WO2017061477A1 - Procédé de fabrication d'un film durci, film durci, élément d'imagerie à semi-conducteur, et dispositif d'affichage d'image - Google Patents

Procédé de fabrication d'un film durci, film durci, élément d'imagerie à semi-conducteur, et dispositif d'affichage d'image Download PDF

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WO2017061477A1
WO2017061477A1 PCT/JP2016/079642 JP2016079642W WO2017061477A1 WO 2017061477 A1 WO2017061477 A1 WO 2017061477A1 JP 2016079642 W JP2016079642 W JP 2016079642W WO 2017061477 A1 WO2017061477 A1 WO 2017061477A1
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group
cured film
film
compound
curable composition
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PCT/JP2016/079642
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English (en)
Japanese (ja)
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久保田　誠
浜田　大輔
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富士フイルム株式会社
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Priority to JP2017544531A priority Critical patent/JP6595613B2/ja
Publication of WO2017061477A1 publication Critical patent/WO2017061477A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation

Definitions

  • the present invention relates to a method for producing a cured film, a cured film, a solid-state imaging device, and an image display device.
  • a solid-state imaging device includes a photographing lens, a solid-state imaging device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographing lens, and a circuit on which the solid-state imaging device is mounted.
  • a substrate This solid-state imaging device is mounted on a digital camera, a mobile phone with a camera, a smartphone, or the like.
  • noise due to reflection of visible light may occur. Therefore, it is widely performed to provide a predetermined light shielding film in the solid-state imaging device.
  • a light shielding film is formed using, for example, a curable composition (photosensitive composition) containing a black pigment such as titanium black.
  • Patent Document 1 discloses a step of applying a curable composition (black polymerizable composition) by spraying.
  • a method for producing a cured film (black cured film) through the above is disclosed (claims 8, 9 etc.).
  • an object of the present invention is to provide a cured film production method having low reflectance and excellent lithography performance, a cured film, and a solid-state imaging device and an image display apparatus having the cured film.
  • the present inventor has found that when a cured film is produced, the ratio between the landing size D1 when forming the first coating film and the landing size D2 when forming the second coating film. Has been found that desired performance can be obtained by being within the predetermined range, and the present invention has been achieved. That is, the present inventor has found that the above problem can be solved by the following configuration.
  • a method for producing a cured film using a curable composition containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent A first step of spray-coating the curable composition so that the landing size is D1 to form a first coating film; A second step of spraying the curable composition so as to have a landing size of D2 to form a second coating film; Carrying out a curing process to form a cured film;
  • [2] The method for producing a cured film according to [1], wherein the second step is performed after the first step.
  • the distance L1 between the tip of the nozzle of the spray device used for spray application in the first step and the surface to be coated is the distance between the tip of the nozzle of the spray device used for spray application in the second step and the surface to be coated.
  • [4] The method for producing a cured film according to [3], wherein the distance L1 is less than 5 cm and the distance L2 is more than 10 cm.
  • a cured film manufacturing method As described below, according to the present invention, it is possible to provide a cured film manufacturing method, a cured film, a solid-state imaging device and an image display apparatus having the same, which have low reflectance and excellent lithography performance.
  • the description which does not indicate substitution and non-substitution includes those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the “radiation” in the present specification means those including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
  • 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.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acrylic and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl
  • (meth) ) Acrylamide refers to acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • the monomer in this specification 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 having 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 method for producing a cured film of the present invention is a method for producing a cured film using a curable composition containing a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, and a solvent, A first step of spraying the curable composition so that the landing size is D1 to form a first coating film, and a second step of spraying the curable composition so that the landing size is D2.
  • the ratio D1 / D2 is 5 to 150.
  • a cured film having low reflectance and excellent lithography performance can be produced.
  • the reason is as follows.
  • the curable composition When the curable composition is sprayed from the nozzle of the spray device, the curable composition flies in the form of a plurality of droplets, which land on the surface to be coated.
  • the liquid droplets that have landed on the surface to be coated are dried to become a granular material composed of the solid content contained in the liquid droplets. A plurality of these granular materials are collected to form one film (coating film).
  • FIG. 1A and FIG. 1B are explanatory views showing an example of a method for producing a cured film of the present invention step by step.
  • the coating film 120 is formed on the substrate 100, and includes a first coating film 120A and a second coating film 120B.
  • the coating film 120 is cured by a curing process (not shown) to become a cured film.
  • the first coating film 120A composed of granular materials having a large landing size is formed using droplets having a large size.
  • the resulting granular material 120a is flat and has a large area. Further, the granular materials 120a are in good contact with each other. Thereby, since the first coating film 120A composed of the plurality of granular materials 120a becomes a flat film with few pinholes, the pattern of the cured film including the first film formed by curing the first coating film 120A Generation of chipping and pinholes is suppressed.
  • the 2nd coating film 120B comprised from the granular material 120b with a small landing size is formed using a droplet with a small size. A small-sized droplet has a small spread when landed on the surface to be coated, and therefore it is easy to maintain its shape after landing.
  • the 2nd coating film 120B comprised from the some granular material 120b has an uneven surface, the reflectance of the cured film containing the 2nd film
  • the curable composition used in the method for producing a cured film of the present invention includes a colorant, a polymerization initiator, a polymerizable compound, a binder polymer, And a solvent.
  • the component contained in the composition of this invention and the component which may be contained are demonstrated.
  • the composition of the present invention contains a colorant.
  • a colorant Various known color pigments and color dyes can be used as the colorant.
  • chromatic dyes chromatic dyes
  • colorants described in paragraphs 0027 to 0200 of JP-A-2014-42375 can also be used.
  • the black dye black dye generally used for black matrix formation or light-shielding film system formation can be used.
  • color pigment examples include chromatic pigments (chromatic pigments such as R (red), G (green), and B (blue)) that form the color pixels of the color filter if used in the manufacture of color filters. ), And black pigments (black pigments) generally used for forming a black matrix or for forming a light-shielding film system.
  • chromatic pigments chromatic pigments such as R (red), G (green), and B (blue)
  • black pigments black pigments
  • black pigments generally used for forming a black matrix or for forming a light-shielding film system.
  • the chromatic pigment various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 ⁇ m. ⁇ 0.1 ⁇ m is preferable, and 0.01 ⁇ m to 0.05 ⁇ m is more 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 as the transmission electron microscope.
  • the 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 the maximum length 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 “average primary particle size” in the examples of the present specification is also the same as the arithmetic average value.
  • inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.
  • Examples of the pigment include conventionally known various inorganic pigments or organic pigments.
  • examples of inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals. The following can be mentioned as an organic pigment. However, the present invention is not limited to these.
  • examples of organic pigments include Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31.
  • Black pigment In the present invention, a black pigment can also be used as the pigment.
  • the black pigment will be described in more detail.
  • Various known black pigments can be used as the black pigment.
  • carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite and the like are preferable from the viewpoint of realizing a high optical density in a small amount, and in particular, at least one of carbon black and titanium black is included.
  • titanium black is preferred from the viewpoint of low absorption in the light absorption wavelength region of the initiator related to the curing efficiency by exposure.
  • Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include, but are not limited to, inorganic pigments such as CI Pigment Black 7.
  • pigments having infrared absorptivity other than the pigments described as black pigments 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 property at wavelengths in the infrared region.
  • a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an initiator related to curing efficiency by exposure and excellent translucency in the visible light region.
  • pigments may be used in combination of two or more, or may be used in combination with a dye described later.
  • chromatic pigments such as black, red, green, yellow, orange, purple, and blue as described above or pigments having infrared light-shielding properties or The aspect which mixes the dye mentioned later is mentioned.
  • the pigment having black or infrared light shielding properties preferably contains a red pigment or dye and a purple pigment or dye, and the pigment having black or infrared light shielding properties particularly preferably contains a red pigment.
  • the black pigment preferably contains titanium black.
  • Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride.
  • 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 can also be treated with a water repellent material as disclosed in JP-A-2007-302836. Is possible.
  • the titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, the average primary particle diameter is preferably in the range of 10 to 45 nm.
  • the specific surface area of titanium black is not particularly limited. However, since water repellency after surface treatment of titanium black with a water repellent agent has a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method is 5 to 150 m 2 / g is preferable, and 20 to 120 m 2 / g is more preferable.
  • Examples of commercially available titanium black 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.) and the like.
  • titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
  • 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). In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
  • a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed.
  • a dispersed material containing Si and Ti as components can be obtained.
  • 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 in which Si / Ti is adjusted to 0.05 or more, for example, can be obtained by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be produced.
  • the composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more).
  • a suitable range for example, 0.05 or more.
  • a residue contains the component derived from compositions, such as a titanium black particle and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less).
  • the adsorptivity of the entire film with the underlying layer is reduced, and this is presumed to contribute to the improvement of the development removal property of the uncured composition (particularly titanium black) in the formation of the light-shielding film.
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is converted into mass)
  • the light-shielding film formed by using a material having a thickness of 0.05 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 light-shielding film obtained by curing the composition Is determined using 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
  • a Si-containing material such as silica
  • silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
  • fine particle type silica examples include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • a tungsten compound and a metal boride can also be used.
  • a tungsten compound and a metal boride are explained in full detail.
  • the curable composition of the present invention can use a tungsten compound and / or a metal boride.
  • Tungsten compounds and metal borides have high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, they have high light shielding 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.
  • the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than that in the visible range used for exposure such as a high pressure mercury lamp, KrF, and ArF used for image formation.
  • 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, 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 preferred, and Cs 0.33 WO 3 is more preferred.
  • the tungsten compound is preferably fine particles.
  • the average particle size 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 particle diameter is in such a range, the tungsten 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.
  • the average particle size is preferably as small as possible.
  • the average 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, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is 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). Further, 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
  • boride Titanium TiB 2
  • zirconium boride ZrB 2
  • hafnium boride HfB 2
  • vanadium boride VB 2
  • tantalum boride TaB 2
  • CrB 2 chromium boride
  • boride One type or two or more types of molybdenum (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 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.
  • the average particle size is preferably as small as possible.
  • the average 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.
  • 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.
  • dye currently disclosed by 194828 gazette etc. can be used.
  • pyrazole azo compounds When classified as 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 colorant having an absorption maximum in the wavelength range of 800 to 900 nm can be used as the colorant.
  • 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, and quaterylenes. Compounds, dithiol metal complex compounds, croconium compounds and the like.
  • the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound the compounds disclosed in paragraphs 0010 to 0081 of JP-A No.
  • 2010-1111750 may be used. Incorporated.
  • 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 colorant having an absorption maximum in the wavelength range of 800 to 900 nm is preferably a pyrrolopyrrole compound.
  • the pyrrolopyrrole compound may be a pigment or a dye, but a pigment is preferred because it is easy to obtain a curable composition capable of forming a film having excellent heat resistance.
  • the description in paragraphs 0017 to 0047 of JP-A-2009-263614 can be referred to, and the contents thereof are incorporated in the present specification.
  • Specific examples thereof include compounds described in paragraphs 0049 to 0058 of JP-A-2009-263614, and the contents thereof are incorporated in the present specification.
  • the dye multimer described in paragraphs 0027 to 0200 of International Publication No. 2014/142144 and the dye multimer described in paragraphs 0018 to 0078 of JP 2011-242752 A can be preferably used.
  • the curable composition of this invention may contain the extender as needed.
  • extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more.
  • the amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant.
  • the colorant and extender can be used with their surface modified with a polymer in some cases.
  • black pigments or pigments that excel in light transmission in the visible wavelength range and have a function of blocking light in the infrared wavelength range red, blue, yellow, green, purple, etc. as required
  • the above-mentioned colored organic pigments or dyes may be included.
  • red pigments or dyes Is preferably used in an amount of 1 to 40% by weight based on a black pigment or a pigment having an excellent light transmittance in the visible wavelength range and a function of blocking light in the infrared wavelength range.
  • Pigment Red 254 is preferable.
  • the content of the colorant (particularly preferably black pigment) in the composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 35 to 60% by mass with respect to the total solid content in the composition. % Is more preferable.
  • the composition of the present invention preferably contains a dispersant.
  • the dispersant contributes to the improvement of the dispersibility of the color pigment such as titanium black described above.
  • a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
  • dispersant examples 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 a dispersion such as a colorant such as a black pigment and a pigment used in combination, if desired, and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
  • adsorbing the surface of titanium black and the above-described dispersion material containing titanium black and Si atoms it is possible to promote the adsorptivity of the polymer compound.
  • the polymer compound preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of colored pigments such as black pigments and dispersion stability after aging because the graft chain has an affinity with a solvent. It is.
  • the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development. When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably has a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
  • the graft chain is made of at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure.
  • the graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
  • the structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.
  • AA-6 trade name, Toa Gosei Co., Ltd.
  • AA-10 Product name, manufactured by Toa Gosei Co., Ltd.
  • AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • AS-6 trade name, produced by Toa Gosei Co., Ltd.
  • AN-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • Co., Ltd. AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation), and the like.
  • the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represents hydrogen. An atom or a methyl group is more preferable, and a methyl group is 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 represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited. 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, etc. Is mentioned.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represents an integer of 2 or more, in Formula (1) and Formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoints of dispersion stability and developability.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
  • X 1, Y 1, Z 1 and n are the same as X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of dispersion stability and developability.
  • X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
  • the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a range of 5 to 30%.
  • the structural unit having a graft chain is contained within this range, the dispersibility of a colored pigment such as a black pigment (especially titanium black particles) is high, and the developability when forming a cured film is good.
  • the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • 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 has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1 to 6
  • An alkyl group (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 Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), or combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and even more preferably 1-10.
  • 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 number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and even more preferably 1-10.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included.
  • bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [4 .4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic 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, fluorine, chlorine, bromine, etc.), or 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 an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Embedded in.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming an interaction with a colored pigment such as a black pigment (particularly titanium black).
  • the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment.
  • the functional group capable of forming an interaction with the colored pigment such as the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit having an acid group, the structural unit having a basic group, or a coordinating group respectively. It is preferable to have a structural unit having or a reactive structural unit.
  • the polymer compound since the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of a colored pigment such as a black pigment has alkali solubility in the composition of the present invention.
  • a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound has a structural unit which has an acid group
  • the acid group in the structural unit having an acid group easily interacts with a color pigment such as a black pigment, and the polymer compound stably disperses the color pigment such as a black pigment, This is presumably because the viscosity of the polymer compound to be dispersed is low and the polymer compound itself is easily dispersed stably.
  • the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and particularly preferred is a carboxylic acid group that has good adsorptive power to colored pigments such as black pigments and has high dispersibility.
  • the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units having an acid group.
  • the polymer compound may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is calculated in terms of mass with respect to the total mass of the polymer compound. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom, There are amide groups and the like, and particularly preferred is a tertiary amino group which has a good adsorptive power to colored pigments such as black pigments and has high dispersibility.
  • the polymer compound can have one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppression of developability inhibition.
  • a coordinating group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment, and a functional group having reactivity
  • a functional group capable of forming an interaction with a colored pigment such as a black pigment
  • a functional group having reactivity for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride
  • examples include acid chlorides.
  • an acetylacetoxy group which has a good adsorptive power to colored pigments such as black pigments and high dispersibility.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
  • the polymer compound in the present invention has a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, it forms an interaction with various colored pigments such as the black pigment as described above.
  • the functional group is not particularly limited as long as the functional group can be introduced, and how these functional groups are introduced, but the polymer compound is represented by the following general formulas (iv) to (vi) It is preferable to have one or more structural units selected from structural units derived from monomers.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
  • R 12 and R 13 are more preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ — , wherein R 31 'represents an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), or combinations thereof, and the like.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and even more preferably 1-10.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group.
  • a carboxylic acid group is more preferable.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, , methyl group, ethyl group, propyl group, etc.), - represents a Z 1 or L 1 -Z 1,.
  • L 1 and Z 1 has the same meaning as L 1 and Z 1 in the above, are the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is methine. Compounds that are groups are preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and L 1 is a single bond or an alkylene group, A compound in which Z is a carboxylic acid group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydride Etc. hydroxyphenyl methacrylamide.
  • the content of the structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment is from the viewpoint of interaction with the colored pigment such as a black pigment, dispersion stability, and permeability to a developer.
  • 0.05 mass% to 90 mass% is preferable with respect to the total mass of the polymer compound, 1.0 mass% to 80 mass% is more preferable, and 10 mass% to 70 mass% is still more preferable.
  • the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and a colored pigment such as a black pigment, as long as the effects of the present invention are not impaired.
  • Other structural units having various functions different from structural units having a functional group capable of forming an interaction for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. More preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g.
  • the range is as follows. 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. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of a colored pigment such as a black pigment (particularly titanium black) or a dispersion containing titanium black and Si atoms can be further suppressed, and coarse particles The number can be reduced, and the temporal stability of the composition can be further improved.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by a GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film.
  • GPC gel permeation chromatography
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • Disperse Aid 6 Disper manufactured by Sannopco Corporation Polymer dispersing agents such as Suede 8, Disperse Aid 15, Disperse Aid 9100, etc., “ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F95, F77, P84, manufactured by ADEKA Corporation F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.
  • Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to paragraphs 0075 to 0133 in US2011 / 0124824.
  • it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the content of the dispersant in the composition of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the composition.
  • the composition of this invention contains a polymerization initiator.
  • a polymerization initiator There is no restriction
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
  • Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and more preferred are trihalomethyltriazine compounds.
  • the curable composition of the present invention when used for the production of a light-shielding film for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it is developed without any problems. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
  • an oxime compound as the photopolymerization initiator.
  • stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low.
  • an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
  • the photopolymerization initiator for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • the photopolymerization initiator include oxime compounds.
  • an oxime initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Examples of the oxime compound that can be suitably used in the present invention 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) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M.
  • oxime compounds other than those described above compounds described in JP-A-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, 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 at the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the 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 oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
  • 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.
  • 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 above-described substituents.
  • 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 above-described substituents.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
  • a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.
  • R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When 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, wherein X is 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 the 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 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the 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 that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and particularly 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 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • For the molar extinction coefficient of the compound a known method can be used.
  • an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
  • the content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to the total solid content of the curable composition. Within this range, better sensitivity and pattern formability can be obtained.
  • the curable composition of the present invention may contain only one type of polymerization initiator or two or more types of polymerization initiators. When two or more types are included, the total amount is preferably within the above range.
  • the content of the polymerization initiator in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and more preferably 1 to 10% by mass with respect to the total solid content in the composition. Further preferred.
  • the composition of this invention contains a polymeric compound.
  • the polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.
  • the polymerizable compound preferably contains 2 to 10 ethylenically unsaturated groups, and is preferably a so-called polyfunctional polymerizable compound. Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C.
  • polyethylene glycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth)
  • compounds obtained by adding (meth) acrylate after adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 as general formula (1) and general formula (2) together with specific examples thereof Can also be used.
  • dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and structures in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferred.
  • oligomer types can also be used.
  • urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having 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.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 are used.
  • a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained.
  • Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Further, ethylenically unsaturated compounds having an acid group are also suitable.
  • Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
  • the polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound. Examples of the tetrafunctional or higher acrylate compound include KAYARD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.).
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination aspect can be suitably set according to the physical property etc. which are requested
  • the aspect which combines 2 or more types of polymeric compounds selected from the polyfunctional acrylate compound mentioned above is mentioned, for example, As an example, dipentaerythritol hexaacrylate is mentioned. And a combination of pentaerythritol triacrylate.
  • the content of the polymerizable compound is preferably 3 to 55% by mass, and more preferably 7 to 50% by mass with respect to the total solid content in the curable composition of the present invention.
  • Binder polymer The composition of the present invention contains a binder polymer.
  • a linear organic polymer is preferably used.
  • a linear organic polymer a well-known thing can be used arbitrarily.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development.
  • an alkali-soluble resin a resin having a group that promotes alkali-solubility
  • the binder polymer is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
  • binder polymer examples include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a carboxyl group alone or copolymerized, having acid anhydrides Examples thereof include resins obtained by hydrolyzing, half-esterifying, or half-amidating an acid anhydride unit by mono- or copolymerizing monomers, and epoxy acrylates obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride.
  • radical polymers having a carboxylic acid group in the side chain such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, Those described
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxyl styrene, and examples of the monomer having an acid anhydride include maleic anhydride.
  • An acid etc. are mentioned.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder polymer.
  • the definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable 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 preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Particularly preferred are carboxylic acid groups.
  • the structural unit having an acid group preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).
  • R 21 , R 22 , and R 23 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 21 , R 22 , and R 23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
  • R 21 and R 23 are more preferably a hydrogen atom.
  • X 2 in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (viii) represents a methine group or a nitrogen atom.
  • L 2 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 41 ′ —
  • R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and even more preferably 1-10.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 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 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 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.), or an alkyl group having 1 to 6 carbon atoms (eg, , methyl group, ethyl group, 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 an 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 methine.
  • Compounds that are groups 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 polymer can be synthesized by the same method as the above-described pigment dispersant having a structural unit having a graft chain, and the preferred acid value and weight average molecular weight are also the same.
  • the binder polymer may have one or more structural units having an acid group.
  • the content of the structural unit having an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder polymer, and more preferably from the viewpoint of suppressing damage to the image strength due to alkali development. 10 to 90%.
  • the content of the binder polymer in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
  • composition of the present invention contains a solvent.
  • the solvent include water and organic solvents.
  • organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • the amount of the solvent contained in the composition of the present invention is preferably 10 to 90% by mass and more preferably 20 to 85% by mass with respect to the total mass of the composition.
  • a silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
  • a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond 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 has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
  • the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded). Includes silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Desirably not.
  • the silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
  • R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
  • the silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
  • the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
  • a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
  • the molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.
  • silane coupling agent X represented by the formula (W).
  • R z1 represents a hydrolyzable group, and the definition is as described above.
  • R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
  • Lz represents a single bond or a divalent linking group.
  • examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR 12 —, —CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
  • a group consisting of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
  • R 12 represents a hydrogen atom or a methyl group.
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
  • Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group, and / or an amino group that can be substituted with an aryl group, silyl Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like.
  • substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group, or a salt thereof.
  • at least one hydrolyzable group is bonded to the silicon atom.
  • the definition of 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 has at least one organic group.
  • the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
  • examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof.
  • substituents may further have a substituent
  • substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
  • the nitrogen atom is couple
  • Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
  • the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
  • the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
  • the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).
  • the content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the composition. More preferably, it is 0 to 6% by mass.
  • composition of the present invention may contain one silane coupling agent or two or more silane coupling agents.
  • silane coupling agents When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
  • the composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
  • an ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292
  • 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 composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition. 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is more preferable.
  • the composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc.
  • the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
  • the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
  • Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC. K etc. are mentioned.
  • 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, Sparse 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-10
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
  • silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.
  • the following components may be further added to the composition of the present invention.
  • Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, and sensitizers, and adhesion to the substrate surface.
  • Accelerators and other auxiliary agents for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.
  • You may add a well-known additive as needed.
  • These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No.
  • JP2008-250074A Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .
  • the solid content concentration of the composition of the present invention is preferably 5 to 50% by mass, and more preferably 15 to 40% by mass in terms of the balance between the thickness of the formed cured film and light shielding properties.
  • composition of the present invention can be prepared by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
  • the composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
  • polypropylene (including high density polypropylene) and nylon are preferable.
  • 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 still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • 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. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter described above 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 method for producing a cured film according to the present invention includes the first step of spray-coating the curable composition so that the landing size is D1, and forming the first coating film, and the curing so that the landing size is D2.
  • a cured film is obtained.
  • the “first coating film” is cured by the curing process to become a “first film”.
  • the “second coating film” is cured by the above curing process to become a “second film”.
  • FIG. 1A and FIG. 1B are explanatory views showing an example of a method for producing a cured film of the present invention step by step as described above.
  • the first step is a step of forming the first coating film by spraying the curable composition so that the landing size is D1.
  • the curable composition when the curable composition is sprayed from the nozzle 210 of the spray device, the curable composition flies as a plurality of droplets, and the plurality of droplets are formed on the substrate. Land on 100 surfaces (surface to be coated). The droplets to which the surface to be coated is attached are dried to become granular materials 120a. The aggregate of a plurality of the granular materials 120a constitutes the first coating film 120A.
  • the type of substrate used is not particularly limited.
  • various members in the solid-state imaging device for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a solid-state imaging
  • the element back surface etc. are mentioned preferably.
  • it does not specifically limit as a spray apparatus A well-known apparatus can be used.
  • the landing size in the present invention is the diameter of a granular material obtained by drying droplets generated by spraying the curable composition from the nozzles of the spray device when the droplets adhere to the glass substrate.
  • I mean.
  • the impact size is determined by observing the granular material adhering to the glass substrate with an optical microscope, assuming that the granular material is a circle (equivalent diameter of a circle), measuring 500 granular materials, and calculating this. Obtained by averaging.
  • the drying conditions in the case of measuring a landing size are not specifically limited, What is necessary is just to carry out on the conditions that 80 mass% or more volatilizes among the volatile components (solvent etc.) contained in a droplet.
  • the landing size D1 is preferably 35 to 150 ⁇ m, more preferably 40 to 145 ⁇ m, and even more preferably 45 to 140 ⁇ m. When the landing size D1 is within the above range, the lithography performance of the cured film is further improved.
  • the landing size can be controlled by appropriately setting spraying conditions.
  • Preferred conditions for controlling the landing size include nozzle height at spray application, atomization pressure, hydraulic pressure, nozzle opening diameter, and the like.
  • the nozzle height at the time of spray coating refers to the distance between the tip of the nozzle of the spray device (portion where the curable composition is ejected from the nozzle) and the surface to be coated (the surface of the substrate 100 in FIG. 1A).
  • the nozzle height L1 (distance L1) is preferably 10 cm or less, more preferably less than 5 cm, further preferably 4 cm or less, and particularly preferably 3 cm or less. Moreover, as a lower limit, 1 cm or more is preferable and 2 cm or more is more preferable. By setting the nozzle height L1 to less than 5 cm, volatilization of volatile components during the flight of droplets can be suppressed, so that the landing size can be increased.
  • the lithography performance of the cured film is further improved. Moreover, since it is possible to suppress the landing droplets from sagging by setting the nozzle height L1 to 1 cm or more, it is possible to suppress the rough surface state of the first coating film and the occurrence of pinholes in the cured film. There is an advantage.
  • An atomization pressure means the pressure applied to a curable composition in order to inject a curable composition from the nozzle of a spray apparatus.
  • Atomization pressure in the first step is preferably 300 ⁇ 500g / cm 2, more preferably 350 ⁇ 490g / cm 2, more preferably 380 ⁇ 480g / cm 2.
  • the atomization pressure is 500 g / cm 2 or less, the amount of gas mixed when the curable composition is ejected from the nozzle can be reduced, so that the droplets are difficult to dry. Thereby, since a landing size can be enlarged, the lithography performance of a cured film can be improved more.
  • the curable composition can be more favorably ejected from the nozzle.
  • the hydraulic pressure refers to the pressure applied to the curable composition in order to supply the curable composition to the nozzle.
  • the fluid pressure in the first step preferably 10 ⁇ 32g / cm 2, more preferably 10 ⁇ 30g / cm 2, more preferably 15 ⁇ 28g / cm 2, 18 ⁇ 25g / cm 2 is particularly preferred. Since the liquid pressure is 32 g / cm 2 or less, it is possible to suppress the landing droplets from sagging, and thus it is possible to suppress the roughness of the surface state of the first coating film. Therefore, the surface roughness Ra of the first film can be reduced. Can be small. Since the landing size can be increased when the liquid pressure is 10 g / cm 2 or more, the lithography performance of the cured film can be further improved.
  • the first coating film is cured into a “first film” by a curing process described later.
  • the film thickness T1 of the first film is preferably 1 to 5 ⁇ m, more preferably 2.2 to 4.0 ⁇ m, and even more preferably 2.5 to 3.8 ⁇ m.
  • the film thickness T1 is 2.2 ⁇ m or more, there is an advantage that generation of pinholes can be further suppressed.
  • the film thickness T1 is 4.0 ⁇ m or less, there is an advantage that the height of the device can be reduced.
  • the film thickness T1 is an average thickness, and is a value obtained by measuring thicknesses of five or more arbitrary points of the first film and arithmetically averaging them.
  • membrane refers to the film thickness obtained by hardening
  • the film thickness can be adjusted by the number of times the coating film is applied, the moving speed of the nozzle, the pitch, and the like.
  • the surface roughness Ra of the first film is preferably 0.01 to 0.6 ⁇ m, more preferably 0.01 to 0.5 ⁇ m, further preferably 0.01 to 0.2 ⁇ m, and 0.01 to 0.1 ⁇ m. Particularly preferred. There exists an advantage that lithography performance improves more because the surface roughness Ra of a 1st film
  • the surface roughness Ra of the first film can be measured using a surface atomic force microscope (Nanoscope 4A, manufactured by Nihon Beco). Further, the surface roughness Ra of the first film means the surface roughness Ra of the film obtained by curing the first coating film obtained by performing only the first process without performing the second process. Point to.
  • the first step may include a process of drying the droplets adhering to the surface to be coated after spraying the curable composition.
  • the method for the drying treatment is not particularly limited, and examples thereof include a method of heating the surface to be coated (substrate) with a hot plate or the like. Such a drying process is sometimes referred to as a pre-bake process.
  • the conditions for the drying treatment are not particularly limited, but it is usually 80 to 120 ° C. for 1 to 5 minutes for a hot plate and 80 to 120 ° C. for 0.5 to 2 hours for an oven.
  • the second step is a step of forming the second coating film by spray coating the curable composition so that the landing size is D2.
  • the second step may be performed before the first step or after the first step, but may be performed after the first step from the viewpoint that the effect of the present invention is more exhibited. preferable.
  • FIG. 1B shows a mode in which the second step is performed after the first step.
  • the curable composition when the curable composition is sprayed from the nozzle 210 of the spray device, the curable composition flies into a plurality of droplets, and the plurality of droplets fly to the surface of the first coating film 120A ( Land on the coated surface.
  • the droplets adhering to the surface of the first coating film 120A are dried to become the granular material 120b.
  • a collection of a plurality of the granular materials 120b constitutes the second coating film 120B.
  • the landing size D2 is preferably 1 to 30 ⁇ m, more preferably 1 to 20 ⁇ m, and even more preferably 1 to 10 ⁇ m.
  • the landing size D2 is within the above range, the reflectance of the cured film can be further reduced.
  • the landing size D2 is obtained by observing the granular material adhering to the glass substrate with an optical microscope, assuming that the granular material is a circle (equivalent circle diameter), measuring 500 granular materials, and calculating the arithmetic average. It is obtained by.
  • the nozzle height L2 (distance L2) is preferably 8 cm or more, more preferably more than 10 cm, still more preferably 12 cm or more, and particularly preferably 13 cm or more. Moreover, as an upper limit, 20 cm or less is preferable and 15 cm or less is more preferable.
  • the nozzle height L2 By setting the nozzle height L2 to more than 10 cm, volatilization of volatile components during the flight of droplets can be promoted, so that the landing size can be further reduced. Thereby, the reflectance of a cured film can be reduced more. Further, by setting the nozzle height L2 to 15 cm or less, it is possible to reduce the number of repetitions of application for obtaining a desired film thickness, and to shorten the process time.
  • the nozzle height L2 (distance L2) refers to the distance between the tip of the nozzle 210 of the spray device and the surface of the first coating film 120A.
  • Atomization pressure in the second step is preferably 300 ⁇ 500 g / cm 2, more preferably 400 ⁇ 500 g / cm 2, more preferably 410 ⁇ 450g / cm 2.
  • the atomization pressure is 450 g / cm 2 or less, the droplets are completely dried until they land after being ejected from the nozzles, and the inside of the coater (in the spray device, the region where the droplets adhere to the coated surface) ) Can be prevented from floating as particles, and hence particles can be prevented from adhering to the coated surface. Thereby, it can suppress that a particle contaminates another apparatus, or it can suppress that a particle adheres to the back surface of a board
  • the amount of the gas mixed when spraying a curable composition from a nozzle can be increased because an atomization pressure is 300 g / cm ⁇ 2 > or more, a droplet becomes easy to dry. Thereby, since a landing size becomes small, the reflectance of a cured film can be reduced more.
  • the fluid pressure in the second step is preferably 10 ⁇ 30 g / cm 2, more preferably 15 ⁇ 25 g / cm 2, more preferably 17 ⁇ 24g / cm 2.
  • the hydraulic pressure is 25 g / cm 2 or less, the landing size can be further reduced.
  • the hydraulic pressure is 10 g / cm 2 or more, the phenomenon that the curable composition is dried in the nozzle and clogging occurs can be suppressed.
  • the second coating film is cured into a “second film” by a curing process described later.
  • the film thickness T2 of the second film is preferably 0.1 to 2 ⁇ m, more preferably 0.1 to 1.5 ⁇ m, and further preferably 0.1 to 1.2 ⁇ m.
  • the film thickness T2 is an average thickness, and is a value obtained by measuring thicknesses of five or more arbitrary points of the second film and arithmetically averaging them.
  • the film thickness of the second film refers to the thickness of the film obtained by curing the second coating film obtained by performing only the second process without performing the first process.
  • the thickness of the obtained cured film is preferably 2.0 to 8.0 ⁇ m, more preferably 2.5 to 6.0 ⁇ m, and 3.0 More preferably, it is -5.0 ⁇ m.
  • the surface roughness Ra of the second film is preferably 0.1 to 2.0 ⁇ m, more preferably 0.1 to 1.5 ⁇ m, and further preferably 0.1 to 1.0 ⁇ m.
  • the surface roughness Ra of the second film can be measured by the same method as that for the first film.
  • the surface roughness Ra of the second film means the surface roughness Ra of the film obtained by curing the second coating film obtained by performing only the second process without performing the first process. Point to.
  • the surface roughness Ra of the obtained cured film is 0.1 to 1 0.2 ⁇ m is preferable, 0.1 to 0.8 ⁇ m is more preferable, 0.1 to 0.5 ⁇ m is further preferable, and 0.1 to 0.3 ⁇ m is particularly preferable.
  • the second step may include a treatment (prebaking treatment) for drying the droplets adhering to the surface to be coated after spraying the curable composition. Since the method and conditions for the drying treatment are the same as those in the first step, the description thereof is omitted.
  • prebaking treatment for drying the droplets adhering to the surface to be coated after spraying the curable composition. Since the method and conditions for the drying treatment are the same as those in the first step, the description thereof is omitted.
  • the landing size D1 and the landing size D2 satisfy the relationship D1> D2.
  • the ratio D1 / D2 between the landing size D1 and the landing size D2 is 5 to 150, preferably 10 to 140, more preferably 10 to 100, and still more preferably 15 to 85.
  • the ratio D1 / D2 is within the above range, the cured film has excellent lithography performance and reflectance.
  • the ratio D1 / D2 is less than 5, there are problems that the lithography performance of the cured film is lowered or the reflectance becomes too high.
  • the ratio D1 / D2 exceeds 150, the lithography performance of the cured film is deteriorated.
  • the nozzle height L1 (distance L1) in the first step is preferably smaller than the nozzle height L2 (distance L2) in the second step. This makes it easy to control the landing size.
  • the ratio T2 / T1 between the film thickness T1 of the first film and the film thickness T2 of the second film is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, 0.75 is more preferable. When the ratio T2 / T1 is within the above range, the lithographic performance and reflectance of the cured film can be further improved.
  • the surface roughness Ra of the first film is preferably smaller than the surface roughness Ra of the second film. Thereby, there exists an advantage that it can suppress that the lithography performance of a cured film falls, or can suppress that a reflectance becomes high.
  • the manufacturing method of the cured film of this invention has the process (cured film formation process) which implements a hardening process and forms a cured film.
  • the first coating film is cured to become the first film
  • the second coating film is cured to become the second film.
  • the cured film forming step may be performed at the respective timings after the first step and the second step, or may be performed collectively after the completion of both the first step and the second step.
  • a photocuring process and a thermosetting process are preferably performed, and a photocuring process (particularly, a curing process by irradiation with actinic rays or radiation) from the viewpoint of easy pattern formation.
  • a photocuring process particularly, a curing process by irradiation with actinic rays or radiation
  • the conditions for the curing treatment are not particularly limited, and may be performed according to known conditions.
  • the cured film of the present invention may be a so-called patterned cured film formed with a pattern.
  • Examples of a method for forming a patterned cured film include an embodiment in which a development process is performed after performing an exposure process in a pattern in the above-described cured film forming process (hereinafter also referred to as an “exposure process”). .
  • the coating film (first coating film and second coating film) formed on the substrate is irradiated with actinic rays or radiation.
  • a cured film that has been exposed in a pattern is formed by performing an exposure process, and then a development process is performed in which the cured film that has been exposed in a pattern is alkali-developed.
  • a 1st process and a 2nd process the description is abbreviate
  • the coating film obtained as described above (the first coating film and the second coating film) is exposed by irradiation with actinic rays or radiation through a mask, and the coating film portion irradiated with light is exposed. Only cure. As a result, a non-irradiated portion and a portion exposed in a pattern (that is, a cured film exposed in a pattern) are formed.
  • the exposure is preferably performed by irradiation with radiation.
  • radiation that can be used for exposure ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is preferred as a light source.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • a development step (Development process) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains. In this way, a patterned cured film is obtained.
  • the developer it is desirable to use an organic alkali developer.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as the inorganic developer, ammonia water, ethylamine, diethylamine as the organic alkali developer.
  • Dimethylethanolamine tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4 , 0] -7-undecene and the like, an alkaline aqueous solution in which the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. It is.
  • a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • the cured film according to the present embodiment is a cured film obtained by using the above-described curable composition and formed on a substrate, from the first surface of the cured film on the substrate side, to the first
  • the void ratio at the position where the thickness of the cured film is 10% toward the second surface of the cured film facing the surface is A1, and the thickness of the cured film is from the second surface toward the first surface.
  • the cured film according to the present embodiment is also simply referred to as “cured film”.
  • the cured film has a low reflectance and excellent lithography performance.
  • the reason is as follows.
  • the curable composition is sprayed from a nozzle of a spray device, the curable composition is ejected as a plurality of droplets, which land on the surface to be coated.
  • the liquid droplets that have landed on the surface to be coated are dried to become a granular material composed of the solid content contained in the liquid droplets.
  • one film (coating film) is formed, and a cured film is obtained by drying the coating film.
  • a gap without a material constituting the cured film is formed in the cured film.
  • the gap is referred to as a “gap”, and a more detailed definition of the gap will be described later.
  • the porosity A1 at a position close to the first surface of the cured film on the substrate side is smaller than the porosity A2 at a position facing the first surface. That is, it can be said that the first surface side on the substrate side has fewer voids than the second surface side, which is the surface of the cured film.
  • the first surface and the region in the vicinity of the first surface are films with few pinholes, the occurrence of pinholes in the cured film is suppressed, and chipping of the pattern shape of the cured film is suppressed.
  • the permeability of the developer and the like is different, and therefore it is assumed that the development near the interface with the substrate proceeds uniformly when the gap is small.
  • the refractive index inside and outside the gap differs between the second surface on the surface side and the region in the vicinity thereof, the reflectance of the cured film can be lowered and the penetration of the developer is promoted. Further, chipping of the pattern shape of the cured film and occurrence of pinholes are suppressed.
  • the ratio A1 / A2 between the porosity A1 and the porosity A2 is preferably 0.00001 or more and less than 0.9 from the viewpoint of obtaining the desired effect of the present application, and is 0.0001 or more and 0. Less than 8 is more preferable. From the viewpoint of obtaining the desired effect of the present application more remarkably, 0.0001 or more and less than 0.7 is particularly preferable.
  • the porosity A1 is preferably 3.5% or less, more preferably 0.001% or more and less than 3%, still more preferably 0.01% or more and less than 3%, and 0.1% % To less than 3% is particularly preferable.
  • the porosity A1 is within this range, the desired effect of the present application is remarkably obtained.
  • the development is promoted when the porosity A1 is 0.001% or more, chipping of the pattern shape of the cured film is more easily suppressed. As described above, chipping of the pattern shape of the cured film, generation of pinholes, and the like are more easily suppressed. A method for measuring the porosity will be described later.
  • the porosity A2 is preferably 0.05 to 35%, more preferably 0.1% or more and less than 30%, further preferably 1 to 20%, particularly 2 to 10%. preferable.
  • the porosity A2 is in the above range, the desired effect of the present application is remarkably obtained. Since the refractive index inside and outside the gap is different within the above range, the reflectance (especially specular reflection light) can be further reduced, and the void near the surface (second surface) of the cured film is developed by the development process. Since the holes are opened to promote the formation of the uneven surface shape of the cured film and diffuse light, the reflectance can be further lowered while maintaining other effects.
  • the void when the void is 1% or more, development is more easily promoted, and when it is less than 30%, a fine pattern shape is more easily formed, and chipping of the pattern shape of the cured film is more easily suppressed.
  • a method for measuring the porosity will be described later.
  • the preferable range and measurement method of the surface roughness Ra of the cured film according to the present embodiment are the same as the surface roughness Ra of the cured film described in the section of the method for producing a cured film described above.
  • the cured film according to the present embodiment preferably has at least two layers.
  • the cured film which concerns on this embodiment is not limited to this, It is preferable that it is manufactured by the method demonstrated by the term of the manufacturing method of the cured film mentioned above.
  • the region (layer) including the first surface and including the position where the porosity is A1 corresponds to the first film described above.
  • the region (layer) including the second surface and including the position where the porosity A2 is obtained corresponds to the above-described second film.
  • the measuring method of each porosity (A1 and A2) mentioned above is as follows.
  • the porosity of the curable composition layer is measured from a photographic image obtained by photographing a cross section of the exposed portion (cured portion) of the cured film by an image analysis method (for example, a cross-sectional image by a scanning electron microscope).
  • the obtained cross-sectional image may be subjected to image analysis as necessary.
  • a region other than the cured film that is, a region not surrounded by the cured film in the cured film
  • the area (number of pixels) of the entire void is determined.
  • the porosity (%) is obtained. More specifically, the porosity A1 is calculated based on a cross-sectional image in the region where the thickness of the cured film is 10 ⁇ 5% from the first surface toward the second surface.
  • the porosity A2 is calculated based on a cross-sectional image in the region where the thickness of the cured film is 10 ⁇ 5% from the second surface toward the first surface.
  • the magnification of the photographic image is not particularly limited as long as it can be easily distinguished, but it is preferably in the range of 3000 to 20000 times.
  • the above-described cured film can be suitably applied as a so-called light shielding film.
  • a light shielding film can be suitably applied to a solid-state imaging device.
  • the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic substrate 5 made of ceramic that holds the circuit board 4. And.
  • the solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) toward the CMOS sensor 3, a photographing lens 7, and a lens holder 8 that holds the photographing lens 7. And a holding cylinder 9 that holds the lens holder 8 movably.
  • a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3.
  • the ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds the side surface of the CMOS sensor 3.
  • the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy adhesive, the same applies hereinafter).
  • an adhesive for example, an epoxy adhesive, the same applies hereinafter.
  • Various circuit patterns are formed on the circuit board 4.
  • a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a.
  • the IR cut filter 6 is formed in a size slightly larger than the opening 5a, and is fixed to the ceramic substrate 5 with an adhesive so as to cover the opening 5a.
  • a CMOS sensor 3 is disposed behind the photographic lens 7 (downward in FIGS. 3 and 4), and an IR cut filter 6 is disposed between the photographic lens 7 and the CMOS sensor 3. The subject light enters the light receiving surface of the CMOS sensor 3 through the photographing lens 7 and the IR cut filter 6. At this time, the infrared light is cut by the IR cut filter 6.
  • the circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2.
  • an electronic device for example, a digital camera
  • CMOS sensor 3 a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.
  • the light shielding film (light shielding layer) 11 described above is disposed over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided. A cut filter is formed.
  • the reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 3 and 4) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus.
  • the reflected light R2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image.
  • the light shielding film 11 shields harmful light such as reflected light R ⁇ b> 1 and R ⁇ b> 2 toward the CMOS sensor 3.
  • the light shielding film 11 corresponds to the above-described cured film. 3 and 4, the thickness of the light shielding film 11 is exaggerated.
  • FIG. 5 shows a solid-state imaging device 20 according to the second embodiment.
  • the solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • the above-described light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference.
  • the light shielding film 21 shields harmful light such as reflected light R ⁇ b> 3 directed toward the CMOS sensor 3.
  • FIG. 6 shows a solid-state imaging device 30 according to the third embodiment.
  • the solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • the light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare is reliably suppressed.
  • FIG. 7 shows a solid-state imaging device 40 according to the fourth embodiment.
  • the solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • the light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
  • a light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5.
  • the cured film of the present invention can also be used for color filters.
  • the color filter can be suitably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and is particularly suitable for a high-resolution CCD or CMOS that exceeds 1 million pixels. It is.
  • the color filter can be used by being disposed, for example, between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for collecting light.
  • the color filter can be preferably used for an organic electroluminescence (organic EL) element.
  • organic EL element a white organic EL element is preferable.
  • the organic EL element preferably has a tandem structure.
  • JP 2003-45676 A supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc.
  • Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate.
  • the lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region.
  • the organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked.
  • the organic EL layer can include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer.
  • the organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked.
  • an organic EL element having an organic EL layer having such a structure can emit white light.
  • the spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm).
  • those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
  • the film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.7 ⁇ m or less.
  • the lower limit can be, for example, 0.1 ⁇ m or more, and can also be 0.2 ⁇ m or more.
  • the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and particularly preferably 1.7 ⁇ m or less.
  • the lower limit can be, for example, 0.1 ⁇ m or more, and can also be 0.2 ⁇ m or more.
  • the cured film (color filter, light-shielding film, etc.) of the present invention can be used for image display devices such as liquid crystal display devices and organic electroluminescence display devices.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic).
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter in the present invention.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
  • TTO-51N trade name: manufactured by Ishihara Sangyo
  • AEROSIL 300 registered trademark
  • Dispersant Disperbyk190 trade name: manufactured by Big Chemie
  • Gave a homogeneous aqueous mixture.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing. After the completion, the collected powder was pulverized in a mortar to obtain a powdery titanium black (A-1) [dispersed material containing titanium black particles and Si atoms] having a powdery specific surface area of 85 m 2 / g.
  • A-1 powdery titanium black [dispersed material containing titanium black particles and Si atoms] having a powdery specific surface area of 85 m 2 / g.
  • composition 1 The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.
  • the dispersant described below (polymer compound (G1); see the following formula) was synthesized with reference to the description in JP-A-2013-249417.
  • the weight average molecular weight of the polymer compound (G1) was 30,000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.
  • Composition 1 -Titanium black A-1 ... 25.0 parts by mass-Propylene glycol monomethyl ether acetate 20% by mass solution of polymer compound (G1) ...
  • ⁇ Curable composition 1> The components shown below were mixed and stirred to obtain a curable composition.
  • the spray coater (product name “DC110”, manufactured by Sanmei Co., Ltd.) performs the operation shown in FIG. 8 to form a film P having a predetermined size on the substrate 100.
  • the nozzle is moved in a first direction in which the curable composition is moved to one side in the first direction X while being sprayed from the nozzle 210 of the spray device, and in a second direction Y orthogonal to the first direction X.
  • the coating film P having a predetermined size is formed.
  • the coating film P of a predetermined size is laminated
  • - atomizing pressure (g / cm 2): In order to inject the curable composition from a nozzle of a spray device, the pressure-fluid pressure applied to the curable composition (g / cm 2): a curable composition to the nozzle Pressure applied to the curable composition to supply, nozzle opening scale: an index indicating the nozzle opening diameter. It shows that the opening diameter of a nozzle is so large that this figure is large.
  • Nozzle height (cm): Distance from the tip of the nozzle to the surface to be coated Speed (mm / s): Nozzle moving speed in the first operation Pitch (mm): Nozzle movement per second operation Distance / Number of times: Number of executions / repetition of the first operation for obtaining a coating film of a predetermined size: Number of times of coating a coating film of a predetermined size
  • a spray coater product name “DC111”, manufactured by Sanmei Co., Ltd.
  • the curable composition was applied to the surface of the 8-inch glass substrate (covered) under the conditions shown in Table 1 below (formation conditions for the first coating film).
  • a coating film was obtained by spraying onto the coated surface.
  • the obtained coating film was heated at 100 ° C. for 2 hours (pre-baking treatment) to obtain a first coating film.
  • the spray device using the spray device, the curable composition is sprayed onto the surface (surface to be coated) of the first coating film under the conditions shown in Table 1 below (formation conditions for the second coating film) to obtain a coating film. It was.
  • the obtained coating film was heated at 100 ° C.
  • the first coating film formed on the substrate is irradiated with light using a proxy exposure apparatus EVG610 (manufactured by EV Group Japan) so that the exposure power is 600 mJ / cm 2 at an irradiation power of 50 mW / cm 2. (Exposure) (exposure process).
  • EVG610 manufactured by EV Group Japan
  • Exposure process Exposure process.
  • the physical film thickness was measured using Dektak XT (manufactured by Bruker).
  • Exposure (exposure process).
  • the physical film thickness was measured using DektakXT (manufactured by Bruker).
  • Total film thickness of the first film and the second film Using a spray coater (product name “DC110”, manufactured by Sanmei Co., Ltd.), the curable composition was applied to the surface (covered) of an 8-inch glass substrate under the conditions shown in Table 1 below (formation conditions for the first coating film).
  • a coating film was formed by spraying onto the coated surface.
  • the obtained coating film was heated for 2 hours using an oven at 100 ° C. (prebaking treatment) to form a first coating film (first step).
  • the curable composition is sprayed onto the surface (application surface) of the first coating film under the conditions shown in Table 1 below (conditions for forming the second coating film). Formed.
  • the obtained coating film was heated for 2 hours using a 100 ° C. oven (prebaking treatment) to form a second coating film (second step).
  • proxy exposure apparatus EVG610 product made from EV group Japan
  • the sample was irradiated with light (exposure) (exposure process).
  • membrane was obtained (2nd film
  • the cured film (first film + second film) thus obtained was measured for physical film thickness using Dektak XT (manufactured by Bruker).
  • each film thickness is an average thickness, and is the value which measured the thickness of arbitrary 5 points
  • the film thicknesses of the first film and the second film are shown in Table 1, and the film thickness of the cured film (first film + second film) is shown in Table 2.
  • the spray coater (product name) is the same as the formation conditions of the first coating film shown in Table 1, except that the “number of times” and “repetition” are set to 1 in the formation conditions of the first coating film shown in Table 1.
  • DC110 manufactured by Sanmei Co., Ltd.
  • the curable composition was sprayed onto the surface (surface to be coated) of an 8-inch glass substrate to form a coating film.
  • the obtained coating film was heated for 2 hours using a 100 ° C. oven (pre-baking treatment) to obtain a sample for measurement of the landing size D1. About the measurement sample, five shots were taken using an optical microscope at a magnification of 50 times so as to include 500 or more landing marks (granular materials).
  • the spray coater (product name) is the same as the formation condition of the second coating film shown in Table 1, except that the “number of times” and “repetition” are set to 1 in the formation conditions of the second coating film shown in Table 1.
  • DC110 manufactured by Sanmei Co., Ltd.
  • the curable composition was sprayed onto the surface (surface to be coated) of an 8-inch glass substrate to form a coating film.
  • the obtained coating film was heated at 100 ° C.
  • the landing size D2 was measured in the same manner as the landing size D1.
  • the measurement results of the landing size D1 and the landing size D2 are shown in Table 1.
  • ⁇ Surface roughness Ra> (Surface roughness Ra of the first film) The first film was formed under the same conditions as the “(film thickness of the first film)”. About the obtained 1st film
  • Example 1 ⁇ Examples 11 to 26, Comparative Example 6>
  • Example 2 the impact sizes D1 and D2 were not changed, and only the atomization pressure, the hydraulic pressure, and the number of repetitions were appropriately adjusted to produce cured films of Examples 11 to 26 shown in Table 3. Evaluation similar to 1 was performed. Further, in Comparative Example 2, the impact sizes D1 and D2 were not changed, and only the atomization pressure, the hydraulic pressure, and the number of repetitions were adjusted as appropriate, and the cured film of Comparative Example 6 shown in Table 3 was produced. Evaluation similar to 1 was performed. Table 3 shows the evaluation results of the examples and comparative examples.
  • the porosity A1 is a cross-sectional image in a region where the thickness of the cured film is 10 ⁇ 5% from the first surface (surface on the substrate side) to the second surface (surface facing the substrate). It was obtained by calculating “the number of white dots / the number of black dots” by the above image analysis.
  • the porosity A2 is determined by the above image analysis based on the cross-sectional image in the region where the thickness of the cured film is 10 ⁇ 5% from the second surface to the first surface. It was obtained by calculating "number”. An image composed of white and black dots by image analysis was observed at a magnification of 10000 and averaged over 10 fields of the predetermined area as a porosity. The calculated porosity was evaluated according to the following criteria.
  • Example 27> When evaluation was performed in the same manner as in Example 2 except that the curable composition 2 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the curing A cured film as good as that of Example 2 was obtained in all of the film surface roughness and lithography performance.
  • ⁇ Curable composition 2> The components shown below were mixed and stirred to obtain a curable composition.
  • Example 28 In the preparation of the pigment dispersion of Example 1, instead of titanium black, carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m 2 / g, by gas black method. A pigment dispersion A was obtained in the same manner except that the produced carbon black was used.
  • a curable composition 3 was obtained in the same manner as in the curable composition 1 used in Example 1, except that the pigment dispersion used in the curable composition 1 was changed to the pigment dispersion A described above.
  • Example 1 When evaluation was performed in the same manner as in Example 1 except that the curable composition 3 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the curing A cured film as good as Example 1 was obtained in all of the film surface roughness and lithography performance.
  • Pigment dispersion B was obtained in the same manner except that Pigment Red 254 (trade name BK-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used instead of titanium black in preparation of the pigment dispersion of Example 1.
  • Pigment Red 254 trade name BK-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • the curable composition 4 was the same as the curable composition 1 except that 40.3 parts by mass of the pigment dispersion of Example 1 was changed to 33 parts by mass and 7.3 parts by mass of the pigment dispersion B was further added. Was made.
  • Example 1 When evaluation was performed in the same manner as in Example 1 except that the curable composition 4 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the curing A cured film as good as Example 1 was obtained in all of the film surface roughness and lithography performance.
  • Example 1 The pigment dispersion in Example 1 was changed from 40.3 parts by mass to 33.0 parts by mass, 1.8 parts by mass of the above-mentioned dye multimer (xanthene Xa) was further added, and PGMEA was further added by 5.5 parts by mass. In the same manner as in the curable composition 1, a curable composition 5 was obtained.
  • Example 1 When evaluation was performed in the same manner as in Example 1 except that the curable composition 5 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the curing A cured film as good as Example 1 was obtained in all of the film surface roughness and lithography performance.
  • Example 31 A curable composition 6 was prepared in the same manner as the curable composition 1 except that the polymerization initiator was changed to IRGACURE-907 (manufactured by BASF Japan).
  • Example 1 When evaluation was conducted in the same manner as in Example 1 except that the curable composition 6 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the cured film were evaluated. As a result, it was possible to obtain a film having the same surface roughness and lithography performance as those in Example 1.
  • the polymerizable compound of the curable composition 1 includes 0.5 parts of KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) and PET-30 (pentaerythritol triacrylate, Nippon Kayaku Co., Ltd.).
  • the curable composition 7 was prepared by the same method except having changed into 1.3 parts.
  • Example 1 When evaluation was performed in the same manner as in Example 1 except that the curable composition 7 was used instead of the curable composition 1, the impact size ratio, the thickness of the cured film, the ratio of the film thickness, the reflectance, and the curing A cured film as good as Example 1 was obtained in all of the film surface roughness and lithography performance.

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  • Optical Elements Other Than Lenses (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un film durci mettant en œuvre une composition durcissable qui contient un agent colorant, un initiateur de polymérisation, un composé polymérisable, un polymère liant, et un solvant, ledit procédé de fabrication de film durci comprenant : une première étape dans laquelle la composition durcissable est appliquée sous forme d'une pulvérisation présentant une taille d'impact D1 de manière à former un premier film de revêtement ; et une seconde étape dans laquelle la composition durcissable est appliquée sous forme d'une pulvérisation présentant une taille d'impact D2 de manière à former un second film de revêtement ; et une étape dans laquelle un processus de durcissement est réalisé de manière à former un film durci, D1 et D2 satisfaisant la relation D1>D2, et le rapport D1/D2 étant 5-150. L'invention concerne un film durci formé sur un substrat et obtenu à l'aide d'une composition durcissable qui contient un agent colorant, un initiateur de polymérisation, un composé polymérisable, un polymère liant, et un solvant, ledit film durci satisfaisant la relation A1<A2, où A1 est la porosité d'un emplacement qui représente 10 % de l'épaisseur du film durci depuis une première surface du film durci, la première surface étant sur le côté substrat, vers une seconde surface du film durci, ladite seconde surface étant opposée à la première surface, et A2 est la porosité d'un emplacement qui représente 10 % de l'épaisseur du film durci depuis la seconde surface vers la première surface.
PCT/JP2016/079642 2015-10-09 2016-10-05 Procédé de fabrication d'un film durci, film durci, élément d'imagerie à semi-conducteur, et dispositif d'affichage d'image WO2017061477A1 (fr)

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CN110095940A (zh) * 2018-01-30 2019-08-06 臻鼎科技股份有限公司 印刷电路板的制备方法以及感光树脂组合物
WO2023091193A3 (fr) * 2021-06-27 2023-10-12 SuperMetalix, Inc. Applications de blindage de borures métalliques et de composites associés

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WO2023091193A3 (fr) * 2021-06-27 2023-10-12 SuperMetalix, Inc. Applications de blindage de borures métalliques et de composites associés

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JP6595613B2 (ja) 2019-10-23
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TW201731927A (zh) 2017-09-16

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