WO2017203979A1 - Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, et procédé de production de film durci - Google Patents

Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, et procédé de production de film durci Download PDF

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WO2017203979A1
WO2017203979A1 PCT/JP2017/017673 JP2017017673W WO2017203979A1 WO 2017203979 A1 WO2017203979 A1 WO 2017203979A1 JP 2017017673 W JP2017017673 W JP 2017017673W WO 2017203979 A1 WO2017203979 A1 WO 2017203979A1
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group
curable composition
compound
cured film
mass
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PCT/JP2017/017673
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English (en)
Japanese (ja)
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裕行 森下
浜田　大輔
明夫 水野
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富士フイルム株式会社
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Priority to JP2018519177A priority Critical patent/JP6896718B2/ja
Priority to KR1020187033076A priority patent/KR102208741B1/ko
Publication of WO2017203979A1 publication Critical patent/WO2017203979A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/17—Amines; Quaternary ammonium 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a curable composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, and a method for producing the cured film.
  • a color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise and improving image quality.
  • portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units.
  • Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.
  • Patent Document 1 includes “a black colorant having an average particle diameter of 40 nm or less and a resin component that can form a coating film disposed on the periphery of an effective pixel region (imaging unit) of a solid-state image sensor.
  • the present inventors examined a light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1, and although there is excellent light-shielding property, there is room for further improvement in the obtained pattern shape. Revealed that there is.
  • the light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1 may have a film thickness at the end that is smaller than the film thickness at the center. Clarified that there is.
  • this invention makes it a subject to provide the curable composition which can obtain the cured film which has the outstanding pattern shape, maintaining the outstanding light-shielding property.
  • the present invention also provides a cured film obtained by using the curable composition, a color filter, a light-shielding film, a solid-state imaging device, an image display device, and a method for producing the cured film, including the cured film. It is also an issue to do.
  • the present inventors diligently studied to achieve the above problems. As a result, it is a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, and a cured film obtained by curing the curable composition is visible.
  • the present inventors have found that a curable composition having an optical density per film thickness of 1.5 ⁇ m in the optical region of 4.0 or more can solve the above-mentioned problems, and completed the present invention. That is, it has been found that the above-described problem can be achieved by the following configuration.
  • a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, wherein a cured film obtained by curing the curable composition is visible A curable composition having an optical density of 4.0 or more per 1.5 ⁇ m film thickness in the optical region.
  • the inorganic pigment is at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin-containing metal pigments, and silver and tin-containing metal pigments.
  • An image display device comprising the cured film according to [18].
  • the method for producing a cured film according to [23], wherein the exposure amount of the curable composition layer in the exposure step is 200 mJ / cm 2 or more.
  • the curable composition layer forming step includes a coating step in which the curable composition is directly coated on the support to form a curable composition layer on the support.
  • the manufacturing method of the cured film as described in any one of. [26] The method according to any one of [23] to [25], further comprising: a developing step for developing the exposed curable composition layer; and a washing step for washing the developed curable composition layer. The manufacturing method of the cured film as described in any one of.
  • the curable composition which can obtain the cured film which has the outstanding pattern shape, maintaining the outstanding light-shielding property can be provided.
  • a cured film obtained by using the curable composition, a color filter, a light shielding film, a solid-state imaging device, an image display device, and a method for producing the cured film, including the cured film. You can also
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent.
  • the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
  • active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by excimer laser, extreme ultraviolet lithography (EUV), X-ray, and Means an electron beam.
  • light means actinic rays and radiation.
  • exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp and far ultraviolet rays such as an excimer laser, X-rays and EUV light, but also an electron beam and an ion beam, etc. Also includes drawing with particle beams.
  • exposure in this specification, “(meth) acrylate” represents an acrylate and a methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • monomer and “monomer” are synonymous.
  • a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group that participates in a polymerization reaction.
  • the curable composition contains a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, and is a film in the visible light region of a cured film obtained by curing the curable composition.
  • the optical density per 1.5 ⁇ m thickness is 4.0 or more.
  • a cured film having an excellent pattern shape can be obtained while maintaining excellent light shielding properties (hereinafter also referred to as “effect of the present invention”).
  • effect of the present invention Although the mechanism by which the effect of the present invention is obtained by the curable composition is not necessarily clear, the present inventors presume as follows. In addition, the mechanism by which the said curable composition exhibits the effect of this invention is not limited by the following assumptions.
  • a conventionally known curable composition containing a colorant such as carbon black and not containing a polyfunctional thiol compound is widely used because a high light-shielding density can be obtained over a wide wavelength region.
  • the optical density (also referred to as OD: optical density) of the curable composition layer Gradually increases from the long wavelength side to the short wavelength side, and the optical density in the short wavelength region is extremely high compared to the long wavelength side. Therefore, for example, when pattern exposure of the curable composition layer with light in the ultraviolet region such as g-line, h-line, and i-line, the light does not reach the inside of the curable composition layer, exposure becomes insufficient, The pattern shape sometimes deteriorated.
  • FIGS. 1 to 3 are cross-sectional views schematically showing a production process of a cured film using a curable composition containing no polyfunctional thiol for each process.
  • a curable composition layer 102 is formed on a support 101 using a curable composition.
  • the curable composition layer 102 is exposed through the opening of the photomask 103 (in FIG. 1, arrows indicate the direction of light irradiation, and the line AB represents the end of the opening of the photomask.
  • the curable composition layer 102 after the exposure is developed to form a patterned cured film 201.
  • the exposure in the above procedure since the optical density of the curable composition layer 102 is high, it is difficult for light to reach the inside of the curable composition layer 102 at the time of exposure, and under the curable composition layer 102, the exposure is insufficient. It becomes. Then, when it develops, a curable composition will elute in the part in which the exposure in the curable composition layer 102 is inadequate (FIG. 2). In such a state, when a post-baking process for heating the cured film 201 is performed, a problem called “thermal sag” occurs in a portion eluted during development. That is, it is presumed that the film thickness is reduced at the end of the post-baked cured film 301 obtained as compared with the central part (FIG. 3).
  • FIG. 4 to 6 are cross-sectional views schematically showing a process for producing a cured film using the curable composition of the present invention for each process.
  • a curable composition layer 401 is formed on a support 101 using the curable composition of the present invention.
  • the curable composition layer 401 is exposed through the opening of the photomask 103.
  • the curable composition layer 401 contains a polyfunctional thiol compound, it is presumed that the inside of the curable composition layer 401 is sufficiently cured for the following reason.
  • a radical polymerization reaction is initiated by the photopolymerization initiator.
  • radicals generated by the photopolymerization initiator may react with oxygen in the curable composition layer 401 to generate peroxy radicals. Since the peroxy radical does not have an action of proceeding the polymerization reaction, the polymerization reaction stops there.
  • the thiol group in the polyfunctional thiol compound donates hydrogen to the peroxy radical, thereby generating a thiyl radical that is less susceptible to polymerization deactivation by oxygen. Then, the polymerization reaction proceeds. Therefore, it is estimated that the curable composition containing the polyfunctional thiol compound is easily cured to the inside of the curable composition layer 401.
  • the cured film obtained by curing the curable composition has an optical density of 4.0 or more per 1.5 ⁇ m thickness in the visible light region, and the curable composition layer 401 has high light shielding properties.
  • the light irradiated to the curable composition layer 401 through the opening of the photomask 103 is diffracted at the opening of the photomask 103 and is also irradiated to the mask light shielding portion 402 outside the line AB. (This is called "leakage light").
  • the light-shielding property of the curable composition layer is low, the light is exposed to the curable composition layer of the mask light-shielding part due to leakage light, leading to deterioration of the pattern shape.
  • the curable composition layer 401 has a high light shielding property, the leakage light is absorbed without exposing the mask light shielding portion 402 (FIG. 4). Accordingly, when the cured film after the exposure is developed, the cured film 501 having an excellent pattern shape is obtained because the light is sufficiently cured to the inside and the light diffracted by the opening of the photomask is absorbed (see FIG. 5). Since the cured film 501 is less likely to cause “thermal sag” even after the post-baking process, the difference in film thickness between the central portion and the end portion of the cured film 601 after the post-baking is reduced, and an excellent pattern shape is obtained. (Fig. 6).
  • the cured film obtained by curing the curable composition has an optical density of 4.0 or more per 1.5 ⁇ m film thickness in the visible light region.
  • the optical density is more preferably 4.1 or more, and even more preferably 4.3 or more, in that a curable composition having the better effect of the present invention can be obtained.
  • the upper limit is not particularly limited, but is generally preferably 8.0 or less.
  • the optical density means the optical density measured by the method described in the examples, and the visible light region means light having a wavelength of 400 to 800 nm. Accordingly, the optical density of 4.0 or more per 1.5 ⁇ m in the visible light region is intended to mean 4.0 or more per 1.5 ⁇ m of film thickness in the entire wavelength range of 400 to 800 nm.
  • the curable composition contains a colorant.
  • the colorant is at least one selected from the group consisting of pigments and dyes.
  • the content of the colorant is preferably 55% by mass or more, more preferably 56% by mass or more, and still more preferably 58% by mass or more based on the total solid content of the curable composition. .
  • the content of the colorant is 55% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
  • the upper limit of content of a coloring agent is not restrict
  • the content of the colorant is not more than the upper limit value, the curable composition has more excellent coatability.
  • the pigment is not particularly limited, and a known inorganic pigment and / or organic pigment can be used. Especially, an inorganic pigment is preferable at the point from which the curable composition which has the more excellent effect of this invention is obtained.
  • the inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
  • examples of inorganic pigments include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (one zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium zirconium blue, Examples include chrome tin pink, ceramic red, and salmon pink.
  • the black inorganic pigment includes a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrogenous substances.
  • the inorganic pigment carbon black, titanium black, metal pigment, etc. (hereinafter referred to as “black pigment”) in that a curable composition capable of forming a cured film having at least a high optical density is obtained.
  • black pigment examples include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Product or metal nitrogen product.
  • the inorganic pigment contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin-containing metal pigments, and silver and tin-containing metal pigments. It is preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride.
  • Carbon black can also be used as the inorganic pigment. Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include inorganic pigments such as CI Pigment Black 7, but are not limited thereto.
  • a pigment having infrared absorptivity other than the pigment described as a black pigment can also be used.
  • a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region.
  • a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of a photopolymerization initiator related to curing efficiency by exposure and transparency of visible light region.
  • Two or more of these pigments may be used in combination, or may be used in combination with a dye described later.
  • a pigment having black or infrared light-shielding properties such as chromatic colors such as red, green, yellow, orange, purple, and blue
  • chromatic colors such as red, green, yellow, orange, purple, and blue
  • the aspect which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment. Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.
  • the black pigment preferably contains titanium black and / or niobium oxynitride.
  • Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide, titanium oxynitride, titanium nitride, and the like.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible. Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small. The same applies to niobium oxynitride. Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.
  • the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM).
  • TEM Transmission Electron Microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length) The shortest length connecting two straight lines perpendicularly) was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the particle diameter.
  • the particle diameter of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
  • the specific surface area of titanium black and niobium oxynitride is not particularly limited. However, since the water repellency after surface treatment of titanium black and niobium oxynitride with a water repellent becomes a predetermined performance, BET (Brunauer, Emmett, Teller) The value measured by the method is preferably 5 m 2 / g or more and 150 m 2 / g or less, more preferably 20 m 2 / g or more and 120 m 2 / g or less.
  • titanium black examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.
  • Titanium oxynitride, titanium nitride, or niobium oxynitride is preferably used as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is more preferable because the resulting cured film has better moisture resistance. preferable. This is presumably because these colorants are hydrophobic.
  • titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • the following means can be used.
  • titanium black particles and silica particles are dispersed by using a disperser to obtain a dispersion, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000 ° C.) to thereby obtain titanium black particles. It is possible to obtain a to-be-dispersed body containing Si and Ti as a main component.
  • the reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
  • titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
  • Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
  • a dispersing agent may be used for the dispersion of titanium oxide and silica particles.
  • the dispersant include those described in the section of the dispersant described later.
  • the dispersion may be performed in a solvent.
  • the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. can do.
  • Curing including this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion including titanium black and Si atoms to a suitable range (for example, 0.05 or more).
  • a suitable range for example, 0.05 or more.
  • the residue includes components derived from a curable composition such as titanium black particles and a resin component. The reason why the residue is reduced is not yet clear, but the above-described dispersion tends to have a small particle diameter (for example, a particle diameter of 30 nm or less), and further contains Si atoms of the dispersion.
  • Titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light, so that the above-described dispersion material containing titanium black and Si atoms (preferably Si / Ti is 0 in terms of mass).
  • a cured film formed using a .05 or more) exhibits excellent light shielding properties.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ). Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the curable composition Can be determined by the method (2) described in paragraph 0035 of JP2013-249417A.
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc.
  • ⁇ atoms may be used in combination with titanium black, if desired, for the purpose of adjusting the light shielding property and the like, as long as the effects of the present invention are not impaired.
  • materials used for introducing Si atoms into the dispersion will be described.
  • a Si-containing material such as silica may be used. Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
  • the particle diameter of the silica particles is smaller than the film thickness when the cured film is formed, the light-shielding property is more excellent, so it is preferable to use fine particle type silica.
  • the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • the curable composition can use a tungsten compound and / or a metal boride as a pigment.
  • Tungsten compounds and metal borides have high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-blocking properties (shielding properties) for infrared rays) and absorption for visible light. It is a low infrared shielding material.
  • the curable composition of this invention can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
  • Tungsten compounds and metal borides have low absorption even for light shorter than the visible range used for exposure of high pressure mercury lamps, KrF, ArF and the like used for image formation. For this reason, by combining with the polymeric compound, alkali-soluble resin, and photoinitiator which are mentioned later, while being able to obtain the outstanding pattern, a development residue can be suppressed more in pattern formation.
  • tungsten compound examples include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
  • composition formula) (I) M x W y O z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001 ⁇ x / y ⁇ 1.1 2.2 ⁇ z / y ⁇ 3.0
  • alkali metal for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.
  • M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.
  • infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
  • z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
  • tungsten oxide compound represented by the general formula (I) examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
  • the tungsten compound is preferably fine particles.
  • the average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less.
  • the average primary particle size is preferably as small as possible.
  • the average primary particle size of the tungsten fine particles is usually 1 nm or more.
  • Two or more tungsten compounds can be used.
  • Tungsten compounds are commercially available.
  • the tungsten oxide compound is, for example, a tungsten oxide compound
  • the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205).
  • the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
  • lanthanum boride LaB 6
  • PrB 6 praseodymium boride
  • NdB 6 cerium boride
  • CeB 6 cerium boride
  • YB 6 yttrium boride
  • titanium boride TiB 2
  • zirconium boride ZrB 2
  • hafnium boride HfB 2
  • vanadium boride VB 2
  • tantalum boride TaB 2
  • CrB, CrB 2 chromium boride
  • molybdenum boride One or more of MoB 2 , Mo 2 B 5 , MoB), tungsten boride (W 2 B 5 ) and the like can be mentioned, and lanthanum boride (LaB 6 ) is preferable.
  • the metal boride is preferably fine particles.
  • the average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle diameter is in such a range, the metal boride fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride fine particles is usually 1 nm or more.
  • Two or more metal borides can be used.
  • the metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.
  • titanium nitride-containing particles As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used.
  • a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
  • the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
  • the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable.
  • RF radio frequency
  • titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles.
  • the thermal plasma method is not limited to the above.
  • the method for producing titanium nitride-containing particles is not particularly limited, but the production methods described in paragraphs ⁇ 0037> to ⁇ 0089> of International Publication No. 2010/147098 can be referred to.
  • the Ag powder of International Publication No. 2010/147098 instead of the Ag powder of International Publication No. 2010/147098, using a component containing Fe and / or a component containing Si, which will be described later, and a mixture of this and a titanium powder material (titanium particles) as a raw material
  • titanium nitride-containing particles contained in the curable composition of the present invention can be produced.
  • the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably of high purity.
  • the titanium powder material is not particularly limited, but a titanium element having a purity of 99.99% or more is preferable, and a material having 99.999% or more is more preferably used.
  • the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms.
  • examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
  • the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material.
  • the titanium powder material contains Si atoms the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material.
  • the content is more preferably from 0.15% by mass, and even more preferably from 0.02 to 0.1% by mass.
  • the patterning property of the cured film is further improved.
  • the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is further stabilized.
  • the water content in the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably less than 1% by mass and less than 0.1% by mass with respect to the total mass of the titanium powder material. It is more preferable that it is not substantially contained.
  • the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source (details will be described later) is 42.6. It becomes easy to adjust to a range of more than 4 ° to 43.5 °.
  • the method for causing the titanium nitride-containing particles to contain Fe atoms is not particularly limited.
  • Fe atoms are introduced in the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles.
  • the method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel that is made of a material containing Fe atoms such as stainless steel (SUS), or a press machine for crushing titanium and By using a material containing Fe atoms as the material of the pulverizer, Fe atoms can be attached to the surface of the titanium particles.
  • SUS stainless steel
  • titanium nitride-containing particles in addition to the titanium particles as raw materials, components such as Fe particles and Fe oxide are added, and these are nitrided by the thermal plasma method.
  • the titanium nitride-containing particles can contain Fe atoms.
  • Fe atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, and sulfides. And oxysulfide may be included in any form.
  • the Fe atom contained in the titanium nitride-containing particle may exist as an impurity at a position between crystal lattices, or may exist as an impurity in an amorphous state at a crystal grain boundary.
  • the present inventors have found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning property and the corrosion resistance of the electrode.
  • the Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particles is considered to adhere to the electrode and the substrate through the Fe atoms.
  • the patterning property of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more.
  • the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to cause corrosion of the electrode. Therefore, it is estimated that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
  • the content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable.
  • the content of Fe atoms is more than 0.001% by mass, the patterning property of the cured film is further improved.
  • the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is further improved (the cured film can be inhibited from corroding the electrode).
  • the content of Fe atoms in the titanium nitride-containing particles is within the above range, excellent patterning properties of the cured film and anticorrosion properties of the electrodes can be obtained.
  • the content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.
  • the titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more.
  • the reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
  • the content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15 The mass is more preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved.
  • the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is further stabilized.
  • the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. It is done.
  • the content of Si atoms in the titanium nitride-containing particles can be measured by the same method as that for Fe atoms.
  • the method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited.
  • Si atoms are introduced at the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles.
  • the method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or Si atom is used as a material for a press machine and a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles.
  • titanium nitride-containing particles in addition to the titanium particles that are raw materials, components such as Si particles and Si oxide are added, and these are nitrided by the thermal plasma method.
  • the titanium nitride-containing particles can contain Si atoms.
  • Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form.
  • Si atoms contained in the titanium nitride-containing particles may be present as impurities at the position between the crystal lattices, or may be present as impurities in the amorphous state at the crystal grain boundaries.
  • the content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and preferably 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 70% by mass.
  • the content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopy.
  • the content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass and preferably 5 to 50% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass.
  • the nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
  • Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during the synthesis and when the particle size is small. , A part of oxygen atoms may be contained.
  • the content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is ⁇ 30% by mass.
  • the oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.
  • 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 (Brunauer, Emmett, Teller) method.
  • the titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
  • Composite fine particles refer 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
  • “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.
  • the metal fine particles are not particularly limited.
  • at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these More preferably, it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
  • the content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the titanium nitride-containing particles. Is more preferable.
  • the titanium nitride-containing particles preferably have a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ ray is used as an X-ray source, more than 42.6 ° and 43.5 ° or less.
  • a cured film (for example, a black matrix) obtained using a curable composition containing titanium nitride-containing particles having such characteristics can achieve a high OD value.
  • TiN has a peak derived from the (200) plane as a strongest peak
  • TiO has a (200 )
  • the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the stability of the particle over time. From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, it is more preferably 42.7 ° or more and less than 43.4 °.
  • the crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
  • the crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm.
  • the transmitted light of the cured film exhibits a blue to blue purple color having a peak wavelength of 475 nm or less, and has high light-shielding properties.
  • a black matrix having both ultraviolet sensitivity can be obtained.
  • the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the volume of the particle is reduced, providing a good balance, and the titanium nitride-containing particles have better heat resistance and / or durability. It becomes.
  • metal nitride-containing particles containing atom A As the inorganic pigment, metal nitride-containing particles which are metal nitride-containing particles and contain a predetermined atom A in the metal nitride-containing particles can also be used.
  • the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and the effect of the present invention in which the curable composition is more excellent.
  • Nb or V is more preferable in that
  • the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.
  • the metal nitride-containing particles contain the atom A the content is not particularly limited, but the content of the atoms A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.
  • the method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.
  • a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
  • the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity.
  • a specific method for producing metal nitride-containing particles by the thermal plasma method for example, a method using a metal fine particle production apparatus (an apparatus similar to a “black composite fine particle production apparatus” described later) can be mentioned.
  • the metal fine particle manufacturing apparatus includes, for example, a plasma torch for generating thermal plasma, a material supply device for supplying metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone for classifying the generated metal fine particles, and metal fine particles It is comprised by the collection
  • the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 ⁇ m containing a metal element.
  • the method for producing metal nitride-containing particles using a metal fine particle production apparatus includes the following steps in that the yield of metal nitride-containing particles having the following predetermined average primary particle diameter is increased. preferable.
  • Step A A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step B A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • Step C Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • Step D A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
  • Step E A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • Step F Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
  • grains may contain the following process G depending on necessity after the said process C and / or the process F.
  • FIG. Step G A step of classifying the obtained particles.
  • Step A2 A step of mixing atoms A into a metal raw material powder containing a transition metal. Further, before the step A2, the following steps A3-1 to A3-3 may be included.
  • Step A3-1 A step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step A3-2 A step of supplying raw material powder containing atoms A to the thermal plasma flame in the plasma torch and evaporating the raw material powder to obtain gas phase atoms A.
  • Step A3-3 A step of cooling the gas phase atoms A to obtain atomized atoms A. Note that a step G may be further included after the step A3-3.
  • the atomized atom A means a particle containing the atom A and having a primary particle diameter of 20 nm to 40 ⁇ m.
  • grains contains the following process H further after the process F (when the process G is included, after the process G after the process F).
  • Step H A step of exposing the metal nitride-containing particles obtained in Step F (or Step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
  • grains may contain the process G further after the process H if desired.
  • Step A is a step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • the generation method of the thermal plasma flame is not particularly limited, and examples thereof include a direct current arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, and the like. preferable.
  • the method of generating a thermal plasma flame by the high frequency plasma method is not particularly limited. For example, a plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the high frequency oscillation coil. The method of obtaining a thermal plasma flame by doing is mentioned.
  • Examples of the plasma gas in the process A include an inert gas that does not contain nitrogen gas.
  • Examples of the inert gas not containing nitrogen gas include argon gas and hydrogen gas.
  • the inert gas which does not contain nitrogen gas may be used individually by 1 type, or may use 2 or more types together.
  • Step A2 is a step of mixing atoms A into a metal raw material powder containing a transition metal.
  • the method for mixing the raw metal powder and the atom A is not particularly limited, and a known method can be used.
  • the material supply device for supplying the metal raw material powder into the plasma torch may contain a mixing and dispersing function.
  • the material supply apparatus described in Paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, the contents of which are incorporated herein.
  • the method for producing metal nitride-containing particles may further include the following steps A3-1 to A3-3 before step A2.
  • Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in the plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • the method for supplying the metal raw material powder to the thermal plasma flame in the plasma torch is not particularly limited, but the obtained gas phase raw material metal may be sprayed using a carrier gas in a more uniform state. preferable.
  • the carrier gas it is preferable to use an inert gas that does not contain nitrogen gas.
  • the aspect of the inert gas not containing nitrogen gas is as described above.
  • the method for producing metal nitride-containing particles includes the above step A2, the metal raw material powder is maintained in a uniform dispersed state until the metal raw material powder is supplied into the plasma torch. Is preferred.
  • Step C is a step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • the cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function.
  • metal fine particles having a desired particle size described below can be generated.
  • the generated metal fine particles are recovered by, for example, a recovery unit.
  • the atmosphere in the chamber is preferably an inert gas that does not contain nitrogen gas.
  • the aspect of the inert gas not containing nitrogen gas is as described above.
  • Step D is a step of generating a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
  • the inert gas containing nitrogen include nitrogen gas and nitrogen gas containing an inert gas.
  • the inert gas include argon gas and hydrogen gas.
  • the nitrogen gas containing the inert gas is not particularly limited, but the nitrogen gas content is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.
  • Step E is a step of supplying metal fine particles containing a transition metal to the thermal plasma flame in the plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • the method for supplying the metal fine particles to the thermal plasma flame in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen.
  • the aspect of the inert gas containing nitrogen is as described above.
  • step E the raw material metal that has become fine metal particles in steps A to C is supplied to the thermal plasma flame, so that a vapor phase raw metal is easily obtained, and the state of the vapor phase raw metal is likely to be more uniform.
  • Step F is a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles containing a transition metal nitride.
  • the suitable aspect of the cooling method is as above-mentioned, as the atmosphere in a chamber, the inert gas containing nitrogen gas is preferable.
  • the suitable aspect of the inert gas containing nitrogen gas is as above-mentioned.
  • Step G is a step of classifying the obtained metal fine particles and / or metal nitride-containing particles.
  • the classification method is not particularly limited, and for example, a cyclone can be used.
  • the cyclone has a container on a cone, and generates a swirling flow in the container and has a function of classifying particles using centrifugal force.
  • the classification is preferably performed in an inert gas atmosphere. The aspect of the inert gas is as described above.
  • Process H is a process in which the metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. Through this step, the metal nitride content in the metal nitride-containing particles can be increased.
  • the method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited.
  • the metal nitride-containing particles are introduced into a thermostatic bath filled with a gas mixed with water vapor and nitrogen gas.
  • There may be mentioned a method of standing or stirring for a predetermined time There may be mentioned a method of standing or stirring for a predetermined time, and it is more preferred that the metal nitride-containing particles are allowed to stand for stabilization of the surface and crystal boundaries.
  • the mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% in the atmosphere.
  • the time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that
  • steps A3-1 to A3-3 an inert gas not containing nitrogen gas is supplied as a plasma gas in the plasma torch to generate a thermal plasma flame (A3-1), and a thermal plasma flame in the plasma torch is used.
  • each process is the above-mentioned process A, process B (instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A), and process C (substituting metal fine particles containing a transition metal)
  • process A instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A
  • process C substituted metal fine particles containing a transition metal
  • Step A A step of supplying an inert gas not containing nitrogen gas as a plasma gas in the plasma torch to generate a thermal plasma flame.
  • Step B A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • Step C A step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • Step G A step of classifying the obtained particles.
  • Step A3-1 A step of supplying an inert gas containing no nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma flame.
  • Step A3-2 Atom A is added to the thermal plasma flame in the plasma torch.
  • Step A3-3 Cooling vapor phase atoms A to obtain atomized atom A G: A step of classifying the obtained particles.
  • Step A2 A step of mixing atoms A (in this case, atomized atoms A) with a metal raw material powder (in this case, metal fine particles) containing a transition metal.
  • Step D A step of supplying an inert gas containing nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma flame.
  • Step E A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • Step F Step of cooling the gas phase raw material metal to obtain metal nitride-containing particles.
  • Step G A step of classifying the obtained particles.
  • Step H A step of exposing the metal nitride-containing particles obtained in Step G to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
  • the metal raw material powder and the metal nitride that can remove impurities contained in the raw material particles and have a desired average primary particle diameter Containing particles can be produced.
  • the reason is that the transition metal and / or atom A is ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are micronized to reflect their melting points. It is guessed. At this time, the atomization with a low melting point is fast, and the atomization with a high melting point is slow.
  • the fine particles (steps B and C and steps A3-2 and A3-3) once plasma-treated are likely to become a single component (single crystal).
  • the impurity particles can be removed depending on the density and / or particle size difference between the transition metal particles and / or the atom A particles and the impurity particles. it can.
  • the classification can be performed, for example, by using a cyclone or the like and appropriately setting the classification conditions.
  • metal raw material powder containing a transition metal that can be used in the above step B (hereinafter simply referred to as "metal raw material powder") and raw material powder containing atom A (hereinafter simply referred to as " Although it does not restrict
  • the content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The same applies to the content of atom A in the raw material powder.
  • Metal raw material powder and / or raw material powder may contain atoms other than the desired transition metal and / or atom A as impurities.
  • impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel, and silver.
  • a metal element etc. are mentioned as an impurity contained in raw material powder.
  • the method for producing metal nitride-containing particles may further include the following step A0 before step B (when step A2 is included, before step A2).
  • Step A0 A step of removing impurities from the metal raw material powder and / or the raw material powder.
  • the metal raw material powder and / or the method for removing impurities from the raw material powder is not particularly limited. A method similar to this can be used for other metal raw material powders and / or raw material powders.
  • the metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having metal nitride-containing particles and a coating layer formed using an inorganic compound that coats the metal nitride-containing particles.
  • a curable composition containing metal nitride-containing particles coated with an inorganic compound has better dispersion stability.
  • the inorganic compound is not particularly limited, and oxides such as SiO 2 , ZrO 2 , TiO 2 , GeO 2 , Al 2 O 3 , Y 2 O 3 , and P 2 O 5 , aluminum hydroxide, and zirconium hydroxide And the like.
  • aluminum hydroxide is preferable in that it can easily form a thinner film and can easily form a film having a higher coverage.
  • the low refractive index film is preferably silicon oxide
  • the high refractive index film is preferably zirconium hydroxide.
  • the method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but the method for producing the metal nitride-containing particles preferably includes the following inorganic compound coating step.
  • An inorganic compound coating process is a process which coat
  • the metal nitride-containing particles are mixed with water to prepare a slurry.
  • a water-soluble compound for example, sodium silicate
  • Alkaline ions are removed by decantation and / or ion exchange resin.
  • the slurry is dried to obtain metal nitride-containing particles coated with an oxide.
  • the above metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry.
  • an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is generated in the slurry, and the slurry is heated at a high temperature. Bake. When the slurry is fired at a high temperature, a sol-gel reaction proceeds, and metal nitride-containing particles coated with an oxide are obtained.
  • a slurry containing an ionic liquid is prepared using urea and aluminum chloride in the presence of metal nitride-containing particles.
  • the metal nitride-containing particles are taken out from the slurry and dried, and then the metal nitride-containing particles are fired to obtain metal nitride-containing particles coated with a hydroxide containing aluminum hydroxide.
  • Organic pigment examples include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24. , 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 Etc.
  • CI Color Index
  • a pigment may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used.
  • pyrazole azo compounds When classified by chemical structure, 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.
  • a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.
  • the colorant may further contain an infrared absorber.
  • the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, wavelength 650 to 1,300 nm).
  • the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
  • Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
  • phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound
  • the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used.
  • the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
  • the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
  • the infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3.
  • General formula 1 In General Formula 1, A 1 and A 2 each independently represents an aryl group, a heteroaryl group, or a group represented by General Formula 1-A below.
  • Formula 1-A In the general formula 1-A, Z 1A represents a nonmetallic atomic group forming a nitrogen-containing heterocycle, R 2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and a wavy line represents a link Represents a hand.
  • R 1a and R 1b each independently represents an alkyl group, an aryl group, or a heteroaryl group
  • R 2 to R 5 each independently represents a hydrogen atom or a substituent
  • R 2 and R 3 , R 4 and R 5 may be bonded to each other to form a ring
  • R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR A R B , or a metal atom
  • R A and R B each independently represent a hydrogen atom or a substituent.
  • R 6 may be covalently bonded or coordinated to R 1a or R 3
  • R 7 may be covalently bonded or coordinated to R 1b or R 5 .
  • General formula 3 In General Formula 3, Z 1 and Z 2 are each a non-metallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be independently condensed
  • R 101 and R 102 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group
  • L 1 represents a methine chain composed of an odd number of methines
  • a and b are each independently 0 or 1
  • X 1 represents an anion
  • c represents the number necessary for
  • the curable composition may contain a pigment derivative.
  • the pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group.
  • a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferable that the pigment derivative has a basic group.
  • the combination of the above-described resin (dispersant) and pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.
  • organic pigment for constituting the pigment derivative examples include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
  • an acidic group which a pigment derivative has a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is still more preferable.
  • a basic group which a pigment derivative has an amino group is preferable and a tertiary amino group is more preferable.
  • the content of the pigment derivative is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be initiated, and a known photopolymerization initiator can be used.
  • the photopolymerization initiator for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. Further, it may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of the polymerizable compound.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • 0.1 mass% or more is preferable with respect to the total solid of a curable composition, 0.5 mass% or more is more preferable, 1 mass% or more is further more preferable, 1 More than mass% is particularly preferable, 30 mass% or less is preferable, 20 mass% or less is more preferable, 10 mass% or less is further preferable, and less than 10 mass% is particularly preferable.
  • content of a photoinitiator is more than 1 mass% and less than 10 mass% with respect to the total solid of a curable composition, the pattern shape of the cured film obtained by hardening
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that the total amount is in the said range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound containing the triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compound trihalomethyltriazine compound, benzyldimethyl ketal compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium compound
  • Preferred are compounds selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.
  • trihalomethyltriazine compounds ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, trihalomethyltriazine compounds, ⁇ - More preferred is at least one compound selected from the group consisting of an aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
  • 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 compound IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound 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 compound commercially available IRGACURE-819 or DAROCUR-TPO (trade names, both manufactured by BASF) can be used.
  • ⁇ Oxime compound More preferred examples of the photopolymerization initiator include oxime compounds (oxime initiators).
  • an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the colorant concentration, and can easily design a high colorant concentration.
  • oxime compound a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, or a compound described in JP-A No. 2006-342166 can be used.
  • Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyl And oxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M. C. S.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
  • N-1919 carboxyl hydroxybenzoic acid
  • An agent manufactured by ADEKA
  • oxime compounds other than those described above compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; dyes Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced; Ketooxime compounds described in International Patent Publication No. 2009-131189; Triazine skeleton and oxime skeleton are the same molecule A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP2014-500852; compounds described in JP2013-164471A (C-3); and the like. This content is incorporated herein.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • 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 Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are 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 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
  • R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
  • halogen R 6 represents 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
  • X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms.
  • R 3 and R 4 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 carbon number of 4 Represents a heterocyclic group of ⁇ 20, and X represents a direct bond or a carbonyl group.
  • R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3)
  • R 5 is, -R 6, -OR 6, -SR 6, Represents —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom or a hydroxyl group
  • R 6 represents 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
  • X is a direct bond or Represents a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
  • oxime compounds preferably used in the curable composition are shown below.
  • the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity, and from 5,000 to 200,000. More preferably, it is 000.
  • a known method can be used for the molar extinction coefficient of the compound.
  • an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use a photoinitiator in combination of 2 or more type as needed.
  • the curable composition contains a polymerizable compound.
  • the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition.
  • the lower limit is more preferably 1.0% by mass or more, still more preferably 3.5% by mass or more, and particularly preferably more than 3.5% by mass.
  • the upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably less than 20% by mass.
  • the pattern shape of the cured film obtained by curing the curable composition is more excellent.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that the total amount is in the said range.
  • the polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred.
  • the upper limit is 15 or less, for example.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof, and is preferably a monomer.
  • the molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.
  • 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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy and A dehydration condensation reaction product of a saturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group A reaction product of an unsaturated carboxylic acid ester or amide containing a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
  • 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 one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
  • 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), di Pentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; 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 an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer).
  • 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 carboxylic acid 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 hydroxy group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having an acid group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably 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 containing 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 properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, by being in the above range, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound containing a caprolactone structure.
  • the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • * represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • * represents a bond
  • Polymerizable compounds containing a caprolactone structure are commercially available from Nippon Kayaku, for example, as the KAYARAD DPCA series. 2) the number of groups represented by 2 and R 1 are all hydrogen atoms), DPCA-30 (wherein m is 1 and the number of groups represented by formula (Z-2) is 3). , Compounds in which R 1 is all hydrogen atoms), DPCA-60 (a compound in which m is 1, the number of groups represented by formula (Z-2) is 6, and R 1 is all hydrogen atoms) DPCA-120 (a compound in which m is 2, the number of groups represented by formula (Z-2) is 6, and all R 1 are hydrogen atoms).
  • a compound represented by the following 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)-.
  • Y represents an integer of 0 to 10
  • X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number 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 still more 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)-in formula (Z-4) or formula (Z-5) is A form 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.
  • all six Xs are acryloyl groups
  • all six Xs are acryloyl groups
  • An embodiment which is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the formula (Z-4) or the formula (Z-5) is a conventionally known process, which is a pentaerythritol or dipentaerythritol by a ring-opening addition reaction with ethylene oxide or propylene oxide. It can be synthesized from the step of bonding a ring-opening skeleton and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxy 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).
  • pentaerythritol derivatives and / or dipentaerythritol derivatives 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 formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate containing six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing 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 containing an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • 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 preferably has an SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
  • SP Solubility Parameter
  • the SP value is obtained by the Hoy method (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 curable composition contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.
  • a polymerizable compound containing a cardo skeleton a polymerizable compound containing 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.
  • X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 5.
  • 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.
  • 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 (
  • a phenyl group or a naphthyl group is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is more preferable.
  • X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • the substituent containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.
  • the aliphatic group containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and 2 to 10 carbon atoms. And more preferably an alkylene group having 2 to 5 carbon atoms.
  • aliphatic group containing 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 preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is oxygen More preferably, it is substituted with an atom.
  • the aliphatic group containing a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two positions with a hetero atom, more preferably at one position with a hetero atom, and Ar 11 to More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by Ar 14 is substituted with a hetero atom.
  • the polymerizable group contained in the aliphatic group containing the polymerizable group represented by X 1 to X 4 is a radically polymerizable or cationically polymerizable group (hereinafter also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). ) Is preferred.
  • radically polymerizable groups As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferable examples thereof include a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization, Can include a vinyl group, a (meth) acryloyloxy group, and the like. Among these, 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 Groups and the like are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
  • the polymerizable group contained in the substituent contained in Ar 11 to Ar 14 is preferably a radical polymerizable group.
  • Two or more of Ar 11 ⁇ Ar 14 comprises a substituent containing a polymerizable group, preferably contains a substituent 2-4 of Ar 11 ⁇ Ar 14 contains a polymerizable group, Ar More preferably, 2 or 3 of 11 to Ar 14 contain a substituent containing a polymerizable group, and two of Ar 11 to Ar 14 contain a substituent containing a polymerizable group. Further preferred.
  • 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 are each independently surrounded by a broken line Even if it is substituted with a benzene 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 5, 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, hydroxy groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups. An aryl group, an alicyclic group, etc. can be mentioned.
  • 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 independently May be 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 are the substituents that Ar 11 to Ar 14 can contain, respectively.
  • e, f, g and h are each independently preferably 0 to 8, 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 may be 0 or 1 Preferably, it is 0.
  • Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
  • Examples of the polymerizable compound containing a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
  • Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the curable composition contains a polyfunctional thiol compound.
  • a polyfunctional thiol compound is intended to contain two or more thiol groups (that is, a group represented by —SH) in the same molecule.
  • the content of the polyfunctional thiol compound is not particularly limited, but is usually 1 to 10% by mass with respect to the content of the colorant. Among these, 1 to 5.5% by mass is preferable, and 1.5 to 3.5% by mass is more preferable in that the curable composition has more excellent effects of the present invention.
  • the content of the polyfunctional thiol compound is preferably 0.55 to 3.5% by mass and more preferably 0.8 to 2.0% by mass with respect to the total solid content of the curable composition.
  • a polyfunctional thiol compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that the sum total is in the said range.
  • the polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more. Specifically, the molecular weight is preferably 100 to 1,500, and more preferably 150 to 1,000.
  • the polyfunctional thiol compound contains 2 or more thiol groups in the molecule, preferably 3 or more, preferably 10 or less, more preferably 6 or less, and 4 or less. More preferably.
  • a polyfunctional thiol compound is trifunctional or more, and it is more preferable that it is trifunctional or tetrafunctional.
  • the curable composition has a more excellent effect of the present invention.
  • the polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula (1).
  • L 1 represents a single bond or —CO—
  • L 2 represents a single bond or a divalent linking group.
  • the divalent linking group for L 2 in the formula (1) is a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group or a substituted alkynylene group), divalent.
  • Aromatic group eg, arylene group, substituted arylene group
  • divalent heterocyclic group oxygen atom (—O—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
  • the divalent linking group is an alkylene group
  • the alkylene group preferably has 1 to 5 carbon atoms, and more preferably 1 to 2.
  • polyfunctional thiol compound a compound represented by the following formula (2) having two or more groups represented by the formula (1) is more preferable.
  • L 1 represents a single bond or —CO—
  • L 2 represents a single bond or a divalent linking group
  • X represents an n-valent linking group
  • n represents an integer of 2 to 6.
  • the plurality of L 1 and L 2 may be the same or different.
  • N in the formula (2) is preferably 2 to 4, and more preferably 3 or 4.
  • X as the n-valent linking group in formula (2) is, for example, a divalent linking group such as — (CH 2 ) m — (m represents an integer of 2 to 6); a trimethylolpropane residue , And — (CH 2 ) p — (p represents an integer of 2 to 6), a trivalent linking group such as an isocyanur ring; a tetravalent linking group such as a pentaerythritol residue; or 5 And hexavalent linking groups such as dipentaerythritol residues.
  • polyfunctional thiol compound examples include, for example, 1,4-butanediol bis (thioglycolate), pentaerythritol tetra (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol Tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,4-bis (3-mercaptobutyloxy) Tan, 1,3,5-tris (3-mercaptobutyloxyethyl
  • the polyfunctional thiol compound includes pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropioate) in that the curable composition has more excellent effects of the present invention. And at least one selected from the group consisting of
  • the curable composition preferably contains a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, the curable composition has better stability over time.
  • the term “stability over time” means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period.
  • the polymerization inhibitor has an action of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition being stored, and it is presumed that the above-described effect can be obtained.
  • the content of the polymerization inhibitor is preferably from 0.1 to 1.5 mass%, more preferably from 0.3 to 1.0 mass%, based on the content of the polyfunctional thiol compound. When the content of the polymerization inhibitor is within the above range, the curable composition has more excellent temporal stability.
  • the content of the polymerization inhibitor is preferably from 0.00055 to 0.055% by mass, more preferably from 0.0015 to 0.01% by mass, based on the total solid content of the curable composition.
  • the polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used.
  • the compound used as the polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
  • the said compound may be used individually by 1 type, or may use 2 or more types together.
  • phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-di- tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert -Butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.
  • phenolic compound a phenolic compound represented by the formula (IH-1) is preferable.
  • R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
  • R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
  • R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group
  • R 2 and R 4 are more preferably a hydrogen atom
  • R 3 is a hydrogen atom
  • an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
  • Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
  • R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
  • R 7 to R 10 in formula (IH-2) each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
  • each of the above compounds may be used alone, in combination of two or in combination of three or more.
  • the polymerization inhibitor preferably contains a phenolic compound. Especially, it is more preferable that a polymerization inhibitor contains 2 or more types of phenolic compounds.
  • a curable composition containing a different phenolic compound has a more excellent effect of the present invention.
  • the polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound.
  • the curable composition containing a phenol compound and a hindered amine compound has a more excellent effect of the present invention.
  • the curable composition preferably contains a solvent.
  • the solvent include water and organic solvents.
  • the curable composition preferably contains an organic solvent.
  • the solid content of the curable composition is preferably 10 to 40% by mass.
  • a viscosity is low and applicability
  • paintability will improve.
  • the concentration of the highly reactive compound is lowered, the stability over time is improved.
  • the solid content of the curable composition is less than or equal to the upper limit value, the viscosity is maintained at a certain level and the applicability is improved.
  • the colorant with a high specific gravity is less likely to settle, and the stability over time is improved.
  • organic solvent When the curable composition contains an organic solvent, the content of the organic solvent is preferably 60 to 90% by mass with respect to the total mass of the curable composition.
  • an organic solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of organic solvents together, it is preferable that the total amount becomes the said range.
  • the organic solvent is not particularly limited.
  • acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • the curable composition may contain water. Water may be intentionally added, or may be inevitably contained in the curable composition by adding each component contained in the curable composition.
  • the water content is preferably 0.01 to 1% by mass relative to the total mass of the curable composition. When the water content is within the above range, the generation of pinholes is suppressed when a cured film is produced, and the moisture resistance of the cured film is further improved.
  • the curable composition preferably contains a dispersant.
  • the dispersant contributes to the improvement of the dispersibility of the colorant.
  • the dispersant and the binder resin described later are different components.
  • the content of the dispersant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the curable composition. 5 mass% or more is still more preferable, 11 mass% or more is especially preferable, and 17 mass% or more is the most preferable.
  • the upper limit of the content of the dispersant is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 22% by mass or less with respect to the total solid content of the curable composition.
  • curing a curable composition as content of a dispersing agent is 17 mass% or more is more excellent.
  • a dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total amount is preferably within the above range.
  • the dispersant for example, a known pigment dispersant can be appropriately selected and used.
  • polymer compounds are preferable.
  • the dispersant include polymer dispersants [for example, 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 type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
  • the 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 the dispersion of the colorant (for example, inorganic pigment) and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a colorant such as a black pigment and the dispersion stability after the lapse of time ( Excellent stability.
  • the polymer compound containing a structural unit containing a graft chain has an affinity for a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain. As a result, it becomes difficult to produce a residue by alkali development.
  • the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the black pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as black pigments is lowered, and the dispersibility of black pigments and the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and excluding hydrogen atoms. More preferred are those having 60 to 500 atoms.
  • 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 contains 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.
  • examples thereof include a structure and a polyether structure.
  • the graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like.
  • a graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferred.
  • the macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.
  • 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, Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation) are preferred.
  • the dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
  • the polycaprolactone structure means a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure means a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
  • Specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
  • dispersant containing a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
  • the polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), 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 (the number of carbon atoms), from the viewpoint of synthesis constraints, Independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more 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 each represent a binding site. Of the structures shown below, (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. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, and the like Is mentioned.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those containing a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • alkyl groups or alkoxy groups are more preferable, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more 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 viewpoint of the temporal stability and developability of the curable composition.
  • 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 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • R 4 is an alkyl group
  • 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 is preferable, and 1 to 20 carbon atoms is preferable.
  • linear alkyl groups having 1 to 6 carbon atoms are more preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • a high molecular compound can contain the structural unit containing the graft chain from which 2 or more types of structures differ. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be included. , And 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, and Formula (3) and Formula ( In 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 viewpoint of temporal stability and developability of the curable composition.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of temporal stability and developability of the curable composition.
  • 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 the formula (3B) from the viewpoint of temporal stability and developability of the curable composition. .
  • 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 contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30%.
  • the structural unit containing a graft chain is included within this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.
  • a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain).
  • a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, ClogP value intends the value calculated by program CLOGP v4.82. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • logP 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 contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more 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 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic 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 aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the carbon number 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 contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. 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 can be mentioned. 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 aliphatic 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 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 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.).
  • Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 .
  • bridged cyclic hydrocarbon rings include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and 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.
  • 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 carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • 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 and heterocyclic group.
  • 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 (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, it represents 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 a divalent linkage containing 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 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 is preferable.
  • 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.
  • radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • representative compounds represented by formulas (i) to (iii) the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. It is.
  • 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 within the above range, good and sufficient pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming interaction with a colorant such as black pigment.
  • the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.
  • the functional group capable of forming an interaction with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
  • the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively.
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the 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 a polymer compound, the polymer compound as a dispersant that contributes to the dispersion of a colorant such as a black pigment in the curable composition contains alkali-solubility.
  • the curable 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.
  • the polymer compound When the polymer compound contains a structural unit containing an acid group, the polymer compound tends to become compatible with the solvent and the coating property tends to be improved. This is because the acid group in the structural unit containing an acid group easily interacts with a colorant such as a black pigment, and the polymer compound stably disperses the colorant such as a black pigment, and the colorant such as a black pigment This is probably because the viscosity of the polymer compound in which the polymer is dispersed is lowered, and the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit. Are different structural units (ie, do not correspond to the hydrophobic structural units described above).
  • the acid group that is a functional group capable of interacting with a colorant such as a black pigment examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. At least one of acid groups and phosphoric acid groups is preferable, and a carboxylic acid group is more preferable in terms of good adsorptive power to a colorant such as a black pigment and high dispersibility of the colorant. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units containing an acid group.
  • the polymer compound may or may not contain a structural unit containing an acid group.
  • the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of interacting with a colorant 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. And an amide group and the like, and a preferable one is a tertiary amino group in that the adsorbing power to a colorant such as a black pigment is good and the dispersibility of the colorant is high.
  • the polymer compound can contain one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. It is preferably 0.01% or more and 50% or less with respect to the mass, and more preferably 0.01% or more and 30% or less from the viewpoint of inhibiting developability inhibition.
  • a coordinating group that is a functional group capable of forming an interaction with a colorant such as a black pigment, and a functional group having reactivity
  • a acetylacetoxy group for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned.
  • Preferable one is an acetylacetoxy group from the viewpoint of good adsorbing power to a colorant such as a black pigment and high dispersibility of the colorant.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less in terms of mass, and more preferably 20% or more and 60% or less from the viewpoint of inhibiting developability inhibition.
  • the polymer compound contains a functional group capable of interacting with a colorant such as a black pigment in addition to the graft chain
  • the functional group capable of interacting with a colorant such as the above various black pigments
  • the polymer compound is derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to contain one or more structural units selected from these structural units.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 in the formulas (iv) to (v) 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—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic 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 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 hydroxy group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
  • 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 include 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 forming an interaction with a colorant 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.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an 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 a divalent oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or 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 a methine group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
  • monomers represented by the formulas (iv) to (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • reaction product a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
  • the content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is from the viewpoint of interaction with the colorant such as a black pigment, stability over time, and permeability to a developer.
  • the amount is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass based on the total mass of the polymer compound.
  • the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a black color as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength.
  • structural units containing functional groups that can interact with colorants such as pigments other structural units having various functions (for example, functional groups having affinity with the dispersion medium used in the dispersion) And the like may be further included.
  • 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 is preferably 0% or more and 80% or less based on the total mass of the polymer compound in terms of mass. 10% or more and 60% or less is more preferable. 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 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and in the range of 20 mgKOH / g to 120 mgKOH / g. A range is more preferred. If the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better.
  • the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of a colorant such as a black pigment can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be reduced. It can be improved.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound is 4 in terms of polystyrene converted by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability. It is preferably 000 or more and 300,000 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.
  • the GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID ⁇ 15 cm) as a column 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.
  • polymer compound examples include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)” manufactured by BYK Chemie, and 110 (copolymers containing acid groups).
  • Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
  • Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPER10K, 2001-DISPERBY, manufactured by BYK Chemie. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co. These polymer compounds may be used alone or in combination of two or more.
  • 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.
  • a graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Can be incorporated and incorporated herein by reference.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the curable composition preferably contains a binder resin.
  • the content of the binder resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.9% by mass or more, based on the total solid content of the curable composition. 9 mass% or more is especially preferable, 30 mass% or less is preferable, 25 mass% or less is more preferable, 18 mass% or less is further more preferable, and 10 mass% or less is especially preferable.
  • the content of the binder resin is 1.9% by mass or more and 10% by mass or less, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
  • Binder resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of binder resin together, it is preferable that the total amount is in the said range.
  • a linear organic polymer is preferably used.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development.
  • alkali-soluble resin (resin containing group which accelerates
  • the binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain).
  • alkali-soluble resins containing a group to be used can be suitably selected from alkali-soluble resins containing a group to be used.
  • polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and (meth) acrylic resins, (meth) acrylamide resins, (meth) acryl / (meth) acrylamide copolymer resins, or polyimide resins are more preferred from the viewpoint of control of developability.
  • Examples of the group that promotes alkali solubility include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin containing a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.
  • binder resin examples include a radical polymer containing a carboxylic acid group in the side chain.
  • examples of the radical polymer containing a carboxylic acid group in the side chain include, for example, JP 59-44615, JP-B 54-34327, JP-B 58-12777, JP-B 54-25957, JP-A 54 -92723, JP-A-59-53836, and JP-A-59-71048.
  • a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group, an acid anhydride obtained by singly or copolymerizing a monomer containing an acid anhydride examples thereof include resins obtained by hydrolysis, half-esterification or half-amidation of units, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
  • the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
  • Examples include acidic cellulose derivatives containing a carboxylic acid group in the side chain.
  • Examples of the monomer containing an acid anhydride include maleic anhydride.
  • a polymer containing a hydroxyl group added to a polymer containing a hydroxyl group is useful.
  • Acetal-modified polyvinyl alcohol binder resins containing acid groups are described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463.
  • An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because of its excellent balance between film strength and developability.
  • polyvinyl pyrrolidone or polyethylene oxide is useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
  • a polyimide resin described in International Publication No. 2008/123097 is also useful.
  • [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / if necessary Other addition-polymerizable vinyl monomers] are preferable because they are excellent in the balance of film strength, sensitivity, and developability.
  • Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai), and Daicel Ornex Cyclomer P (ACA) 230AA.
  • a known radical polymerization method can be applied.
  • Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when the binder resin is produced by the radical polymerization method.
  • the binder resin it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group).
  • the definition of the structural unit containing the graft chain is synonymous with the structural unit containing the graft chain contained in the dispersant, and the preferred range is also the same.
  • the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable. Carboxylic acid groups are more preferred.
  • the structural unit containing an acid group preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (vii) to (ix).
  • R 21 , R 22 , and R 23 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 21 , R 22 , and R 23 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or More preferred is a methyl group.
  • R 21 and R 23 are each particularly preferably a hydrogen atom.
  • X 2 in the formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (viii) represents a methine group or a nitrogen atom.
  • L 2 in the formulas (vii) to (ix) 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 group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR 41 ′ —
  • R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic 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 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 hydroxy group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
  • 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 42 , where R 42 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 2 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 2 may include 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 2 is an acid group, preferably a carboxylic acid group.
  • R 24 , R 25 , and R 26 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, an ethyl group, a propyl group, etc.), - represents a Z 2, or L 2 -Z 2.
  • L 2 and Z 2 has the same meaning as L 2 and Z 2 in the above, and preferred examples are also the same.
  • R 24 , R 25 and R 26 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or a divalent oxyalkylene structure.
  • a compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
  • R 21 is a hydrogen atom or a methyl group
  • L 2 is an alkylene group
  • Z 2 is a carboxylic acid group
  • Y is a methine group.
  • Compounds are preferred.
  • a compound in which R 24 , R 25 and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
  • the binder resin can be synthesized by the same method as the dispersant containing the structural unit containing the graft chain, and the preferred acid value and weight average molecular weight are also the same.
  • the binder resin may have one or more structural units containing an acid group.
  • the content of the structural unit containing an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder resin. % Is more preferable.
  • the curable composition preferably contains a surfactant.
  • Surfactant contributes to the applicability
  • the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total mass of the curable composition, preferably 0.005 to 1.0 mass% is more preferable.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable 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, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the compound (F-1) represented by the following formula is also exemplified as the fluorosurfactant.
  • the structural units represented by formulas (A) and (B) are 62 mol% and 38 mol%, respectively.
  • the weight average molecular weight of the following compound is 15,311, for example.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin 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 (Lubrizol Japan Co., Ltd.), and the like.
  • Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101 Pionein D
  • 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 (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 Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • a silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule.
  • a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond 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 hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
  • the silane coupling agent contains fluorine atoms and silicon atoms (except for silicon atoms to which hydrolyzable groups are bonded) in order to improve the adhesion between the substrate and the cured film.
  • the silane coupling agent preferably contains 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 contains 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.
  • 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 1,000 from the viewpoint of handleability, preferably 270 or more, and more preferably 270 to 1,000.
  • 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.
  • Lz represents a divalent linking group
  • the divalent As the linking group an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
  • 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 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602)
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-tri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603)
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602)
  • ⁇ -aminopropyl- Trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903)
  • ⁇ -aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and containing a hydrolyzable group bonded to the silicon atom.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. 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 silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, alkyl group and / or aryl group, an amino group, a halogen atom, a sulfonamide group, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, or a salt thereof.
  • at least one hydrolyzable group is bonded to the silicon atom.
  • the definition of the hydrolyzable group is as described above.
  • the silane coupling agent Y may contain a group represented by the formula (Z).
  • the silane coupling agent Y has at least one nitrogen atom in the molecule, and 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 contains 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 preferably bonded to the curable functional group via any organic linking group.
  • Preferred examples of the organic linking group include a substituent that can be introduced into the nitrogen atom and 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 contain two or more curable functional groups. From the viewpoint of sensitivity and stability, the curable functional group is preferably contained in the molecule in an amount of 2 to 20, more preferably 4 to 15, and even more preferably 6 to 10.
  • the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above ranges (preferably 270 or more).
  • the content of the silane coupling agent in the curable composition 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 curable composition. More preferably, the content is 0.0 to 6% by mass.
  • the curable composition may contain one type of silane coupling agent or two or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
  • the curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
  • an ultraviolet absorber salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl ultraviolet absorber (trade name, UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. preferable.
  • the manufacturing method of a curable composition contains the following mixing and dispersion
  • a mixing and dispersing process is a process of mixing the said component with a well-known mixing method (For example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser), and obtaining a curable composition.
  • a well-known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser
  • each component constituting the curable composition may be mixed at once, or may be sequentially added after each component is dissolved or dispersed in an organic solvent. There are no particular restrictions on the charging sequence and working conditions when blending.
  • the mixing and dispersing step may include a step of producing a dispersion.
  • the step of preparing the dispersion is a step of mixing the colorant, the dispersant, and the solvent, and dispersing the colorant by the above method to prepare the dispersion.
  • a curable composition can be manufactured by mixing other components with the prepared dispersion.
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion.
  • the pigment may be refined by a salt milling step.
  • materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
  • the manufacturing method of a curable composition contains the process of obtaining the said coloring agent by a thermal plasma method.
  • the step of obtaining the colorant is performed before mixing the above-described components.
  • the aspect of the specific manufacturing process of the colorant by the thermal plasma method is as described above.
  • the colorant may be subjected to the following standing step before being subjected to the mixing and dispersing step or the step of producing a dispersion.
  • the standing step refers to a predetermined time (preferably 12 to 72 hours, more preferably, in a sealed container in which the colorant obtained by the thermal plasma method is not exposed to the atmosphere after its production and the oxygen concentration is controlled. 12 to 48 hours, more preferably 12 to 24 hours). At this time, it is more preferable that the moisture content in the sealed container is controlled.
  • the oxygen (O 2 ) concentration and the water content in the sealed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and still more preferably 1 ppm or less.
  • the oxygen (O 2 ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container.
  • the inert gas nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
  • the surface of the colorant and the crystal grain boundary become stable. Thereby, generation
  • a filtration process is a process of filtering the curable composition manufactured by the said mixing and dispersion
  • a filter In the filtration step, foreign substances can be removed from the curable composition and / or defects can be reduced.
  • Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene or polypropylene (PP) (containing high density and ultra high molecular weight), and the like.
  • PTFE polytetrafluoroethylene
  • nylon polyamide resin
  • PP polyolefin resin
  • polyethylene or polypropylene (PP) containing high density and ultra high molecular weight
  • polypropylene containing high density and ultra high molecular weight
  • the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and about 0.3 to 0.7 ⁇ m. Further preferred. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. You may combine the 1st filter of a different hole diameter within said range.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter can be used.
  • the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
  • the cured film is obtained by curing the curable composition.
  • the cured film contains a colorant.
  • the cured film is preferably used as a light-shielding film, and specifically used for light-shielding the periphery of the light receiving portion of the image sensor.
  • a case where the cured film is used as a light shielding film around the light receiving portion of the image sensor will be described as an example.
  • the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less, and preferably 0.3 ⁇ m or more and 10 ⁇ m or less, in that the light-shielding film has more excellent effects of the present invention. Is more preferably 0.3 ⁇ m or more and 5 ⁇ m or less. Since the curable composition has a high optical density per unit volume (because of its high light-shielding property), the film thickness can be reduced as compared with a curable composition using a conventional black pigment.
  • the size of the light-shielding film (the length of one side of the light-shielding film provided around the sensor light-receiving portion) is preferably 0.001 mm or more and 10 mm or less in that the light-shielding film has more excellent effects of the present invention.
  • 05 mm or more and 7 mm or less are more preferable, and 0.1 mm or more and 3.5 mm or less are still more preferable.
  • the manufacturing method of a cured film contains the following curable composition layer formation process and an exposure process.
  • the method for producing a cured film preferably further includes a development step.
  • Curable composition layer forming step A step of forming a curable composition layer on a support.
  • Exposure process The process of exposing the said curable composition layer.
  • Development step a step of developing the curable composition layer after exposure to form a patterned cured film (light-shielding film).
  • the curable composition is applied to the substrate directly or via another layer to form a curable composition layer (curable composition layer forming step), and a predetermined mask pattern is formed.
  • the cured film can be produced by curing only the coating film portion exposed to light through light (exposure process) and developing with a developer (development process). Hereafter, each said process is demonstrated.
  • the curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as “substrate”). Among them, it is preferable to include a coating step in which a curable composition is applied on a support to form a curable composition layer, and the curable composition is directly applied on the support to form a curable composition layer on the support. It is more preferable to include a coating step of forming a curable composition layer.
  • the substrate examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices and the like, and those obtained by attaching a transparent conductive film to these, photoelectric devices used for solid-state imaging devices, and the like.
  • Examples include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
  • an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
  • various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
  • the coating film thickness of the curable composition is preferably 0.35 ⁇ m or more and 1.5 ⁇ m or less from the viewpoint of resolution. More preferably, it is 40 ⁇ m or more and 1.0 ⁇ m or less.
  • the curable composition applied on the substrate is usually dried at 70 ° C. to 110 ° C. for 2 minutes to 4 minutes. Thereby, a curable composition layer can be formed.
  • the exposure step is a step in which the curable composition layer (coating film) formed in the curable composition layer forming step is exposed through a mask and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation with actinic rays or radiation, in particular, ultraviolet rays such as g-line, h-line, and i-line are preferable, and a high-pressure mercury lamp is more preferable.
  • Exposure is not particularly limited but is preferably 200 mJ / cm 2 or more, more preferably 200 ⁇ 1,500mJ / cm 2, more preferably 200 ⁇ 1,000mJ / cm 2, particularly preferably 200 ⁇ 500mJ / cm 2.
  • the cured film production method has more excellent stability and productivity. From the viewpoint of improving resolution, exposure with an i-line stepper is preferable in forming a light-shielding film for a solid-state imaging device.
  • a development process is a process of developing the exposed curable composition layer.
  • a patterned cured film can be obtained by the development step. It is preferable that the manufacturing method of the said cured film contains a image development process and the following washing
  • an alkali development treatment (development process) is performed, and the light non-irradiated part in the exposure process is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
  • the developer when producing a light-shielding color filter containing a black matrix for a solid-state image sensor, an organic alkali developer that does not damage the underlying circuit or the like is preferable.
  • the development temperature is usually preferably 20 to 30 ° C., and the development time is preferably 20 to 90 seconds.
  • Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
  • As the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1 is used.
  • An alkaline aqueous solution dissolved so as to be in mass% can be mentioned.
  • organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.0]- Examples thereof include an alkaline aqueous solution in which an alkaline compound such as 7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution.
  • a developing method for example, a paddle developing method and a shower developing method can be used.
  • the washing step is a step of washing (rinsing) the developed curable composition layer with pure water or the like.
  • the cleaning method is not particularly limited, and a known cleaning method can be used.
  • the manufacturing method of the said cured film may contain the post-baking process which heats a cured film, and / or the hardening process which exposes a cured film whole surface after the said image development process.
  • a color filter containing a cured film is suitable for a solid-state imaging device such as a CCD image sensor and / or a CMOS image sensor. Particularly, it is suitable for a CCD image sensor and / or a CMOS image sensor having a high resolution exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state imaging device.
  • the color filter may contain 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 cured film (black matrix) is disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor and a microlens for condensing light.
  • the solid-state imaging device contains the cured film (black matrix).
  • the solid-state imaging device preferably contains a color filter containing a black matrix and, if necessary, a patterned film composed of pixels of other colors (three colors or four colors).
  • the solid-state imaging device is not particularly limited as long as it contains the above-described black matrix and functions as a solid-state imaging device. Examples include a solid-state imaging device that includes a plurality of photodiodes, a light-receiving element made of polysilicon, and the like, and that includes the black matrix on the surface opposite to the light-receiving element formation surface of the substrate.
  • 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.
  • the solid-state imaging device containing such a structure include the solid-state imaging devices described in JP2012-227478A and JP2014-179577A.
  • the cured film can be suitably used for an image display device (for example, a liquid crystal display device and an organic electroluminescence display device).
  • an image display device for example, a liquid crystal display device and an organic electroluminescence display device.
  • image display devices For the definition of image display devices and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)” and “Display Device (Junsho Ibuki, Industrial Books ( (Issued in 1989)).
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the cured film is suitable for, for example, a liquid crystal display device of the method described in the “next generation liquid crystal display technology”.
  • the liquid crystal display device containing the cured film for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) are provided between a pair of substrates at least one of which is light transmissive And a liquid crystal display device containing at least a method.
  • the liquid crystal display device includes a plurality of pixel groups, and each pixel constituting the pixel group includes a color filter separated from each other by the cured film (black matrix).
  • At least one of the light transmissive substrates contains at least a color filter, a liquid crystal layer, and liquid crystal driving means
  • the liquid crystal driving means is an active element (for example, TFT (Thin Film Transistor)) and a color filter containing the cured film (black matrix) between the active elements.
  • the color filter containing the cured film is suitable for a liquid crystal display device of a color TFT (Thin Film Transistor) type.
  • 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 color filter is a liquid crystal display device with a wide viewing angle, 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 STN (Super-Twist).
  • the color filter is suitable for a bright, high-definition COA (Color-filter On Array) type liquid crystal display device.
  • COA Color-filter On Array
  • the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics.
  • the COA type liquid crystal display device containing the color filter has better resolution or better durability.
  • a resin film may be further included on the color filter layer.
  • the liquid crystal display device includes 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 can be applied to a liquid crystal display device composed of these known members.
  • these materials for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” "Fuji Chimera Research Institute, Ltd., published in 2003)”.
  • backlights SID meeting Digest 1380 (2005) (A. Konno et.al) and / or Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi) It is described in.
  • the cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, bar code readers, and automatic teller machines ( ATM (automated teller machine), industrial equipment such as personal authentication using high-speed camera and face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope and catheter; biosensor, Optical filters used in space devices such as biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Module shading member and shading And further is suitable for anti-reflection member and the antireflection layer.
  • OA Office Automation
  • ATM automatic teller machine
  • industrial equipment such as personal authentication using high-speed camera and face image authentication
  • in-vehicle camera equipment medical camera equipment such as endoscope, capsule endoscope and catheter
  • biosensor Optical filters used in space devices such as biosensors, military
  • the cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • the cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
  • Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
  • the cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, the said cured film is suitable as a member which provides a light-shielding function and an antireflection function.
  • quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
  • Ti nanoparticles (TC-200, manufactured by Toho Tech Co., Ltd.) were formed into Ti nanoparticles by plasma treatment in Ar gas.
  • the Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under conditions of an O 2 concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere. Then, it was allowed to stand at 30 ° C. for 24 hours in a state where O 2 gas was introduced into the Ar atmosphere so that the O 2 concentration was 100 ppm (pretreatment of Ti particles).
  • the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain a powder of Ti particles.
  • the primary particle size of the obtained powder was 120 nm when the average particle size of 100 particles was determined by arithmetic average by TEM observation.
  • the titanium nitride-containing particles TiN-1 were produced using an apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098.
  • a high frequency voltage of about 4 MHz and about 80 kVA is applied to a high frequency oscillation coil of a plasma torch, and argon gas 50 L / min and nitrogen 50 L / min are used as plasma gases from a plasma gas supply source. Then, an argon-nitrogen thermal plasma flame was generated in the plasma torch.
  • a carrier gas of 10 L / min was supplied from the spray gas supply source of the material supply apparatus.
  • This mixture was supplied together with argon gas as a carrier gas into a thermal plasma flame in a plasma torch, evaporated in the thermal plasma flame, and highly dispersed in a gas phase state. Further, nitrogen was used as a gas supplied into the chamber by the gas supply device.
  • the flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1,000 L / min.
  • the pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value). In this way, titanium nitride-containing particles TiN-1 were obtained.
  • the obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms by ICP emission spectroscopy.
  • ICP emission spectroscopic analysis an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
  • the nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and was calculated by an inert gas melting-thermal conductivity method.
  • X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed 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 in the vicinity of the diffraction angle 2 ⁇ (42.6 °) was measured.
  • the crystallite size constituting the particle was determined using Scherrer's equation. As a result, the peak diffraction angle was 42.62 ° and the crystallite size was 10 nm. Note that no X-ray diffraction peak due to TiO 2 was observed.
  • Ti-particles residue / Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1, except that the mixture was mixed to 0.5 / 1.
  • the peak diffraction angle measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.
  • Titanium Black A-1 100 g of titanium oxide MT-150A (trade name, manufactured by Teika Co., Ltd.) having an average particle diameter of 15 nm and silica particles AEROSIL300 (registered trademark) 300/30 (Evonik) having a BET (Brunauer, Emmett, Teller) specific surface area of 300 m 2 / g 25 g) and Disperbyk190 (trade name, manufactured by Big Chemie) were weighed 100 g, and these were added to 71 g of ion electroexchanged water to obtain a mixture.
  • the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes using a MURASTAR KK-400W manufactured by KURABO to obtain a uniform aqueous mixture solution.
  • This aqueous mixture was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the inside of the small rotary kiln was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature.
  • the recovered powder was pulverized in a mortar to obtain a powdery titanium black (dispersed material containing titanium black particles and Si atoms) having a powder specific surface area of 73 m 2 / g (hereinafter referred to as “titanium”). Black A-1 ”).
  • Niobium nitride-containing particles containing Fe atoms were produced by the following method. First, niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemicals was prepared as a raw material (hereinafter also referred to as “metal raw material powder”). Next, the metal raw material powder was subjected to plasma treatment in Ar gas to form Nb nanoparticles. The conditions for the plasma treatment were the following plasma treatment (1).
  • Plasma treatment (1) was performed by the following method. Plasma treatment (1) was performed under the following conditions using an apparatus according to the above black composite fine particle production apparatus. ⁇ High frequency voltage applied to the coil for high frequency oscillation: frequency about 4 MHz, voltage about 80 kVA ⁇ Plasma gas: Argon gas (Supply rate: 100 L / min) Carrier gas: Argon gas (Supply amount: 10 L / min) -Chamber atmosphere: Argon gas (Supply rate: 1,000 L / min, chamber flow rate: 5 m / sec) ⁇ Cyclone atmosphere: Argon gas, internal pressure 50kPa ⁇ Material supply speed from chamber to cyclone: 10 m / s (average value)
  • Fe powder JIP270M, manufactured by JFE Steel Co., Ltd.
  • JFE Steel Co., Ltd. was prepared and subjected to plasma treatment under the conditions of plasma treatment (1) to form Fe nanoparticles.
  • Nb nanoparticles and Fe nanoparticles obtained as described above were mixed to obtain a raw metal powder.
  • This raw metal powder was subjected to plasma treatment in nitrogen gas to obtain niobium nitride-containing particles.
  • the conditions for the plasma treatment were the following plasma treatment (2).
  • Plasma treatment (2) was performed by the following method.
  • the apparatus used was the same as in the plasma treatment (1).
  • Plasma gas Argon gas and nitrogen gas (Supply amount 50L / min each)
  • Carrier gas Nitrogen gas (Supply amount: 10L / min)
  • Atmosphere in the chamber Nitrogen gas (amount supplied: 1,000 L / min, flow velocity in the chamber: 5 m / sec)
  • Cyclone atmosphere Nitrogen gas, internal pressure 50kPa ⁇ Material supply speed from chamber to cyclone: 10 m / s (average value)
  • niobium nitride-containing particles NbN
  • Nitrogen gas was supplied to the separator.
  • the obtained niobium nitride-containing particles were measured for the content of iron (Fe) atoms by ICP emission spectroscopy, and found to be 50 ppm by mass.
  • VN vanadium nitride-containing particles containing Fe atoms
  • Fe atoms were used in the same manner except that the metal vanadium powder VHO manufactured by Taiyo Mining Co. was used instead of Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemicals.
  • SH-4 penentaerythritol tetra (3-mercaptopropionate), which corresponds to a tetrafunctional thiol compound
  • SH-3 corresponds to trimethylolpropane tris (3-mercaptopropionate), trifunctional thiol compound
  • SH-2 corresponds to 1,4 butanediol bis (thioglycolate), bifunctional thiol compound
  • Dispersant A having the following structure was used as the dispersant.
  • the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
  • Binder resin As the binder resin, the following resin A was used. The numerical value described in each structural unit intends mol% of each structural unit with respect to the total structural unit. In the formula of resin A, each abbreviation represents the following. BzMA: benzyl methacrylate MMA: methyl methacrylate
  • Polymerizable compound M1 dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD”, see the following formula)
  • OXE-02 Irgacure OXE02 (trade name, manufactured by BASF Japan)
  • IRG-379 IRGACURE 379 (trade name, manufactured by BASF Japan)
  • a coating film was formed by spin coating on each of the curable compositions on a 10 mm square glass plate (Eagle XG, manufactured by Corning) having a thickness of 0.7 mm. At this time, the rotational speed was adjusted so that a cured film having a thickness of 1.5 ⁇ m was obtained. The formed coating film was dried by heat treatment at 100 ° C. for 2 minutes on a hot plate and exposed at an exposure amount of 500 mJ / cm 2 to obtain a cured film. About the glass substrate containing the obtained cured film, OD value was measured with the spectrophotometer U-4100 (made by Hitachi High-Technologies). The higher the OD value, the better the light-shielding property of the cured film.
  • the results are summarized in Table 1-1, Table 1-2, and Table 2.
  • the OD values shown in Table 1-1, Table 1-2, and Table 2 are minimum values at wavelengths of 400 to 800 nm. That is, the cured film (film thickness 1.5 ⁇ m) of each example has an OD value equal to or greater than the OD values shown in Table 1-1, Table 1-2, and Table 2 in the entire wavelength range of 400 to 800 nm.
  • the exposed coating film was subjected to paddle development for 30 seconds using a coater developer ACT8 manufactured by Tokyo Electron, using tetramethylammonium hydroxide as a developer. After the development, a shower rinsing process was performed with pure water for 20 seconds. The developed coating film was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the coating film after post-baking was measured with a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the pattern end / film thickness at the center) was calculated and evaluated according to the following criteria. The results are summarized in Table 1-1, Table 1-2, and Table 2.
  • the ratio is more than 0.90 and not more than 0.92, and the film thickness at the end is thin and distorted, but there is no practical problem.
  • -2 The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but the practical level is possible.
  • -1 The ratio is 0.80 or less, the film thickness at the end is thin, and is not acceptable.
  • the curable composition of Example 48 in which the content of the colorant is 55% by mass or more based on the total solid content of the curable composition, the content of the dispersant is the same, and the content of the colorant Compared with the curable composition of Example 49 whose quantity is 53%, the pattern shape of the hardened
  • the curable compositions of Example 1, Example 2, and Example 3 in which the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant are the same as those in Example 4. Compared with the curable composition, the pattern shape of the obtained cured product was more excellent.
  • the curable composition of Example 45 containing two or more phenolic compounds as a polymerization inhibitor was cured at a lower exposure dose than the curable composition of Example 36, and the pattern of the cured product The shape was excellent.
  • the curable composition of Example 46 containing a phenolic compound and a hindered amine compound as a polymerization inhibitor was cured at a lower exposure amount than the curable composition of Example 36, and the pattern shape of the cured product was obtained.
  • the curable composition of Example 5 in which the polyfunctional thiol compound is trifunctional was more excellent in the pattern shape of the cured product than the curable composition of Example 9.
  • the curable composition of Example 1 whose polyfunctional thiol compound is tetrafunctional was more excellent in the pattern shape of hardened
  • the curable composition of Example 34 in which the photopolymerization initiator was an oxime compound, was more excellent in the pattern shape of the cured product than the curable composition of Example 25.
  • the curable compositions of Example 13 and Example 48, in which the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition, are Example 50 and Example. Compared with 51 curable composition, the pattern shape of hardened
  • the curable compositions of Example 13 and Example 48 in which the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass with respect to the total solid content of the curable composition, are the examples 50 and Compared with the curable composition of Example 51, the pattern shape of the cured product was more excellent. Compared with the curable composition of Example 13 and Example 54, the curable composition of Example 2 and Example 48 whose content of a dispersing agent is 17 mass% or more has a pattern shape of hardened
  • a curable composition was prepared in the same manner as in Example 1 except that the surfactant F-1 was not used, and evaluation was performed using this. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.
  • CB dispersion Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition
  • the colorant is carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, carbon produced by a gas black method.
  • a carbon black dispersion (CB dispersion) was obtained in the same manner except that it was black.
  • chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]
  • PY dispersion A chromatic pigment dispersion was prepared in the same manner as in the preparation of the colorant dispersion, except that Pigment Yellow 150 (trade name: 6150 Pigment Yellow 5GN, manufactured by Hangzhou Star-up Pigment Co., Ltd.) was used as the colorant. (PY dispersion) was obtained.
  • chromatic pigment dispersion (PR dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PR dispersion) was obtained in the same manner except that Pigment Red 254 (manufactured by Ciba Specialty Chemicals) was used.
  • PB dispersion Preparation of chromatic pigment dispersion (PB dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PB dispersion) was obtained in the same manner except that Pigment Blue 15: 6 (manufactured by DIC Corporation) was used.
  • chromatic pigment dispersion (PV dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PV dispersion) was obtained in the same manner except that Pigment Violet 23 (manufactured by Clariant) was used.
  • Example 1 In the preparation of the curable composition of Example 1, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the above-mentioned titanium nitride-containing composition was used.
  • the above-mentioned titanium nitride-containing composition was used.
  • a curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same light shielding property and pattern shape as those of Example 1 were obtained, and further, a film having excellent light shielding properties in the infrared region was obtained.
  • the above-mentioned titanium nitride-containing composition was used.
  • the composition was prepared and evaluated using the composition. As a result of the evaluation, it was found that the same light shielding property and pattern shape as those of Example 1 were obtained, and further, a film having excellent light shielding properties in the infrared region was obtained.

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Abstract

La présente invention concerne une composition durcissable qui permet d'obtenir un film durci présentant une excellente forme de motif, tout en conservant d'excellentes propriétés de blocage de lumière; un film durci; un filtre de couleur; un film de blocage de lumière; un élément d'imagerie à l'état solide; un dispositif d'affichage d'image; et un procédé de production d'un film durci. Ladite composition durcissable contient un agent colorant, un initiateur de photopolymérisation, un composé polymérisable et un composé thiol polyfonctionnel; et un film durci qui est obtenu par durcissement de ladite composition durcissable présente une densité optique de 4,0 ou plus pour une épaisseur de film de 1,5 µm dans la région de la lumière visible.
PCT/JP2017/017673 2016-05-27 2017-05-10 Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, et procédé de production de film durci WO2017203979A1 (fr)

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KR1020187033076A KR102208741B1 (ko) 2016-05-27 2017-05-10 경화성 조성물, 경화막, 컬러 필터, 차광막, 고체 촬상 소자, 화상 표시 장치, 및 경화막의 제조 방법

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WO2021215155A1 (fr) * 2020-04-20 2021-10-28 日産化学株式会社 Composition photodurcissable
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JPWO2017203979A1 (ja) 2019-04-11
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