polymerization initiator.
  • a polymerization initiator There is no restriction
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
  • Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones
  • the resin film of the present invention when used for the production of a light-shielding film for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is preferred that From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
  • an oxime compound as the photopolymerization initiator.
  • stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.
  • oxime compound can improve the color transfer.
  • paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
  • acylphosphine-based initiator commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.
  • Resin composition A preferably contains an oxime compound represented by the following formula (I) as a polymerization initiator.
  • R a represents an alkyl group, an acyl group, an aryl group, or a heterocyclic group
  • R b represents an alkyl group, an aryl group, or a heterocyclic group
  • a plurality of R c are each independently , A hydrogen atom, an alkyl group, or a group represented by —OR h .
  • R h represents an electron withdrawing group or an alkyl ether group.
  • at least one of the plurality of R c represents a group represented by —OR h .
  • R a represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, preferably an aryl group or a heterocyclic group, and more preferably a heterocyclic group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the acyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms. Examples of the acyl group include an acetyl group and a benzoyl group.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • the aryl group may be a single ring or a condensed ring.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and 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.
  • R a may be unsubstituted or may have a substituent.
  • substituents include an alkyl group, aryl group, heterocyclic group, nitro group, cyano group, halogen atom, —OR X1 , —SR X1 , —COR X1 , —COOR X1 , —OCOR X1 , —NR X1 R X2 , —NHCOR X1 , —CONR X1 R X2 , —NHCONR X1 R X2 , —NHCOOR X1 , —SO 2 R X1 , —SO 2 OR X1 , —NHSO 2 R X1 and the like can be mentioned.
  • R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the number of carbon atoms of the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 is preferably 1-20.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom).
  • part or all of the hydrogen atoms may be substituted with the above substituents.
  • the aryl group as a substituent and the aryl group represented by R X1 and R X2 preferably have 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aryl group may be a single ring or a condensed ring.
  • part or all of the hydrogen atoms may be substituted with the above substituents.
  • the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably 5-membered rings or 6-membered rings.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and 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 the hetero group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the heterocyclic group represented by R a is preferably a group represented by the following formula (II).
  • Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent
  • R 3 represents an alkyl group or an aryl group
  • * represents a bonding position.
  • Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the ring of the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring.
  • Ar 1 and Ar 2 are 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.
  • substituents that Ar 1 and Ar 2 may have include the substituent described in Ra .
  • Ar 1 is preferably unsubstituted.
  • Ar 2 may be unsubstituted or may have a substituent.
  • —COR X1 is preferable.
  • R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group.
  • the aryl group may have a substituent or may be unsubstituted.
  • the substituent include an alkyl group having 1 to 10 carbon atoms.
  • 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.
  • the substituent include the substituents described in the above-mentioned R a.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • the aryl group may be a single ring or a condensed ring
  • Rb represents an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group, and more preferably an alkyl group.
  • An alkyl group, an aryl group, and a heterocyclic group are synonymous with the group demonstrated by Ra . These groups may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in R a.
  • a plurality of R c each independently represents 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.
  • at least one of the plurality of R c represents a group represented by —OR h .
  • the alkyl group represented by R c preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • R h in -OR h for example, a nitro group, a cyano group, a fluorine atom, at least one hydrogen atom and an alkyl group of carbon number of 1 to 20 substituted by a fluorine atom Can be mentioned.
  • an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom is preferable.
  • the alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 4 carbon atoms, and may be linear, branched or cyclic, and is preferably linear or branched.
  • Alkyl ether group represented by R h in -OR h refers to an alkyl group substituted with an alkoxy group.
  • the alkyl group in the alkyl ether group and the alkyl group in the alkoxy group in the alkyl ether group preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and 1 to 4 carbon atoms. Is particularly preferred.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the total number of carbon atoms of the alkyl ether group is preferably 2 to 8, more preferably 2 to 6, and more preferably 2 to 4.
  • one or two is preferably a group represented by —OR h .
  • R h in -OR h is an electron withdrawing group (e.g., at least one alkyl group having 1 to 20 carbon atoms in which a hydrogen atom has been substituted with a fluorine atom), and the remaining R c, A hydrogen atom is preferred.
  • R h in -OR h is an alkyl ether group, the remaining R c, it is preferred that one is an other is hydrogen atom in an alkyl group.
  • the alkyl group represented by R c or group represented by -OR h, the ortho or It is preferably located in the para position.
  • photopolymerization initiator represented by formula (I) or formula (II) include the following compounds.
  • Resin composition A preferably contains an oxime compound represented by the following formula (III) as a polymerization initiator.
  • R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
  • R 5 represents —R 6 , —OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom or a hydroxyl group, wherein R 6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a group having 7 to 30 carbon atoms. Represents an arylalkyl group or a heterocyclic group having 4 to 20 carbon atoms, and a represents an integer of 0 to 5.
  • R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the compound represented by the formula (III) include compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
  • the commercially available polymerization initiator is not particularly limited, and IRGACURE OXE 01 (1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] manufactured by BASF Japan Ltd.] ), IRGACURE OXE 02 (ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) Examples include thioxanthen-9-one, O-acyloxime compounds (for example, Adekaoptomer N-1919, Adeka Arkles NCI-831, manufactured by ADEKA), Adeka Arkles NCI-930, and the like. Incorporated in the description.
  • the content of the polymerization initiator is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, still more preferably from 1 to 10% by mass, based on the total solid content of the composition. Particularly preferred is 1 to 7% by mass.
  • Resin composition A may contain only one type of polymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • Resin composition A may contain a silane coupling agent.
  • the “silane coupling agent” is a compound having a hydrolyzable group and other functional group in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the “hydrolyzable group” refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • 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 alkenyloxy group having 4 or less carbon atoms is preferable.
  • the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded).
  • silicon atoms excluding silicon atoms bonded with hydrolyzable groups
  • alkylene groups substituted with silicon atoms straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Preferably not.
  • the silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
  • R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
  • the silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
  • the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
  • an epoxy group is preferable from the viewpoints of improving adhesion, developing resistance, and solvent resistance.
  • a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
  • the molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.
  • silane coupling agent X represented by the formula (W).
  • R z1 represents a hydrolyzable group, and the definition is as described above.
  • R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
  • Lz represents a single bond or a divalent linking group.
  • examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR 12 —, —CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
  • a group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
  • R 12 represents a hydrogen atom or a methyl group.
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
  • Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like.
  • substituents further include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group, an amino group, a halogen atom, and a sulfonamide group.
  • An alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof may be substituted.
  • at least one hydrolyzable group is bonded to the silicon atom.
  • the definition of the hydrolyzable group is as described above.
  • the silane coupling agent Y may contain a group represented by the above formula (Z).
  • the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group.
  • the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
  • 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.
  • substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
  • the nitrogen atom is couple
  • Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
  • the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
  • the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to have two or more curable functional groups from the viewpoint of sensitivity and stability.
  • the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and include the above-described ranges (preferably 270 or more).
  • the content of the silane coupling agent in the resin composition A is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total solid content in the composition, 1.0% More preferably, it is ⁇ 6% by mass.
  • the resin composition A may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
  • the resin composition A may contain a polymerizable compound.
  • the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, further preferably 3 or more, and particularly preferably 5 or more.
  • the upper limit is 15 or less, for example.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
  • 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, 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 esters thereof, amides, and multimers thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds for example, acrylic acid, methacrylic acid, itac
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, or the above unsaturated carboxylic acid is also preferably used.
  • reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups
  • a reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
  • the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.
  • the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.
  • the polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.).
  • Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454, SR499 commercially available from Sartomer) preferable. These oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, Mention may be made of ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” Indicates a bond.
  • R 1 represents a hydrogen atom or a methyl group, "*" indicates a bond.
  • polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O).
  • — Each independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
  • the total of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40 .
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60 .
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents oxygen
  • a form in which the end on the atom side is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the general formula (Z-4) or (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 (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • the polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
  • SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 .
  • the resin composition A has a polymerizable compound having a cardo skeleton from the viewpoint of improving development resistance.
  • a polymerizable compound having a cardo skeleton a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
  • Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line.
  • a and b each independently represents an integer of 1 to 5
  • c and d each independently represents an integer of 0 to 4.
  • R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively. This is a value obtained by subtracting a, b, c or d from the number of substituents which can be possessed.
  • Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings
  • X 1 to X 4 and R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.
  • X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • the substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, and is preferably an aliphatic group having a polymerizable group.
  • the aliphatic group having a polymerizable group represented by X 1 to X 4 is not particularly limited, and is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and an alkylene group having 2 to 10 carbon atoms. And more preferably an alkylene group having 2 to 5 carbon atoms.
  • aliphatic group having a polymerizable group represented by X 1 to X 4 when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom.
  • R is a substituent
  • the non-adjacent —CH 2 — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is More preferably, it is substituted with an oxygen atom.
  • the aliphatic group having a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar 11 to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line 14 is substituted with a heteroatom.
  • a polymerizable group capable of radical polymerization or cationic polymerization hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively
  • radical polymerizable group a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one.
  • examples thereof include a vinyl group and a (meth) acryloyloxy group.
  • a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
  • cationic polymerizable group generally known cationic polymerizable groups can be used.
  • alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group examples include groups. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
  • the polymerizable group contained in the substituent contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.
  • Two or more of Ar 1 ⁇ Ar 4 includes a substituent having a polymerizable group, preferably contains a substituent 2-4 of Ar 1 ⁇ Ar 4 has a polymerizable group, Ar 1 ⁇ Ar More preferably, 2 or 3 out of 4 contain a substituent having a polymerizable group, and more preferably 2 out of Ar 1 to Ar 4 contain a substituent having a polymerizable group.
  • X 1 to X 4 are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
  • c and d each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably c and d are both 0.
  • R 1 to R 4 each independently represents a substituent.
  • the substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, heteroaryls. Group, alicyclic group and the like.
  • the substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group.
  • R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar 11 to Ar 14 can have.
  • the value obtained by subtracting a, b, c, or d from the number of. e, f, g and h are each independently preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.
  • Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.
  • Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
  • Examples of the polymerizable compound having a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
  • Examples of the commercially available polymerizable compound having a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.), ogsol (manufactured by Osaka Gas Chemical Co., Ltd.), and the like.
  • the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition.
  • the lower limit is, for example, more preferably 0.5% by mass or more, and further preferably 2% by mass or more.
  • the upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the mass ratio (M / B) of the total content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin described above is 0.3-2. 0 is preferred, and 0.45 to 1.5 is more preferred from the viewpoint of better abrasion resistance.
  • the resin composition A may contain an organic solvent.
  • the organic solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the resin composition A. In consideration of the solubility, coating property, and safety of the polymerizable compound, the binder resin, and the like. It is preferable to be selected.
  • organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
  • Alkyl oxyacetate eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
  • alkyl 3-oxypropionate Esters for example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • 2-oxypropionic acid alkyl esters for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl
  • the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the organic solvent in the resin composition A is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. More preferable is 50 mass%.
  • the resin composition A may contain only one type of organic solvent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • various additives such as a filler, an adhesion promoter, an antioxidant, a polymerization inhibitor, an anti-aggregation agent, a surfactant, an infrared absorber, an ultraviolet absorber and the like are added as necessary. Can be contained. Examples of these additives include those described in JP-A-2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
  • the resin composition A can contain, for example, a sensitizer or light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same publication, and the like.
  • pigments or dyes other than the titanium nitride-containing particles can also be blended. Examples of other pigments include the following.
  • Examples of the pigment include conventionally known various inorganic pigments or organic pigments.
  • examples of inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and tungsten, and composite oxides of the above metals. The following can be mentioned as an organic pigment. However, the present invention is not limited to these.
  • Examples of the dye include various conventionally known dyes.
  • Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Japanese Patent No. 2592207, and US Pat. No. 4,808,501.
  • dye currently disclosed by 194828 gazette etc. can be used.
  • pyrazole azo compounds When classified as chemical structures, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
  • organic pigments or dyes can be used alone or in various combinations in order to increase color purity. Two or more kinds may be used in combination.
  • the red pigment and the titanium nitride-containing particles in combination from the viewpoint of adjusting the color, and although not particularly limited, Pigment Red 254 is preferable as the red pigment.
  • a yellow pigment and the said titanium nitride containing particle together from a viewpoint of improving light-shielding property, although it does not specifically limit, It is preferable that it is pigment yellow 150 as a yellow pigment.
  • the composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
  • a compound containing at least one of a fluorine atom and a silicon atom is not included in the fluorine-based surfactant described here.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (Nippon Lubrizol Co. tetrazole Co.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101,
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.
  • silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like. Note that a resin having a polysiloxane structure, which will be described later, and reactive silicone are not included in the silicone-based surfactant described here.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, and more preferably 0.005 to 1.0% by mass with respect to the total solid content of the composition of the present invention. 0.98% by mass is most preferred.
  • a resin having a polysiloxane structure is contained in the resin film.
  • the material constituting the resin film include at least the titanium nitride-containing particles described above, a binder resin, and a resin having a polysiloxane structure.
  • the resin film can be formed by forming a resin composition containing the above-described constituent materials or precursor materials thereof and applying the resin composition onto a substrate.
  • the said resin composition can also be used as the photosensitive resin composition which has exposure and developability.
  • a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition.
  • a binder resin a polymerizable compound, a dispersion resin described later, and the like may be used as the alkali-soluble material.
  • resin composition B the various materials contained in the resin composition mentioned above (henceforth "resin composition B") are explained in full detail.
  • the material in the resin composition B is the same except that the filler in the resin composition A is a reactive silicone, and the same applies to preferred embodiments.
  • a resin having a polysiloxane structure can be contained in the resin film.
  • the resin having a polysiloxane structure is preferably a resin formed from reactive silicone described later.
  • Reactive silicone is an organic-inorganic hybrid material and has a low free surface energy. For this reason, when a resin composition containing reactive silicone and a binder resin (further, the above-described polymerizable compound) is applied on a substrate, the reactive silicone is in contrast to the binder resin (further described below). It is unevenly distributed on the surface without being compatible, and forms an uneven shape.
  • a resin having a polysiloxane structure also corresponds to a compound containing at least one of a fluorine atom and a silicon atom.
  • Reactive silicone resin is a reactive type modified by substitution of substituents such as amino group, epoxy group, carboxyl group, hydroxyl group, methacryl group, mercapto group, phenol group at the side chain, one end or both ends of polysiloxane. Silicone resin.
  • amino-modified silicone resins include KF-860, KF-861, X-22-161A, X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3331, FM-3325 (and above, Manufactured by Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E and X-22-3710 (above, Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins Are KF-6001, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made
  • X-22-170DX, X-22-2426, X-22-176F manufactured by Shin-Etsu Chemical Co., Ltd.
  • one-end reactive silicone resins can also be used as the reactive silicone resin.
  • the content ratio of the reactive silicone to the binder resin is 100: 1 to 100: 30 because the uneven shape is stably and better expressed and the stability of the coating solution. It is preferable that the ratio is 100: 5 to 100: 30.
  • the content thereof is preferably 0.2 to 20% by mass, and preferably 0.5 to 15% by mass with respect to the total solid content in the composition. More preferably, it is 1 to 15% by mass, still more preferably 1 to 10% by mass.
  • Resin composition B may contain only one type of reactive silicone or two or more types of reactive silicone. When two or more types are included, the total amount is preferably within the above range.
  • Resin compositions A and B can be prepared by mixing the aforementioned components, respectively.
  • the respective components constituting the resin compositions A and B may be mixed together, or may be sequentially mixed after each component is dissolved or dispersed in a solvent.
  • the charging sequence and working conditions when blending are not particularly limited.
  • the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, each component is appropriately used as two or more solutions or dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
  • the resin compositions A and B are preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
  • Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter.
  • PTFE polytetrafluoroethylene
  • PP polypropylene
  • the filter has a pore size of about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth resin composition in a post process.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • select from various filters provided by Nippon Pole Co., Ltd. DFA4201NXEY, etc.
  • Advantech Toyo Co., Ltd. Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.) can do.
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
  • the resin film of the first embodiment is preferably manufactured using the resin composition A or the resin composition B.
  • substrate and forming a resin film It is preferable to have at least a resin film forming step.
  • the resin composition A or B is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound
  • the resin composition A or B is a substrate as a method for producing a resin film.
  • a process of forming a coating film (coating film forming process) and a process of exposing the coating film (exposure process).
  • the resin composition A or B is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, a patterned resin film can be formed.
  • the coating film forming step, the step of exposing the coating film in a pattern (pattern exposure step), and the step of developing and removing unexposed portions to form a patterned resin film (developing step) a process of forming a coating film (coating film forming process) and a process of exposing the coating film (exposure process).
  • the manufacturing method of the resin film which has a coating-film formation process, a pattern exposure process, and a image development process as a representative example among the said procedures is explained in full detail.
  • the procedure itself of the resin film forming step is the same as the procedure of the coating film forming step.
  • the exposure process and the pattern exposure process are the same procedure except that the exposure is performed in a pattern in the pattern exposure process.
  • a coating film is formed on the substrate using the resin composition A or B.
  • the coating film is a film formed by the resin composition A or B.
  • a coating film having the above-described titanium nitride-containing particles, a binder resin, a filler, and an actinic radiation curable material such as a polymerization initiator and a polymerizable compound is formed.
  • the activity of the above-described titanium nitride-containing particles, a binder resin, a resin having a polysiloxane structure formed from reactive silicone, and the like, a polymerization initiator, a polymerizable compound, and the like A coating film having a wire curable material is formed.
  • the substrate include a transparent substrate made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like.
  • a thin film transistor for driving an organic electroluminescence (organic EL) element may be formed on these transparent substrates.
  • a solid-state imaging device substrate in which a solid-state imaging device (light receiving device) such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is provided on the substrate can be used.
  • a method for applying the resin composition A or B on the substrate various methods such as a slit coating method, an ink jet method, a spin coating method, a spray coating method, a casting coating method, a roll coating method, and a screen printing method are used. be able to. From the point that the film thickness of the coating film can be obtained uniformly, the spin coating method and the spray coating method are preferable. In the case where the substrate surface is not flat, the spray coating method and the ink jet method are preferable because the film thickness is uniform.
  • prebaking heat-process
  • substrate you may heat-process (prebaking) with respect to the coating film formed on the board
  • the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds. Heating can be performed with a hot plate, oven, or the like.
  • a resin film is formed on the substrate by performing the procedure described in the coating film forming step. be able to.
  • This step is a step of exposing the coating film obtained in the coating film forming step in a pattern.
  • pattern exposure can be performed by exposing through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
  • radiation (light) that can be used for exposure ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
  • Irradiation dose exposure dose
  • the actinic radiation curable material is cured.
  • This step is a step of developing and removing an unexposed portion to form a patterned resin film.
  • the development removal of the unexposed portion can be performed using a developer.
  • the developer is preferably an organic alkali developer that does not damage the underlying solid-state imaging device and circuit.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
  • organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
  • aqueous solution in which these alkali agents are dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.005 to 6% by mass, particularly preferably 0.01 to 5% by mass.
  • the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metasuccinate is preferable.
  • a surfactant may be used for the developer.
  • a nonionic surfactant is preferable.
  • clean (rinse) with a pure water after image development.
  • the resin film may be composed of one layer of a pigment layer containing titanium nitride-containing particles, or may have a plurality of pigment layers. From the viewpoint of further improving the low reflectivity and moisture resistance, it is preferable that the pigment layer X1 and the pigment layer X2 each containing titanium nitride-containing particles are laminated adjacently. At this time, the concentration of the titanium nitride-containing particles contained in the pigment layer X2 is smaller than the concentration of the titanium nitride-containing particles contained in the pigment layer X1, and the surface roughness of the surface on the pigment layer X2 side of the resin film Ra is preferably 100 to 2000 cm.
  • the pigment layer (pigment layer X2) having the smallest concentration of titanium nitride-containing particles is located on the outermost surface side (layer position farthest from the substrate) of the resin film, so It can exhibit excellent light scattering with respect to light and can be more excellent in low reflectivity.
  • concentration of the titanium nitride-containing particles contained in the pigment layer X1” and “the concentration of the titanium nitride-containing particles contained in the pigment layer X2” are titanium nitride relative to the total solid content of each pigment layer. This corresponds to the content of the contained particles.
  • 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%. More preferably, it is mass%.
  • the concentration of 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.
  • (concentration of titanium nitride-containing particles contained in pigment layer X1) ⁇ (concentration of titanium nitride-containing particles contained in pigment layer X2) is preferably 5 to 40% by mass.
  • the resin film according to the second embodiment is adjacent to a pigment layer (hereinafter simply referred to as “pigment layer”) including a titanium nitride-containing particle containing one or more metal atoms other than the above-described titanium atoms. And a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom (hereinafter simply referred to as “surface layer”).
  • the thickness of the resin film is not particularly limited and is preferably 0.2 to 25 ⁇ m, more preferably 1.0 to 10 ⁇ m.
  • the above thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the resin film and arithmetically averaging them.
  • the thickness of the surface layer in the resin layer is preferably 0.050 to 0.200 ⁇ m.
  • the resin film contains at least a titanium nitride-containing particle containing at least one metal atom other than the titanium atom described above, a binder resin, and a compound containing at least one of a fluorine atom and a silicon atom ( Hereinafter, it can be formed by preparing “resin composition C”) and applying it onto a substrate.
  • the resin composition C uses a compound containing at least one of a fluorine atom and a silicon atom described below (preferably a resin containing at least one of a fluorine atom and a silicon atom). Indicates surface free energy. Therefore, for example, in a coating film formed by applying the resin composition C on a substrate, the compound is likely to be concentrated in the vicinity of the coating film surface on the side opposite to the substrate. This surface uneven distribution is particularly prominent when a resin containing at least one of a fluorine atom and a silicon atom is used as the compound.
  • the resulting coating film has a pigment layer (lower layer) containing titanium nitride-containing particles that are black pigments, and a surface layer (including a compound containing at least one of fluorine atoms and silicon atoms). It has a two-layer structure with the upper layer). When such a two-layer structure is formed, the light reflected on the surface of the surface layer and the light reflected on the interface between the surface layer and the pigment layer are canceled out by interference, and low reflectivity is achieved. Can do.
  • the resin film includes titanium nitride-containing particles as a black pigment in the pigment layer, and the titanium nitride-containing particles and the compound containing at least one of fluorine atoms and silicon atoms synergize. It has been confirmed that it exhibits excellent moisture resistance.
  • Resins such as (meth) acrylic polymers contain a small amount of radical initiators and unreacted monomers. In a humid heat environment, the polymer is cleaved by heat, oxygen, and moisture, and the chain caused by radicals generated at the time of cleaving. Cause haze accompanied by yellowing of the resin and deterioration of transparency (see paragraph [0017] of Japanese Patent Laid-Open No. 2011-65146).
  • a compound containing at least one of a hydrophobic fluorine atom and a silicon atom is unevenly distributed on the surface, thereby preventing moisture from being mixed into the film and preventing the resin from deteriorating. Further, although the mechanism is not clear, it is considered that even if there is moisture mixed in the film, titanium nitride-containing particles containing one or more metal atoms other than titanium atoms supplement the generated radicals.
  • the said resin composition C can also be used as the photosensitive resin composition which has exposure and developability.
  • a polymerization initiator, a polymerizable compound, etc. may be further blended in the resin composition C.
  • a binder resin, a polymerizable compound, a dispersion resin, or the like may be used as the alkali-soluble material.
  • Resin composition C contains a compound containing at least one of a fluorine atom and a silicon atom.
  • the compound containing at least one of a fluorine atom and a silicon atom (hereinafter also referred to as “specific compound”) is not particularly limited, and may have at least one of a fluorine atom and a silicon atom, and a curable functional group. preferable.
  • a specific compound has a fluorine atom from a viewpoint that the reflectance of a resin film is lower, the pattern linearity of a resin film is more excellent, and the crack of a resin film does not produce more easily.
  • the specific compound may be a monomer, a multimer, or a polymer.
  • the specific compound is preferably a (meth) acrylate polymer, more preferably a (meth) acrylate polymer having a fluorine atom.
  • One preferred embodiment of the specific compound is a compound having no benzene ring structure, and more preferably a compound having a fluorine atom and not having a benzene ring structure.
  • the silane coupling agent mentioned above is not contained in a specific compound.
  • the specific compound contains a fluorine atom
  • the specific compound is at least one selected from the group consisting of an alkylene group substituted with a fluorine atom, an alkyl group substituted with a fluorine atom, and an aryl group substituted with a fluorine atom. It is preferable to have one.
  • the alkylene group substituted with a fluorine atom is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the number of carbon atoms in the alkylene group substituted with a fluorine atom and the alkyl group substituted with a fluorine atom is preferably 1-20, more preferably 1-10, and even more preferably 1-5. preferable.
  • the aryl group substituted with a fluorine atom the aryl group is preferably directly substituted with a fluorine atom or substituted with a trifluoromethyl group.
  • the alkylene group substituted with a fluorine atom, the alkyl group substituted with a fluorine atom, and the aryl group substituted with a fluorine atom may further have a substituent other than the fluorine atom.
  • alkyl group substituted with a fluorine atom and the aryl group substituted with a fluorine atom for example, paragraphs 0266 to 0272 of JP2011-100089A can be referred to, the contents of which are described in this specification. Incorporated.
  • the specific compound includes an alkylene group substituted with a fluorine atom and an oxygen atom.
  • a group X (group represented by the formula (X) (repeating unit)) linked to each other, and more preferably a perfluoroalkylene ether group.
  • Formula (X) - (L A -O ) - L A represents an alkylene group substituted with a fluorine atom.
  • the number of carbon atoms in the alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-5.
  • the alkylene group substituted with the fluorine atom may contain an oxygen atom.
  • the alkylene group substituted with a fluorine atom may be linear or branched.
  • the “perfluoroalkylene ether group” intends that L A is a perfluoroalkylene group.
  • the “perfluoroalkylene group” intends a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms.
  • the group (repeating unit) represented by the formula (X) may be linked repeatedly, and the number of repeating units is not particularly limited, and is preferably 1 to 50 in terms of more excellent effects of the present invention. ⁇ 20 is more preferred. That is, a group represented by the formula (X-1) is preferable.
  • Partial structure (S) When the specific compound contains a silicon atom, an alkylsilyl group, an arylsilyl group, or the following partial structure (S) (* represents a bonding site with another atom) is preferable. Partial structure (S)
  • the total number of carbon atoms in the alkyl chain of the alkylsilyl group is preferably 1-20, more preferably 1-10, still more preferably 1-6. Alkylsilyl groups and trialkylsilyl groups are preferred. Examples of the aryl group in the arylsilyl group include a phenyl group.
  • a cyclic structure may be formed including the partial structure (S).
  • the partial structure (S) preferably employed in the present invention is preferably —Si (R) 2 —O—Si (R) 2 — (R is an alkyl group having 1 to 3 carbon atoms) or an alkoxysilyl group.
  • paragraphs 0277 to 0279 of JP2011-100089A can be referred to, and the contents thereof are incorporated in this specification.
  • the specific compound may have at least one of fluorine atoms and silicon atoms, and may have two or more. Moreover, the specific compound may have a combination of a fluorine atom and a silicon atom.
  • the specific compound preferably has one or more curable functional groups, and may have two or more curable functional groups. Only one type of curable functional group may be used, or two or more types may be used.
  • the curable functional group may be a thermosetting functional group or a photocurable functional group.
  • the curable functional group is (meth) acryloyloxy group, epoxy group, oxetanyl group, isocyanate group, hydroxyl group, amino group, carboxyl group, thiol group, alkoxysilyl group, methylol group, vinyl group, (meth) acrylamide group It is preferably at least one selected from the group consisting of styryl group and maleimide group, and at least one selected from the group consisting of (meth) acryloyloxy group, epoxy group and oxetanyl group Is more preferable.
  • the amount of the ethylenically unsaturated group in the specific compound is preferably 0.001 to 10.0 mmol / g, and 0.01 to 5.00 mmol / g Is more preferable.
  • the number of one or more groups selected from a fluorine atom and a silicon atom in one molecule is preferably 1 to 20, and more preferably 3 to 15.
  • the number of curable functional groups in one molecule is not particularly limited, and is preferably 2 or more and more preferably 4 or more in terms of more excellent effects of the present invention.
  • the upper limit is not particularly limited and is often 10 or less, more often 6 or less.
  • the structure preferably includes a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group, and is represented by the following formula (B1). And a repeating unit represented by the following formula (B2) and a repeating unit represented by the formula (B3).
  • R 1 to R 11 each independently represents a hydrogen atom, an alkyl group, or a halogen atom.
  • L 1 to L 4 each independently represents a single bond or a divalent linking group.
  • X 1 represents a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group
  • X 2 represents an alkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, an alkylsilyl group, an arylsilyl group, or Represents a group containing the partial structure (S)
  • X 3 represents a repeating unit represented by the formula (X-1).
  • R 1 to R 11 are preferably each independently a hydrogen atom or an alkyl group.
  • R 1 to R 11 represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable.
  • R 1 to R 11 represent a halogen atom, a fluorine atom is preferable.
  • L 1 to L 4 represent a divalent linking group
  • the divalent linking group includes an alkylene group which may be substituted with a halogen atom, and a halogen atom substituted.
  • a group consisting of a combination with one kind of group is preferable, an alkylene group having 2 to 10 carbon atoms which may be substituted by a halogen atom, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
  • R 12 represents a hydrogen atom or a methyl group.
  • repeating unit represented by the formula (B1) include the following, but the present invention is not limited thereto.
  • X 1 represents a hydrogen atom, —CH 3 , —F or —CF 3, and more preferably a hydrogen atom or a methyl group.
  • Me represents a methyl group.
  • repeating unit represented by the above formula (B3) examples include the following, but the present invention is not limited thereto.
  • l, m, n, h, j, and k represent an integer of 1 to 100.
  • the content of the repeating unit represented by the formula (B1) is preferably 5 to 98 mol%, more preferably 30 to 95 mol%, based on all repeating units in the specific compound.
  • the total content of the repeating unit represented by the formula (B2) and the repeating unit represented by the formula (B3) is preferably 1 to 70 mol% with respect to all the repeating units in the specific compound, More preferably, it is 5 to 60 mol%.
  • the content of the repeating unit represented by Formula (B2) is 0 mol%.
  • the content of the repeating unit represented by the formula (B3) is preferably in the above range.
  • the specific compound may have a repeating unit other than the repeating units represented by the above formulas (B1) to (B3).
  • the content of other repeating units is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units in the specific compound.
  • the weight average molecular weight (Mw: in terms of polystyrene) is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000.
  • the dispersity (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.
  • the GPC (gel permeation chromatography) method uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation) as columns. Based on a method using THF (tetrahydrofuran) as an eluent.
  • the specific compound is preferably capable of forming a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm with the specific compound alone. That is, the refractive index at a wavelength of 550 nm of a film formed only from the specific compound is preferably 1.1 to 1.5.
  • the preferred range of the refractive index is preferably 1.2 to 1.5, more preferably 1.3 to 1.5, from the viewpoint of low reflectivity of the resin film.
  • a reactive silicone contained in the resin composition B can also be used as a compound containing at least one of a fluorine atom and a silicon atom.
  • the preferred embodiment of the reactive silicone is as described above.
  • the content of the specific compound in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and more preferably 1 to 15% by mass with respect to the total solid content in the resin composition. More preferred is 1 to 10% by mass.
  • the composition may contain one specific compound or two or more specific compounds. When a composition contains 2 or more types of specific compounds, the total should just be in the said range.
  • the material in the resin composition C is the same except that the filler in the resin composition A is a compound containing at least one of a fluorine atom and a silicon atom, and the same applies to preferred embodiments.
  • Resin composition C can be prepared by mixing the aforementioned components.
  • the method for preparing the resin composition C is also the same as that of the resin compositions A and B described above, and the preferred embodiment is also the same.
  • the resin composition of the present invention preferably does not contain impurities such as metals other than those contained in titanium nitride-containing particles, metal salts containing halogens, acids and alkalis.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
  • Examples of the method for removing impurities such as metals from various materials include filtration using a filter or purification steps by distillation (particularly thin film distillation, molecular distillation, etc.).
  • the purification process by distillation is, for example, “ ⁇ Factory Operation Series> Augmentation / Distillation, Issued July 31, 1992, Chemical Industry Co., Ltd.” or “Chemical Engineering Handbook, Issued September 30, 2004, Asakura Shoten, pp. 95-102” Page ".
  • the filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • the filter material is preferably a polytetrafluoroethylene, polyethylene or nylon filter.
  • the filter may be a composite material combining these materials and ion exchange media. You may use the filter previously wash
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different hole diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • a raw material having a low metal content is selected as a raw material constituting each material, filter filtration is performed on the raw materials constituting various materials, or Examples of the method include distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
  • adsorbent a known adsorbent can be used.
  • an inorganic adsorbent such as silica gel or zeolite
  • an organic adsorbent such as activated carbon
  • the resin film of the second embodiment is preferably manufactured using the resin composition C.
  • the method of forming a surface layer using the compound containing at least one of a fluorine atom and a silicon atom on the upper surface of a pigment layer is not prevented.
  • the resin composition C is provided on a board
  • the resin composition C is a curable composition containing an actinic radiation curable material such as a polymerization initiator and a polymerizable compound, as a method for producing a resin film
  • the resin composition C is applied on a substrate. It is preferable to have a step of forming a coating film (coating layer forming step) and a step of exposing the coating film (exposure step).
  • a patterned resin film can be formed.
  • the coating film forming step the step of exposing the coating film in a pattern (pattern exposure step), and the step of developing and removing unexposed portions to form a patterned resin film (developing step) ).
  • pattern exposure step the step of exposing the coating film in a pattern
  • developing step the step of developing and removing unexposed portions to form a patterned resin film
  • the resin film of the first embodiment is made of titanium nitride-containing particles containing at least one metal atom other than the above-described titanium atoms.
  • the roughness Ra may be 100 to 2000 mm.
  • the compound which contains at least one of a fluorine atom and a silicon atom is the same as that of what was mentioned above with the resin composition C, and the same also about a suitable aspect (a compounding quantity is included).
  • the manufacturing method of the resin film of 3rd Embodiment is the same as that of 1st Embodiment, The suitable aspect is also the same.
  • the resin film in the fourth embodiment is a resin film in which a pigment layer Y1 and a pigment layer Y2 each containing titanium nitride-containing particles containing at least one metal atom other than the above-described titanium atom are laminated adjacently. Yes, the concentration of titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 is different from each other.
  • the concentration of the titanium nitride-containing particles contained in the pigment layer Y1” and “the concentration of the titanium nitride-containing particles contained in the pigment layer Y2” are titanium nitride relative to the total solid content of each pigment layer. This corresponds to the content of the contained particles.
  • the method for producing the resin film in the fourth embodiment is not particularly limited, and the pigment layer is formed on the substrate using a resin composition for forming the pigment layer Y1 (hereinafter also referred to as “resin composition D”).
  • the pigment layer Y2 is formed on the pigment layer Y1 using a step of forming Y1 (pigment layer Y1 formation step) and a resin composition (hereinafter also referred to as “resin composition E”) that forms the pigment layer Y2. Step (pigment layer Y2 forming step).
  • the concentrations of the titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other, and either the pigment layer Y1 or the pigment layer Y2 is a pigment layer having a smaller concentration of titanium nitride-containing particles.
  • the concentration of titanium nitride-containing particles contained in the pigment layer Y1 and the pigment layer Y2 are different from each other, and either the pigment layer Y1 or the pigment layer Y2 is a pigment layer having a smaller concentration of titanium nitride-containing particles.
  • the pigment layer Y2 is a pigment layer having a smaller concentration of titanium nitride-containing particles and light is incident from the pigment layer Y2 side
  • the light reflected from the surface of the pigment layer Y1, the pigment layer Y1 and the pigment layer Y2 The light reflected at the interface with the light is canceled out by the interference, so that low reflectivity can be achieved.
  • the same effect can be obtained when the pigment layer Y1 on the substrate side is a pigment layer having a smaller concentration of titanium nitride-containing particles and light is incident from the pigment layer Y1 side.
  • the concentration of titanium nitride-containing particles in the pigment layer at 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 at a low concentration is preferably 1 to 45% by mass, and more preferably 1 to 40% by mass.
  • the absolute value of (concentration of titanium nitride-containing particles contained in pigment layer Y1) ⁇ (concentration of titanium nitride-containing particles contained in pigment layer Y2) is preferably 5 to 40% by mass.
  • the film thicknesses of the pigment layers Y1 and Y2 are each preferably 0.3 to 1.2 ⁇ m, and more preferably 0.4 to 1.0 ⁇ m.
  • the total film thickness of both layers is preferably 0.5 to 2.0 ⁇ m, and more preferably 1.0 to 1.5 ⁇ m.
  • the above-mentioned thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the film and arithmetically averaging them.
  • the optical density (optical density, hereinafter referred to as “OD value”) of the resin film is preferably 3 or more, more preferably 4 to 5 in the visible light range of a wavelength of 380 to 700 nm. If the overall OD value is less than 3, part of the light from the backlight is transmitted, causing a reduction in contrast. On the other hand, when it exceeds 5, the addition amount of the black pigment increases and the reflectance tends to be relatively high.
  • the OD value of the pigment layer where the concentration of titanium nitride-containing particles is low is preferably 0.5 to 2.0, more preferably 0.8 to 1.5.
  • the OD value of the pigment layer at which the concentration of titanium nitride-containing particles is high is preferably 1.0 to 5.0, and more preferably 2.0 to 3.5.
  • the method further comprises a step of exposing the pigment layer (exposure step). May be.
  • the exposure step is a step of exposing the pigment layer in a pattern
  • a step (development step) of forming a colored pattern by developing and removing unexposed portions after the exposure step may be further provided.
  • the preferred embodiments of the coating film forming step, the exposure step, and the developing step are the same as the pigment layer forming step, the exposing step, and the developing step in the first embodiment, respectively, and the preferred embodiments are also the same.
  • the resin film of the first to fourth embodiments of the present invention can be preferably used as a color filter or a light shielding film.
  • a film obtained by curing the resin film by exposure can be preferably used.
  • the light shielding film is appropriately disposed on each member, and may be disposed in a frame shape, for example.
  • the color filter can be suitably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. It is.
  • the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
  • the color filter can be preferably used for an organic EL element.
  • the organic EL element a white organic EL element is preferable.
  • the organic EL element preferably has a tandem structure.
  • JP 2003-45676 A supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc.
  • Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate.
  • the lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region.
  • the organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked.
  • the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer.
  • the organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light.
  • the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
  • the light shielding film is formed and used on various members in the image display device or the sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a back surface of a solid-state imaging device, etc.). it can. Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
  • the thickness of the light shielding film is not particularly limited, and is preferably 0.2 to 25 ⁇ m, more preferably 1.0 to 10 ⁇ m.
  • the thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light shielding film and arithmetically averaging them.
  • the reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less.
  • the reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High Technology.
  • the solid-state imaging device of the present invention includes the resin film (color filter, light shielding film, etc.) of the first to fourth embodiments described above.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as the configuration includes the resin film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
  • 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.
  • the display device For the definition of the display device or details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., issued in 1990)”, “Display Device (Junsho Ibuki, Industrial Book Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention is not limited to a liquid crystal display device such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and an STN (Super-Twist).
  • IPS In Plane Switching
  • MVA Multi-domain Vertical Alignment
  • STN Super-Twist
  • Nematic Nematic
  • TN Transmission Nematic
  • VA Very Alignment
  • OCS On-chip spacer
  • FFS Fluor field switching
  • R-OCB Reflective Optic
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above.
  • the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device of the present invention may be composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlights in addition to SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. It is described in.
  • the cured film obtained by curing the curable composition is a portable device such as a personal computer, tablet, mobile phone, smartphone or digital camera; OA (Office Automation) device such as a printer multifunction device or scanner; , Barcode readers, automated teller machines (ATMs), high-speed cameras, or industrial devices such as personal authentication using facial image authentication; in-vehicle camera devices; endoscopes, capsule endoscopes, catheters, etc.
  • OA Office Automation
  • ATMs automated teller machines
  • Medical camera equipment space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather / ocean observation cameras, land resource exploration cameras, or exploration cameras for space astronomy and deep space targets
  • Shading member for optical filter or module used for etc., shading It can be used for anti-reflective member or anti-reflective layer.
  • curing a curable composition can also be used for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). It does not specifically limit, In addition to the optical filter or optical film used for micro LED or micro OLED, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function. Examples of the micro LED or the micro OLED include those disclosed in Japanese Patent Application Publication No. 2015-500562 and Japanese Patent Application Publication No. 2014-533890.
  • curing a curable composition can be used also for uses, such as a quantum dot display. It does not specifically limit, In addition to the optical filter or optical film used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
  • quantum dot displays include those of U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, or U.S. Patent Application Publication No. 2014/0035960. Can be mentioned.
  • Black pigment Pig-1 A black pigment Pig-1 was produced under the following conditions. High frequency power 5.5kW Plasma gas flow rate Argon 5L / min + Nitrogen 5L / min Spray gas flow rate Nitrogen 20L / min Powder supply JEOL powder supply equipment TP-99010FDR Supply gas Nitrogen 15L / min Supply amount 15g / min Powder Ti powder Toho Titanium TC-200 Ag powder Mitsui Kinzoku SPQ03R Fe powder JIP steel JIP 270M
  • the O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. And allowed to stand at 30 ° C. for 24 hours.
  • the obtained titanium nitride-containing particles (black pigment Pig-1) were measured for the content of titanium (Ti) atoms and metal atoms by ICP emission spectroscopic analysis.
  • the Ti atom content was 60% by mass
  • the Ag atom content was 15% by mass
  • the Fe atom content was 1% by mass with respect to the total amount (100% by mass) of the black pigment Pig-1.
  • an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
  • the nitrogen and oxygen atom contents were measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and calculated by the inert gas melting-thermal conductivity method. did.
  • the content of nitrogen atoms was 19% by mass relative to the total amount of black pigment Pig-1 (100% by mass), and the content of oxygen atoms was the total amount of black pigment Pig-1 (100% by mass). It was 5 mass% with respect to.
  • the black pigment Pig-1 was subjected to an X-ray diffraction test by the following method.
  • X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder.
  • the X-ray source is CuK ⁇ ray
  • the output is 50 kV / 200 mA
  • the slit system is 1 ° -1 ° -0.15 mm-0.45 mm
  • the measurement step (2 ⁇ ) is 0.02 °
  • the scan speed is It was 2 ° / min.
  • the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2 ⁇ 46 ° was measured. As a result, the diffraction angle 2 ⁇ 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 by vacuum degassing at 100 ° C. using a highly accurate fully automatic gas adsorption device (“BELSORP” 36) manufactured by Nippon Bell Co., Ltd., and then the liquid nitrogen temperature of N 2 gas (77K) The adsorption isotherm in was measured, and this isotherm was determined by the BET method. As a result, the specific surface area of the black pigment Pig-1 determined by using the BET method was 29 m 2 / g.
  • BELSORP fully automatic gas adsorption device
  • Black pigment Pig-2 A black pigment Pig-2 was prepared under the following conditions. High frequency power 5.5kW Plasma gas flow rate Argon 5L / min + Nitrogen 5L / min Spray gas flow rate Nitrogen 20L / min Powder supply JEOL powder supply equipment TP-99010FDR Supply gas Nitrogen 15L / min Supply amount 15g / min Powder Ti powder Toho Titanium TC-200 Ag powder Mitsui Kinzoku SPQ03R Ni powder Toho Titanium
  • the O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. And allowed to stand at 30 ° C. for 24 hours.
  • the obtained titanium nitride-containing particles (black pigment Pig-2) were measured for content of titanium (Ti) atoms and metal atoms by ICP emission spectroscopic analysis.
  • the content of Ti atoms was 65% by mass
  • the content of Ag atoms was 8% by mass
  • the content of Ni atoms was 2% by mass.
  • an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
  • the nitrogen and oxygen atom contents were measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and calculated by the inert gas melting-thermal conductivity method. did.
  • the content of nitrogen atoms is 20% by mass with respect to the total amount of black pigment Pig-2 (100% by mass), and the content of oxygen atoms is the total amount of black pigment Pig-2 (100% by mass). It was 5 mass% with respect to.
  • the black pigment Pig-2 was subjected to an X-ray diffraction test by the following method.
  • X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder.
  • the X-ray source is CuK ⁇ ray
  • the output is 50 kV / 200 mA
  • the slit system is 1 ° -1 ° -0.15 mm-0.45 mm
  • the measurement step (2 ⁇ ) is 0.02 °
  • the scan speed is It was 2 ° / min.
  • the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2 ⁇ 46 ° was measured. As a result, the diffraction angle 2 ⁇ 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 by vacuum degassing at 100 ° C. using a highly accurate fully automatic gas adsorption device (“BELSORP” 36) manufactured by Nippon Bell Co., Ltd., and then the liquid nitrogen temperature of N 2 gas (77K) The adsorption isotherm in was measured, and this isotherm was determined by the BET method. As a result, the specific surface area of the black pigment Pig-2 obtained by using the BET method was 33 m 2 / g.
  • V powder refers to vanadium powder. Powder Ti powder Toho Titanium TC-200 Ag powder Mitsui Kinzoku SPQ03R V powder made by Taiyo Mining Co., Ltd. VN200
  • O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. And left at a temperature of 100 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-3) was measured by the same method as that for black pigment Pig-2.
  • the content of Ti atoms was 50% by mass
  • the content of Ag atoms was 20% by mass
  • the content of V atoms was 1% by mass.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the nitrogen atom content was 19% by mass with respect to the total amount (100% by mass) of the black pigment Pig-3
  • the oxygen atom content was the total amount (100% by mass) of the black pigment Pig-3. It was 10 mass% with respect to.
  • the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-3 was 42.8. °.
  • the specific surface area of the black pigment Pig-3 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 25 m 2 / g.
  • Black pigment Pig-4 A black pigment Pig-4 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Note that W powder refers to tungsten powder. Powder Ti powder Toho Titanium TC-200 W powder Nippon New Metal WH Fe powder JIP steel JIP 270M
  • the O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. And left at a temperature of 200 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-4) was measured by the same method as that for the black pigment Pig-2.
  • the content of Ti atoms is 50% by mass
  • the content of W atoms is 12.99% by mass
  • the content of Fe atoms is 0.01% by mass. %Met.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the content of nitrogen atoms was 20% by mass with respect to the total amount of black pigment Pig-4 (100% by mass), and the content of oxygen atoms was the total amount of black pigment Pig-4 (100% by mass). It was 17 mass% with respect to.
  • the peak diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-4 was 43.0. °.
  • the specific surface area of the black pigment Pig-4 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 27 m 2 / g.
  • Black Pigment Pig-5 A black pigment Pig-5 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Powder Ti powder Toho Titanium TC-200 Ni powder Toyo Titanium Fe powder JFE Steel JIP 270M
  • the O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 1000 ppm. And left at a temperature of 200 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-5) was measured by the same method as that for black pigment Pig-2.
  • the content of Ti atoms was 52% by mass
  • the content of Ni atoms was 5% by mass
  • the content of Fe atoms was 2% by mass.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the content of nitrogen atoms was 20% by mass with respect to the total amount of black pigment Pig-5 (100% by mass)
  • the content of oxygen atoms was the total amount of black pigment Pig-5 (100% by mass). It was 21 mass% with respect to.
  • the peak diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-5 was 43.5. °.
  • the specific surface area of the black pigment Pig-5 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 34 m 2 / g.
  • Black Pigment Pig-6 A black pigment Pig-6 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Powder Ti powder Toho Titanium TC-200 Ag powder Mitsui Kinzoku SPQ03R W powder Nippon New Metal WH V powder made by Taiyo Mining Co., Ltd. VN200
  • the O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. And left at a temperature of 30 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-6) was measured by the same method as that for black pigment Pig-2.
  • the content of Ti atoms is 57% by mass
  • the content of Ag atoms is 10% by mass
  • the content of W atoms is 7.9% by mass
  • the V atom content was 0.01% by mass.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the content of nitrogen atoms was 18% by mass with respect to the total amount of black pigment Pig-6 (100% by mass), and the content of oxygen atoms was the total amount of black pigment Pig-6 (100% by mass). It was 7 mass% with respect to.
  • the peak diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-6 was 42.7. °.
  • the specific surface area of the black pigment Pig-6 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 32 m 2 / g.
  • Black Pigment Pig-7 A black pigment Pig-7 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Powder Ti powder Toho Titanium TC-200 Ag powder Mitsui Kinzoku SPQ03R Fe powder JIP steel JIP 270M
  • O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 1000 ppm. And left at a temperature of 300 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-7) was measured by the same method as that for black pigment Pig-2.
  • the content of Ti atoms was 50% by mass
  • the content of Ag atoms was 5% by mass
  • the content of Fe atoms was 2% by mass.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the content of nitrogen atoms was 20% by mass with respect to the total amount of black pigment Pig-7 (100% by mass)
  • the content of oxygen atoms was the total amount of black pigment Pig-7 (100% by mass). It was 23 mass% with respect to.
  • the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-7 was 43.7. °.
  • the specific surface area of the black pigment Pig-7 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 30 m 2 / g.
  • Black Pigment Pig-8 A black pigment Pig-8 was produced in the same manner as the black pigment Pig-2 except that the following powder was used. Powder Ti powder Toho Titanium TC-200 Ni powder V powder made by Toho Titanium V powder made by Taiyo Mining Co., Ltd.
  • O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 1000 ppm. And left at a temperature of 300 ° C. for 24 hours.
  • the content of titanium (Ti) atoms and metal atoms in the obtained titanium nitride-containing particles (black pigment Pig-8) was measured by the same method as that for black pigment Pig-2.
  • the Ti atom content was 47% by mass
  • the Ni atom content was 10% by mass
  • the V atom content was 2% by mass.
  • the contents of nitrogen atoms and oxygen atoms were also measured by the same method as that for the black pigment Pig-2.
  • the content of nitrogen atoms was 18% by mass with respect to the total amount of black pigment Pig-8 (100% by mass)
  • the content of oxygen atoms was the total amount of black pigment Pig-8 (100% by mass). It was 23 mass% with respect to.
  • the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane was evaluated by the same method as that of the black pigment Pig-2, the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane of the black pigment Pig-8 was 43.7. °.
  • the specific surface area of the black pigment Pig-8 was determined by the same method as that for the black pigment Pig- 2 , the specific surface area was 26 m 2 / g.
  • composition, production method and physical properties of black pigment Pig-1 to black pigment Pig-8 are shown in Table 1 below.
  • composition 1 Components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion A.
  • the resin (X-1) described below was synthesized with reference to the description in JP2013-249417A.
  • the weight average molecular weight of the resin (X-1) was 30,000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.
  • the obtained dispersion A was subjected to a dispersion treatment under the following conditions using NPM Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a pigment dispersion A.
  • ⁇ Bead diameter ⁇ 0.05mm
  • Bead filling rate 65% by volume
  • Mill peripheral speed 10m / sec ⁇
  • Separator peripheral speed 11m / s ⁇
  • Amount of liquid mixture for dispersion treatment 15.0 g ⁇ Circulating flow rate (pump supply amount): 60 kg / hour ⁇ Processing liquid temperature: 20-25 °C ⁇
  • a pigment dispersion B was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with Pig-2.
  • a pigment dispersion C was prepared in the same manner as the pigment dispersion A except that the black pigment Pig-1 was replaced with “13M-T (trade name)” manufactured by Mitsubishi Materials Corporation.
  • the pigment particles contained in “13M-T (trade name)” manufactured by Mitsubishi Materials Corporation are titanium oxynitride.
  • a pigment dispersion D was prepared in the same manner as the pigment dispersion A, except that the resin (X-1) was replaced with a resin (X-2) having the following structure.
  • the weight average molecular weight of the resin (X-2) was 25000, the acid value was 53 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 72.
  • a pigment dispersion E was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-3.
  • a pigment dispersion F was prepared in the same manner as the preparation of the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-4.
  • a pigment dispersion G was prepared in the same manner as the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-5.
  • a pigment dispersion H was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-6.
  • a pigment dispersion I was prepared in the same manner as the pigment dispersion A, except that the black pigment Pig-1 was replaced with the black pigment Pig-7.
  • a pigment dispersion J was prepared in the same manner as the preparation of the pigment dispersion A except that the black pigment Pig-1 was replaced with the black pigment Pig-8.
  • ⁇ P-4 After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Japanese Patent No. 3120476; Example 1), 40 parts by mass of glycidyl methacrylate was added. Then, after reprecipitating with purified water, the solid content is collected by filtration, and the solid content is dried to obtain an acrylic polymer having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g) as polymer 4. A powder was obtained.
  • Mw average molecular weight
  • each of S-1 and S-2 is a polymer compound containing a repeating unit containing at least one of a fluorine atom and a silicon atom and a repeating unit having a polymerizable group in the side chain.
  • solvent -PGMEA: Propylene glycol monomethyl ether acetate-PGME: 1-methoxy-2-propanol-High boiling point solvent: Hisolv BDM (diethylene glycol butyl methyl ether, boiling point 212 ° C, manufactured by Toho Chemical Co., Ltd.)
  • K-1 Irgacure OXE02 (BASF Japan)
  • K-2 Compound represented by the following structure
  • K-3 NCI-831 (manufactured by Adeka Co., Ltd.)
  • K-4 Irgacure 369 (BASF)
  • K-5 KAYACURE DETX-S (manufactured by Shoji Sangyo Co., Ltd.)
  • M-2 OGSOL EA-0200 (Osaka Gas Chemical Co., Ltd.)
  • M-3 Aronix TO-2349 (Toagosei Co., Ltd.) Note that M-2 corresponds to a polymerizable compound having a cardo structure and having a 9,9-bisarylfluorene skeleton.
  • Example 1 In a 200 g container (dispo cup), 14 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 10 g of PGMEA, 21 g of Thruria 5320 (20% MIBK solution), 55 g of pigment dispersion A, In this order, the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • P-1 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • 10 g of PGMEA propylene glycol monomethyl ether acetate
  • Thruria 5320 20% MIBK solution
  • Example 2 Resin composition similar to Example 1 except that Surria 5320 (20% MIBK solution) was replaced with Silica 1 (FF-D-B1, particle distribution maximum: 300 nm, manufactured by Koshin Chemical Co., Ltd.) (72 wt% PGME solution) A product was prepared. In addition, it was set as the desired solid content density
  • Example 3 A resin composition was prepared in the same manner as in Example 1, except that through rear 5320 (20% MIBK solution) was replaced with acrylic particles 2 (MP-300, particle distribution maximum value: 100 nm, manufactured by Soken Chemical Co., Ltd.). In addition, it was set as the desired solid content density
  • Example 4 To a 200 g container (dispo cup), add 6 g of P-1, 35 g of PGMEA, 4 g of KF-6001 (S-3), 55 g of pigment dispersion A in this order, and stir with a stirrer for 30 minutes for resin composition A product was prepared.
  • Example 5 A resin composition was prepared in the same manner as in Example 1 except that the pigment dispersion A was changed to the pigment dispersion B.
  • Example 6 To a 200 g container (dispo cup), add 6 g of P-4, 28 g of PGMEA, 7 g of ethyl lactate, 4 g of KF-6001 (S-3), 55 g of pigment dispersion A in this order, and add 30 minutes with a stirrer.
  • the resin composition was prepared by stirring.
  • Comparative Example 1 A resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the pigment dispersion A was changed to the pigment dispersion C.
  • Example 7 In a 200 g container (dispo cup), 30 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 13 g of NMP (N-methylpyrrolidone), and P-3 (20% PGMEA (propylene glycol monomethyl ether) 7 g of acetate) solution), 17 g of thruria 5320 (20% MIBK solution), pigment dispersion A (black pigment: 8.2 g, resin X-1: 2.5 g, PGMEA: 13 g, butyl acetate: 9.1 g) Were added in this order and stirred for 30 minutes with a stirrer to prepare a resin composition.
  • P-2 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • P-3 20% PGMEA (propylene glycol monomethyl ether) 7 g of acetate) solution
  • Example 8 In a 200 g container (dispo cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 22 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • P-2 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • 22 g of PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • Thruria 5320 14 g of (20% MIBK solution) Thruria 5320 14 g of (20% MIBK solution
  • 55 g of pigment dispersion A were added in this order, and
  • Example 9 In 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, 1 g of Irgacure OXE02 (manufactured by BASF Japan), silica 1 (FF-D-B1, particle distribution maximum value: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, silica is 42 wt% in the solid content) 4 g, pigment dispersion A 55 g are added in this order.
  • the resin composition was prepared by stirring for a minute.
  • Example 10 A resin composition was prepared in the same manner as in Example 8, except that through rear 5320 (20% MIBK solution) was replaced with acrylic particles 1 (MX-80H3wT, particle distribution maximum value: 800 nm, manufactured by Soken Chemical Co., Ltd.) (powder). . In addition, it was set as the desired solid content density
  • Example 11 In a 200 g container (dispo cup), 5 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 33 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), KF- 3 g of 6001 (S-3) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • KF- 3 g of 6001 (S-3) 55 g of pigment dispersion A
  • Example 12 A resin composition was prepared in the same manner as in Example 8 except that the pigment dispersion A was changed to the pigment dispersion B.
  • Example 13 In a 200 g container (disposable cup), 5 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 17 g of PGMEA, 1 g of K-2, Thruria 5320 (20% MIBK) Solution) 13 g, 12 g of red dispersion (prepared by the method of paragraph ⁇ 0409> of WO2015 / 029643), 50 g of pigment dispersion A (black pigment: 12 g, resin X-1: 3.7 g, PGMEA: 21.3 g, butyl acetate: 13 g) were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Example 14 In a 200 g container (dispo cup), 5 g of M-1 and 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), P-5 (40% PGMEA (propylene glycol monomethyl ether acetate) solution) 1 g, PGMEA 34 g, Irgacure OXE02 (BASF Japan) 1 g, KF-6001 3 g, Pigment dispersion A 55 g in this order, and a stirrer for 30 minutes to prepare a resin composition.
  • P-2 PGMEA (propylene glycol monomethyl ether acetate) solution
  • P-5 propylene glycol monomethyl ether acetate
  • Example 15 In a 200 g container (dispo cup), 3 g of M-1, 9 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 18 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • Thruria 5320 14 g of (20% MIBK solution) Thruria 5320 14 g of (20% MIBK solution
  • 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • Example 16 In a 200 g container (dispo cup), 5 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 24 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 14 g of (20% MIBK solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • Thruria 5320 14 g of (20% MIBK solution) Thruria 5320 14 g of (20% MIBK solution
  • 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • Example 1A In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 32 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), silica 2 (FF-B-B1, particle distribution maximum: 30 nm, manufactured by Koshin Chemical Co., Ltd., 60 wt% PGME solution, silica is 10 wt% in the solid content) 7 g, pigment dispersion A 55 g, in this order, 30
  • the resin composition was prepared by stirring for a minute.
  • Example 2A In a 200 g container (dispo cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 31.7 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Add 0.3 g of silica 1 (FF-D-B1, maximum particle distribution: 300 nm, manufactured by Koshin Chemical Co., Ltd., 72 wt% PGME solution, silica is 42 wt% in solid content), and 55 g of pigment dispersion A in this order.
  • the resin composition was prepared by stirring with a stirrer for 30 minutes.
  • the reflectance was evaluated using the produced substrate with a resin film. Specifically, light of 400 to 700 nm was incident on the resin film with an incident angle of 5 ° with respect to the produced substrate with the resin film, and the reflectance was measured with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. . In the table, the smaller the value of reflectance, the lower the reflectivity. The results are shown in Tables 2 and 3.
  • Example 7 the contact angle was 110 ° C., the reflectance was 2% (the reflectance at 400 nm), and the surface roughness was 300 mm.
  • the moisture resistance of Example 7 was “B”, and the rubbing test was “A”.
  • Example 8 (M / B: about 0.9) in which the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin is different, respectively. Comparing Example 15 (M / B: 0.39) and Example 16 (M / B: 1.1), Example 8 and Example in which M / B is in the range of 0.45 to 1.5 In 16, it was confirmed that the abrasion resistance was superior.
  • Example 16 the total amount of the binder resin and the polymerizable compound was not changed, and the photosensitive resin was similarly prepared except that the amount of the binder resin and the polymerizable compound was adjusted so that M / B was 1.6. A composition was prepared. When the same evaluation as in Example 16 was performed, the same result as in Example 16 was obtained except that the result of the rubbing test was “B”.
  • Example 9 and 1A when Examples 9 and 1A were compared, it was confirmed that the moisture resistance was low in Example 1A in which the maximum value in the maximum distribution of the added filler was 30 nm. Further, when Examples 9 and 10 were compared, in Example 10 in which the maximum value in the maximum distribution of the added filler was 800 nm, the result of the rubbing test was low.
  • Example 9 when Example 9 and Example 2A were compared, in Example 2A in which the filler content was less than 1.0% by mass, the moisture resistance was low.
  • the moisture resistance was lower than that of the resin film of Examples.
  • trace amounts of radical initiators and unreacted monomers are present in (meth) acrylic polymer-based resin films, and these generate radicals by heat, oxygen, and moisture in a humid heat environment.
  • the polymer may be cleaved and chain decomposition may occur due to radicals generated during the cleaving.
  • the resin film of the example contains titanium nitride-containing particles containing metal atoms other than titanium atoms, and radicals generated in the film are trapped by the metal atoms, so that the film is hardly deteriorated. Presumably excellent in moisture resistance.
  • the resin film of Comparative Example 1 was surface-affected by radicals, resulting in poor moisture resistance.
  • the resin film of Comparative Example 2 did not have a predetermined uneven structure on the surface, neither the low reflectivity nor the moisture resistance satisfied a desired level.
  • the filler (particularly silica particles) contained as an unevenness forming component is unevenly distributed on the surface of the resin film and has a function of suppressing contact between the titanium nitride-containing particles and moisture. ing. In Comparative Example 2, the fact that this filler was not included is considered to reduce the moisture resistance.
  • resin components Examples 1C to 6C were prepared by mixing respective components as shown in Table 6 described later.
  • the compositions of Examples 1C to 6C are the same as those of Example 20 except that the types of dispersion liquid are different.
  • Example 17 In a 200 g container (dispo cup), 20 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 20 g of PGMEA, Megafax RS-72-K (S-1) (30 wt% PGMEA solution) 5 g and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • P-1 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • S-1 Megafax RS-72-K
  • Example 18 Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 5 g, Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) 1.7 g and Megafuck RS-55 (S -2) (100 wt% solution)
  • a resin composition was prepared in the same manner as in Example 17 except that 1 g was used. In addition, it was set as the desired solid content density
  • Example 19 Resin composition as in Example 17 except that 20 g of P-1 (40% PGMEA (propylene glycol monomethyl ether acetate) solution) was replaced with 40 g of P-3 (20% PGMEA (propylene glycol monomethyl ether acetate) solution) was prepared. In addition, it was set as the desired solid content density
  • Example 20 In a 200 g container (dispo cup), 5 g of M-1, 4 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 29 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Mega Fuck 6 g of RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • Mega Fuck 6 g of RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • Example 21 Megafuck RS-72-K (S-1) (30 wt% PGMEA solution) is replaced with Megafuck RS-55 (S-2) (100 wt% solution), and the polymerization initiator is Irgacure OXE02 (manufactured by BASF Japan).
  • a resin composition was prepared in the same manner as in Example 20 except that K-2 was used. In addition, it was set as the desired solid content density
  • 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 used the same composition as Comparative Example 2 described in Table 2 above.
  • Comparative Example 3 A resin composition of Comparative Example 3 was prepared in the same manner as in Example 17 except that the pigment dispersion A was changed to the pigment dispersion C.
  • Example 3B A resin composition of Example 3B was prepared in the same manner as in Example 20 except that the dispersion A was changed to the dispersion B.
  • Example 1C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion E.
  • Example 2C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion F.
  • Example 3C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion G.
  • Example 4C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion H.
  • Example 5C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion I.
  • Example 6C A resin composition was prepared in the same manner as in Example 20 except that the pigment dispersion A was changed to the pigment dispersion J.
  • Each of the resin films of the above-described embodiments has a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom adjacent to each other on a substrate. It was confirmed that it was excellent in low reflectivity and also in moisture resistance.
  • Example 20 (M / B: about 0.9) in which the mass ratio (M / B) of the content (M) of the polymerizable compound to the total content (B) of the dispersion resin and the binder resin is different, respectively. Comparing Example 1B (M / B: 0.37) and Example 2B (M / B: 1.2), Example 20 and Example in which M / B is in the range of 0.45 to 1.5 In 2B, more excellent abrasion resistance was confirmed.
  • Example 2B the total amount of the binder resin and the polymerizable compound was not changed, and the photosensitive resin was similarly prepared except that the amount of the binder resin and the polymerizable compound was adjusted so that M / B was 1.6.
  • a composition was prepared.
  • the same evaluation as in Example 2B was performed, the same result as in Example 2B was obtained except that the result of the rubbing test was B.
  • Example 20 and Example 3B when particles containing silver and iron as metal atoms were used as titanium nitride-containing particles containing metal atoms other than titanium atoms, moisture resistance It was confirmed to be excellent.
  • the resin film of Comparative Example 2 since a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom was not formed, neither the low reflectivity nor the moisture resistance satisfied a desired level.
  • the resin film of Comparative Example 3 also had a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom adjacent to each other on the substrate. Since the nitride-containing particles did not contain metal atoms other than titanium atoms, the moisture resistance was poor. Furthermore, it is clear from the comparison between the comparative example 2 and the comparative example 3 and the example that the resin film of the example significantly improves the low reflectivity and the moisture resistance.
  • Example 1C to 6C good low reflectivity and moisture resistance were obtained as in Example 20. Moreover, although it turned out that the optical density of Example 3C falls a little and optical density falls further in Example 5C and Example 6C, there was no problem practically.
  • the resin film 3 corresponds to a patterned resin film obtained by exposing and developing the resin film 1 or the resin film 2 described above.
  • Example 23 In a 200 g container (dispo cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 21 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Example 24 A resin composition was prepared in the same manner as in Example 23 except that the polymerization initiator K-1 was changed to the polymerization initiator K-2.
  • Example 25 A resin composition was prepared in the same manner as in Example 23 except that the polymerization initiator K-1 was changed to the polymerization initiator K-3.
  • Example 26 In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 16 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 20.7 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution), 0.3 g of LS-2940, and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes. A composition was prepared.
  • Example 27 A resin composition was prepared in the same manner as in Example 23 except that the polymerizable compound M-1 was changed to the polymerizable compound M-2.
  • Example 28 In a 200 g container (dispo cup), 4 g of M-1, 2 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 15 g of PGMEA, 2 g of Highsolve BDM, Irgacure OXE02 (manufactured by BASF Japan) 1 g, 21 g of Thruria 5320 (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred for 30 minutes with a stirrer to prepare a resin composition. .
  • Example 29 A resin composition was prepared in the same manner as in Example 23 except that 1 g of the polymerization initiator K-1 was changed to 0.8 g of the polymerization initiator K-4 and 0.2 g of K-5.
  • Example 30 Resin as in Example 23, except that the polymerization initiator K-1 was changed to the polymerization initiator K-3, and 4 g of the polymerizable compound M-1 was changed to 2 g and M-2 of the polymerizable compounds M-1 A composition was prepared.
  • Example 31 Polymerization initiator K-1 was replaced with polymerization initiator K-3, PGMEA 15 g was replaced with PGMEA 7 g and PGME 8 g, and polymerizable compound M-1 4 g was replaced with polymerizable compounds M-1 2 g and M-3 2 g.
  • a resin composition was prepared in the same manner as in Example 23 except that.
  • Example 32 Example except that Pigment Dispersion A was replaced with Pigment Dispersion D, Polymerization Initiator K-1 was replaced with Polymerization Initiator K-2, and Polymerizable Compound M-1 was replaced with Polymerizable Compound M-2 A resin composition was prepared in the same manner as in No. 23.
  • Example 33 In a 200 g container (dispo cup), 5 g of M-1, 7 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 20 g of PGMEA, 1 g of Irgacure OXE02 (manufactured by BASF Japan), Thruria 5320 21 g of (20% MIBK solution), 2 g of F-1 (1% PGMEA solution) and 44 g of pigment dispersion A were added in this order, and the mixture was stirred for 30 minutes with a stirrer to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Example 34 In a 200 g container (dispo cup), 5 g of M-1, 4 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 27 g of PGMEA, F-1 (1% PGMEA) 2 g of the solution), 6 g of Megafax RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of the pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • P-2 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • K-2 propylene glycol monomethyl ether acetate
  • K-2 propylene glycol monomethyl ether acetate
  • F-1 1% PGMEA
  • S-1 Megafax RS-72-K
  • Example 1D In a 200 g container (disposable cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1.5 g of K-2, 29 g of PGMEA, F-1 (1 % PGMEA solution) 2 g, MegaFac RS-72-K (S-1) (30 wt% PGMEA solution) 0.5 g, and Pigment dispersion A 55 g were added in this order, and stirred with a stirrer for 30 minutes to obtain a resin composition. (Content of S-1 based on the total solid content of the composition: 0.5% by mass) was prepared.
  • Example 2D In a 200 g container (dispo cup), 4 g of M-1, 1 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 22 g of PGMEA, F-1 (1% PGMEA) 2 g of solution), 15 g of Megafax RS-72-K (S-1) (30 wt% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition ( S-1 content based on the total solid content of the composition: 17% by mass).
  • S-1 content based on the total solid content of the composition: 17% by mass
  • Example 35 A resin composition was prepared in the same manner as in Example 34 except that the polymerization initiator K-2 was changed to the polymerization initiator K-3.
  • Example 36 In a 200 g container (dispo cup), 4 g of M-1, 3 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of K-2, 27 g of PGMEA, F-1 (1% PGMEA) 2 g of solution), 1 g of LS-2940, 55 g of pigment dispersion A, and MegaFac RS-72-K (S-1) (30 wt% PGMEA solution): 6 g in this order, and stirred and mixed with a stirrer for 30 minutes Thus, a resin composition was prepared.
  • P-2 50% PGMEA (propylene glycol monomethyl ether acetate) solution
  • K-2 propylene glycol monomethyl ether acetate
  • K-2 propylene glycol monomethyl ether acetate
  • F-1 1% PGMEA
  • S-1 MegaFac RS-72-K
  • Example 37 A resin composition was prepared in the same manner as in Example 34 except that the polymerization initiator K-2 was changed to the polymerization initiator K-1 and the polymerizable compound M-1 was changed to the polymerizable compound M-2.
  • Comparative Example 6 A resin composition of Comparative Example 6 was prepared in the same manner as in Example 34 except that the pigment dispersion A was changed to the pigment dispersion C.
  • (2) Production and evaluation of resin film ⁇ Evaluation of adhesion>
  • Each of the resin compositions of Examples and Comparative Examples was spin-coated on a glass substrate (Corning 1737 [trade name], manufactured by Corning), and then heat-treated (prebaked) for 2 minutes using a hot plate at 100 ° C. It was. In addition, the following evaluation was performed with the film thickness that the OD value at this time was 2.
  • Proxy exposure (exposure apparatus UX3100-SR (manufactured by Ushio Electric Co., Ltd.), exposure amount 1000 mJ / cm 2 ) was performed on the substrate after pre-baking through a predetermined mask (150 ⁇ m ⁇ type island pattern). Thereafter, using a TMAH (tetramethylammonium hydroxide) 2.38 wt% developer, the obtained substrate was subjected to paddle development for 10 to 60 seconds (the time required for resolution when pattern exposure was performed). . After washing with water and drying, the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to produce a substrate having a pattern.
  • TMAH tetramethylammonium hydroxide
  • the obtained island pattern was subjected to a tape pull test in accordance with JIS-K5400.
  • the case where the entire pattern was left was A
  • the case where a part of the pattern was peeled off was B
  • the case where the whole pattern was peeled was C.
  • the results are shown in Tables 7 and 8.
  • the obtained substrate was subjected to paddle development for 10 to 60 seconds (the time required for resolution when pattern exposure was performed). .
  • the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to produce a substrate having a pattern.
  • the obtained pattern was observed with an optical microscope, and the minimum line width ( ⁇ m) where the line and space pattern was not peeled was taken as the resolution value. For example, when a line and space of 100 ⁇ m is resolved and peeling does not occur, it is determined that the resolution is 100 ⁇ m.
  • the surface roughness (arithmetic mean Ra) of each of the resin films of Examples 23 to 33 was 100 to 2000 mm before the exposure process.
  • the method for measuring the surface roughness (arithmetic mean Ra) is as described above.
  • a pigment layer containing a black pigment and a surface layer containing a compound containing at least one of a fluorine atom and a silicon atom were formed adjacent to each other on the substrate. ing.
  • Example 33 the reflectance was 2% (the reflectance at 400 nm), the moisture resistance was “A”, and the adhesion was “A”.
  • Comparative Example 4 it is presumed that the addition of the filler also causes unevenness on the side wall of the pattern, which also reduces the resolution. Further, by comparing Examples 34 to 37, it was found that the resolution can be further improved by using K-2 or K-3 as the polymerization initiator. Further, by comparing Example 34 and Examples 1D and 2D with a resin having at least one of fluorine atoms and silicon atoms in an amount of 1 to 15% by mass based on the total solid content of the composition, moisture resistance and resolution can be achieved. It was confirmed that the properties can be compatible with each other.
  • Example 38 After spin-coating the resin composition of Example 34 (pigment concentration 50%) on a glass substrate (Corning 1737 [trade name], manufactured by Corning), heat treatment (prebaking) for 2 minutes using a hot plate at 100 ° C. Went. Thereafter, an exposure process (exposure apparatus UX3100-SR (manufactured by Ushio Inc.), exposure amount of 1000 mJ / cm 2 ) was performed on the coating film obtained above through a predetermined mask. Thereafter, the substrate was heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to prepare a pigment layer Y1. Application was performed with a film thickness at which the OD value was 1.0.
  • exposure apparatus UX3100-SR manufactured by Ushio Inc.
  • Example 33 the resin composition of Example 33 (pigment concentration 40%) was spin-coated on the obtained pigment layer Y1, and then heat-treated (prebaked) for 2 minutes using a 100 ° C. hot plate. Thereafter, an exposure process (exposure apparatus UX3100-SR (manufactured by Ushio Inc.), exposure amount of 1000 mJ / cm 2 ) was performed on the coating film obtained above through a predetermined mask. Thereafter, the substrate was subjected to a heat treatment (post-bake) for 300 seconds using a 220 ° C. hot plate to form the pigment layer Y2, and a resin film having the pigment layer Y1 and the pigment layer Y2 adjacent to each other was obtained. . In addition, it apply
  • the OD value is a value obtained by the following method.
  • a pigment layer having a desired film thickness is formed on an alkali-free glass having a thickness of 0.7 mm, and the intensities of incident light and transmitted light are measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.). Calculated.
  • OD value log 10 (I 0 / I) I 0 : Incident light intensity I: Transmitted light intensity
  • Example 39 In accordance with the method for producing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced.
  • the pigment layer Y1 was applied and formed with a film thickness such that the OD value was 0.5, and then the pigment layer Y2 was applied thereon so that the OD of the pigment layer Y2 alone was 1.0. Formed.
  • light of 400 to 700 nm was incident on the resin film at an incident angle of 5 ° from the substrate surface side opposite to that in Example 38, and the reflectance was measured. At this time, the reflectance at 400 nm was 2.5%.
  • a high-temperature and high-humidity test for 750 hours was performed on the substrate with the resin film using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.) under the conditions of a temperature of 85 ° C. and a humidity of 95%.
  • EHS-221 manufactured by Espec Corp.
  • the change rate ⁇ T (%) was less than 0.5%.
  • Example 40 In a 200 g container (dispo cup), 6 g of M-1, 6 g of P-2 (40% PGMEA (propylene glycol monomethyl ether acetate) solution), 1 g of Irgacure OXE02 (manufactured by BASF Japan), 30 g of PGMEA, F-1 2 g of (1% PGMEA solution) and 55 g of pigment dispersion A were added in this order, and the mixture was stirred with a stirrer for 30 minutes to prepare a resin composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • Irgacure OXE02 manufactured by BASF Japan
  • the reflectance at 400 nm was 4.0%.
  • a high-temperature and high-humidity test for 750 hours was performed on this resin film-coated substrate under conditions of a temperature of 85 ° C. and a humidity of 95% using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.).
  • the change rate ⁇ T (%) was less than 1%.
  • Example 41 In accordance with the method for producing a substrate with a resin film of Example 38, a substrate with a resin film having a pigment layer Y1 and a pigment layer Y2 adjacent to each other was produced.
  • the resin composition prepared in Example 40 was used, and a coating film was laminated on a glass substrate so as to be OD0.5 (pigment layer Y1) and OD1.0 (pigment layer Y2) in this order.
  • 400 to 700 nm of light was incident on the resin film from the substrate surface side at an incident angle of 5 °, and the reflectance was measured. At this time, the reflectance at 400 nm was 4.0.

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Abstract

La présente invention concerne : une composition de résine apte à former un film de résine qui présente de faibles propriétés de réflexion et une grande résistance à l'humidité ; un film de résine qui présente de faibles propriétés de réflexion et une grande résistance à l'humidité ; un filtre coloré ; un film de protection contre la lumière ; un élément d'imagerie à semi-conducteur ; et un dispositif d'affichage d'image. La composition de résine comprend des particules contenant du nitrure de titane contenant au moins un type d'atome métallique autre que l'atome de titane, une résine liante et une charge et/ou un composé contenant un atome de fluor et/ou un atome de silicium.
PCT/JP2017/003918 2016-02-29 2017-02-03 Composition de résine, film de résine, filtre coloré, film de protection contre la lumière, dispositif d'imagerie à semi-conducteur, et dispositif d'affichage d'image Ceased WO2017150069A1 (fr)

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