WO2017208771A1 - 組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像装置及び画像表示装置 - Google Patents

組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像装置及び画像表示装置 Download PDF

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WO2017208771A1
WO2017208771A1 PCT/JP2017/017856 JP2017017856W WO2017208771A1 WO 2017208771 A1 WO2017208771 A1 WO 2017208771A1 JP 2017017856 W JP2017017856 W JP 2017017856W WO 2017208771 A1 WO2017208771 A1 WO 2017208771A1
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group
composition
compound
examples
pigment
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PCT/JP2017/017856
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English (en)
French (fr)
Japanese (ja)
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久保田　誠
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富士フイルム株式会社
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Priority to JP2018520758A priority Critical patent/JPWO2017208771A1/ja
Priority to KR1020187034341A priority patent/KR102149158B1/ko
Publication of WO2017208771A1 publication Critical patent/WO2017208771A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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 composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.
  • the black light shielding film is used for various applications.
  • the light shielding film is used in a solid-state imaging device.
  • a solid-state imaging device includes a photographing lens and a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor, complementary metal oxide semiconductor) disposed behind the photographing lens.
  • An element hereinafter, the solid-state image sensor is also referred to as an “image sensor”) and a circuit board on which the solid-state image sensor is mounted.
  • noise due to reflection of visible light may occur. Therefore, there is a case where a predetermined light shielding film is provided in the solid-state imaging device for the purpose of suppressing the generation of noise.
  • Another application of the light shielding film is a so-called black matrix.
  • Patent Document 1 states that “a black resin composition for a resin black matrix containing at least a light shielding material, a resin and a solvent, and containing at least titanium nitride particles as a light shielding material, and using CuK ⁇ rays as an X-ray source.
  • a black resin composition for a resin black matrix having a diffraction angle 2 ⁇ of a peak derived from the (200) plane of the titanium nitride particles of 42.5 ° or more and 42.8 ° or less is disclosed. 1).
  • the present inventor made a light-shielding film of a color filter disposed in a solid-state imaging device, a liquid crystal image device or the like using a black composition prepared based on Patent Document 1, and examined various performances thereof. It came to know that the light-shielding performance in a specific wavelength region is low (in other words, the optical density is low).
  • a dispersant is often used from the viewpoint of improving the dispersibility of the pigment.
  • the content of the dispersant in the composition is relatively increased, resulting in the light shielding performance of the resulting light shielding film. May decrease. Therefore, it is desirable to improve the light shielding performance of the light shielding film by means other than increasing the pigment concentration.
  • An object of this invention is to provide the composition which can form the light shielding film excellent in light-shielding performance in view of the said situation.
  • Another object of the present invention is to provide a cured film having excellent light shielding performance, a color filter including the cured film, a light shielding film, a solid-state imaging device, and an image display device.
  • an inorganic pigment preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride
  • the present invention has been completed by finding that the above-mentioned problems can be solved by using a composition containing. That is, it has been found that the above object can be achieved by the following configuration.
  • a composition comprising an inorganic pigment and a black dye.
  • the inorganic pigment is a pigment containing nitride or oxynitride.
  • the black dye has a polymerizable group.
  • the polymerizable group is an acryloyl group or a methacryloyl group.
  • the black dye is a xanthene dye or an azo dye.
  • compositions as described in (7) whose acid value of the said dispersing agent is 50 mgKOH / g or more.
  • (11) The composition according to any one of (1) to (10), further comprising an organic solvent.
  • the composition which can form the light shielding film excellent in light shielding performance can be provided.
  • 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.
  • the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also 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).
  • Actinic light or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. .
  • light means actinic rays or radiation.
  • exposure in the present specification is not limited to exposure with a deep ultraviolet ray, an X-ray, EUV light or the like represented by a mercury lamp or an excimer laser, but also a particle beam such as an electron beam and an ion beam. Include drawing in exposure.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acrylic and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • monomer and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from oligomers and polymers, 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 composition of the present invention contains an inorganic pigment (preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride) and a black dye.
  • an inorganic pigment preferably a black inorganic pigment described later, more preferably a pigment containing nitride or oxynitride
  • a black dye preferably a pigment containing nitride or oxynitride
  • a light shielding film having excellent light shielding performance can be formed. That is, according to the composition of the present invention, there is no reduction in the light shielding performance in a specific wavelength region, and the minimum optical density (hereinafter also referred to as “minimum OD value”) in a predetermined region (eg, visible light region to 1200 nm). It is possible to form a light shielding film in a range where sufficient light shielding ability can be provided.
  • the composition of the present invention is characterized in that it contains a black dye.
  • the content of the dispersant used for the purpose of improving the dispersibility of the inorganic pigment in the composition is relatively increased, resulting in this.
  • the light shielding performance of the resulting light shielding film may deteriorate.
  • the composition of the present invention does not require a dispersant and contains a black dye having absorption over almost the entire wavelength region of visible light, the minimum of the light-shielding film without increasing other components such as a dispersant.
  • the optical density can be improved.
  • the present inventor has recently found out that the above-described black dye preferably has a polymerizable group.
  • the black dye when the black dye has a polymerizable group, the dye is incorporated into the matrix constituting the film via the polymerizable group. It is known that dyes are generally inferior in heat resistance to pigments. When a dye is used as a constituent component of a light shielding film, the light shielding film may be inferior in heat resistance due to the dye.
  • the matrix constituting the film and the black dye are chemically bonded to each other by a polymerizable group, thereby improving heat resistance.
  • reworkability is required.
  • a color filter (cured film) produced using a composition containing an inorganic pigment, a black dye having a polymerizable group, an alkali-soluble resin, or the like is used, such as TMAH (tetramethylammonium hydroxide).
  • the black dye In the case of removing with an alkaline aqueous solution, since the black dye is chemically bonded to a film including an alkali-soluble resin, the dye can be removed (peeled) together with the matrix.
  • the black dye does not have a polymerizable group, that is, when the black dye is not chemically bonded to the matrix, the dye generally does not dissolve in an alkaline aqueous solution, so that the residue alone on the solid-state image sensor It becomes difficult to remove. That is, it is inferior to reworkability.
  • the black dye has an acryloyl group or a methacryloyl group as a polymerizable group
  • the patterning property (hereinafter also referred to as “resolution”) of the coating film formed by the composition of the present invention is further improved. I have also confirmed that.
  • the black dye is preferably a dye multimer. Heat resistance improves more because black dye is a dye multimer.
  • the black dye is preferably a dye multimer having a polymerizable group.
  • the composition of the present invention contains an inorganic pigment.
  • the inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
  • examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( 1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink.
  • a black inorganic pigment and as the inorganic pigment, carbon black, titanium black, and at least a content capable of forming a cured film having a high optical density is obtained.
  • Metal pigments are preferred. Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Products, metal nitrides, and metal oxynitrides.
  • inorganic pigments metal pigments containing titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, chromium oxide, chromium nitride, chromium oxynitride, iron oxide, iron oxynitride, silver, It is preferably at least one selected from the group consisting of a metal pigment containing tin and a metal pigment containing silver and tin. Especially, it is more preferable that an inorganic pigment is at least 1 sort (s) selected from the pigment containing the nitride or oxynitride mentioned later. In addition, an inorganic pigment may be used individually by 1 type, or may use 2 or more types together.
  • the content of the inorganic pigment is preferably 30 to 70% by mass with respect to the total solid content of the composition.
  • the content of the inorganic pigment is 30% by mass or more based on the solid content, the light shielding performance of the obtained light shielding film is further improved, and the heat resistance is also improved.
  • the content of the inorganic pigment is 70% by mass or less with respect to the solid content, reworkability and patterning property are further improved.
  • the content of the inorganic pigment is more preferably 35 to 70% by mass, and still more preferably 40 to 70% by mass with respect to the total solid content of the composition.
  • the inorganic pigment preferably has an average primary particle size in the range of 10 to 80 nm, and more preferably in the range of 10 to 50 nm.
  • the average primary particle diameter can be measured, for example, by the following method.
  • the average primary particle diameter of the inorganic pigment can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length)
  • Dmax maximum length at two points on the contour of the particle image
  • DV-max maximum vertical 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 is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
  • the inorganic pigment is preferably a pigment containing nitride or oxynitride.
  • the pigment containing nitride or oxynitride include pigments such as titanium nitride, titanium oxynitride, niobium nitride, niobium oxynitride, vanadium nitride, vanadium oxynitride, iron oxynitride, and tungsten oxynitride. It is done. Among them, those having absorption in the wavelength region of 400 to 1200 nm are preferable.
  • the absorption wavelength and optical density of the inorganic pigment and black dye described later can be measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). From the viewpoint of realizing a high optical density in a small amount, for example, titanium nitride, titanium oxynitride, niobium nitride, or vanadium nitride is preferable, and titanium nitride or titanium oxynitride is more preferable. Although it does not specifically limit as titanium nitride or titanium oxynitride, The titanium nitride as described in international publication 2008/123097 gazette, international publication 2010/147098 gazette, and patent 5777659 gazette can be used.
  • the content of nitride or oxynitride is the total mass of the pigment.
  • the content is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.
  • Titanium black Titanium black particles that are titanium oxynitride pigments will be described below.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility or suppressing aggregation. It is possible to coat titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a surface treatment of titanium black is possible with a water repellent material as disclosed in JP-A-2007-302836. Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small. Specifically, an average primary particle diameter in the range of 10 nm to 80 nm is preferable. The average primary particle diameter can be measured, for example, by the above method.
  • the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance It is preferably 5 m 2 / g or more and 150 m 2 / g or less, and more preferably 20 m 2 / g or more and 120 m 2 / g or less.
  • Examples of commercially available products of titanium black include titanium black 10S, 12S, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), and Tilac. ) D (trade name: manufactured by Ako Kasei Co., Ltd.).
  • 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 is performed in an atmosphere of a reducing gas such as ammonia.
  • titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). Titanium oxide is not limited to this, but preferably has a primary particle size of 5 nm or more and 70 nm or less, more preferably 7 nm or more and 50 nm or less. These mixed crystals may be used.
  • silica particles examples include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).
  • a dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
  • the dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. can do.
  • 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.
  • the above-described dispersion tends to have a small particle size (for example, a particle size of 30 nm or less), and the component containing Si atoms in the dispersion It is estimated that this increases the adsorptivity with the base of the entire film, which contributes to the improvement of the development removability 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.
  • the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is in terms of 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 ).
  • 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. In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black. Moreover, in this to-be-dispersed body, as long as the effect of this invention is not impaired, other colorants (an organic pigment, dye, etc.) may be used together as desired, as long as the effect of the present invention is not impaired. Good.
  • materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
  • silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used. Furthermore, if the particle size of the silica particles is smaller than the film thickness when the light shielding film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • a titanium nitride containing particle can also be used, for example.
  • a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
  • the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
  • the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable.
  • titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles.
  • the thermal plasma method is not limited to the above.
  • the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a peak diffraction angle 2 ⁇ (details will be described later) derived from the (200) plane when CuK ⁇ rays are used as an X-ray source, It becomes easy to adjust to the range of 42.8 ° or more and 43.5 ° or less.
  • the content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, and preferably 55 to 85% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 55 to 80% by mass.
  • the content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectroscopy.
  • the content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 15 to 50% by mass and preferably 15 to 45% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 40% by mass.
  • the nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
  • the titanium nitride-containing particles may have a diffraction angle 2 ⁇ of a peak derived from the (200) plane of 42.8 ° or more and 43.5 ° or less when an X-ray diffraction spectrum is measured using CuK ⁇ ray as an X-ray source.
  • a light-shielding film obtained using a composition containing titanium nitride-containing particles having such characteristics has an appropriate OD value and is excellent in patterning properties (resolution).
  • the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8 ° and not more than 43.5 ° as described above, and is 42.85 to 43.3 °. Is more preferably 42.9 to 43.2 °.
  • Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed during the synthesis and when the particle diameter is small. Some may contain oxygen atoms. However, a smaller amount of oxygen contained in the titanium nitride-containing particles is preferable because a higher OD value (optical density) can be obtained.
  • the titanium nitride-containing particles preferably contains no TiO 2 as an auxiliary component.
  • TiO 2 is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.
  • the crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
  • the crystallite size is preferably 20 nm or more, more preferably 20 to 50 nm.
  • the specific surface area of the titanium nitride-containing particles can be determined by the BET method and is preferably 40 to 60 m 2 / g, more preferably 40 to 58 m 2 / g, and 42 to 55 m 2 / g. More preferably.
  • the specific surface area of the titanium nitride-containing particles By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m 2 / g, the obtained light-shielding film has an OD (optical density) value in an appropriate range, and is excellent in patternability (resolution).
  • the average primary particle diameter of the titanium nitride-containing particles is preferably 10 to 30 nm, and more preferably 10 to 25 nm.
  • the obtained light shielding film has an OD (optical density) value in an appropriate range, and is excellent in patterning properties (resolution).
  • the average primary particle diameter can be measured, for example, by the above method.
  • the composition of the present invention may also contain inorganic pigments other than those listed above as the inorganic pigment.
  • examples of other pigments include tungsten compounds and metal borides. Tungsten compounds and metal borides have a feature of high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) with respect to infrared rays). Note that the tungsten compound and the metal boride have a low absorption with respect to visible light as compared with a light shielding property against infrared rays. In addition, the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image 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 preferable, and Cs 0.33 WO 3 is more preferable.
  • the tungsten compound is preferably fine particles.
  • the average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. For reasons such as ease of handling during production, the average particle diameter of 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 or more of molybdenum (MoB 2 , Mo 2 B 5 , MoB) and tungsten boride (W 2 B 5 ) can be used, 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 still more preferably 100 nm or less.
  • 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-07AH manufactured by Sumitomo Metal Mining Co., Ltd.
  • the inorganic pigment may be an extender pigment.
  • extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite.
  • the extender is preferably used in combination with a color pigment (for example, a black inorganic pigment).
  • a color pigment for example, a black inorganic pigment.
  • 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 pigment can be used with their surface modified with a polymer.
  • the composition of the present invention comprises a black dye.
  • the black dye those having absorption over the entire wavelength region of visible light (380 nm to 780 nm) are preferable.
  • the black dye include C.I. I.
  • the black dye include xanthene dyes, azo dyes, and aniline dyes.
  • the black dye preferably has an optical density of 2 or more, more preferably 4 or more in the entire wavelength region of 400 to 500 nm.
  • the black dye preferably has a polymerizable group.
  • the polymerizable group is a functional group that can form a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group.
  • a radical polymerizable group is preferable from the viewpoint of more excellent reactivity.
  • radical polymerizable group examples include acryloyl group, methacryloyl group, acrylic acid ester group (acryloyloxy group), methacrylic acid ester group (methacryloyloxy group), itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group,
  • unsaturated carboxylic acid ester groups such as maleic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups are exemplified.
  • a methacryloyl group or an acryloyl group is more preferable.
  • Two or more polymerizable groups may be contained in the black dye.
  • the number of polymerizable groups contained in the black dye is not particularly limited, and may be one or two or more.
  • the black dye may be either a dye monomer or a dye multimer, but is preferably a dye multimer from the viewpoint of further improving heat resistance. Especially, it is preferable that it is a dye multimer which has a structural unit represented by the following general formula (1), has a polymeric group, and has the structural unit represented by the following general formula (1) More preferred is a multimer.
  • R A to R C each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • L represents a single bond or a divalent linking group
  • Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye.
  • R A to R C each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Of these, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is preferable.
  • L represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —S—, —NR 1 —, —CO—, a vinylene group, an ethynylene group, and an alkylene group (which may be cyclic, branched, or linear). Or an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof.
  • R 1 is, for example, a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, an I atom ) And aryl groups (preferably aryl groups having 6 to 20 carbon atoms).
  • a hydrogen atom or an alkyl group is preferable.
  • Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a black dye. Although it does not specifically limit as black dye, The black dye mentioned above is mentioned. Of these, xanthene dyes or azo dyes are preferred from the viewpoint of forming a light-shielding film having better light-shielding performance.
  • the position of the polymerizable group in the dye multimer is not particularly limited. As the position of the polymerizable group in the dye multimer, for example, Dye may have a polymerizable group or may have a structural unit having a polymerizable group.
  • Dye having a polymerizable group intends that the dye residue represented by Dye, which is obtained by removing one arbitrary hydrogen atom from a black dye, has a polymerizable group.
  • the content of the structural unit represented by the general formula (1) in the dye multimer is preferably 80% by mass or more based on the total structural unit, and 85 More preferably, it is 90 mass% or more, and 95 mass% or more is especially preferable.
  • the dye multimer having the structural unit represented by the general formula (1) can be produced by a known method.
  • the black dye is a dye multimer
  • its molecular weight is not particularly defined, but as a polystyrene equivalent value by GPC (gel permeation chromatography) method
  • the weight average molecular weight (Mw) is preferably 1000 or more and 20000 or less. More preferably, it is 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.
  • 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. ).
  • Examples of commercially available black dyes having a polymerizable group include RDW series manufactured by Wako Pure Chemical Industries, Ltd., and specific examples include RDW-K01.
  • the content of the black dye is preferably 0.3 or less in terms of mass ratio (black dye / inorganic pigment) to the content of the inorganic pigment from the viewpoint of further improving reworkability, and is 0.25 or less. Is more preferable, and it is still more preferable that it is 0.2 or less. In addition, although the minimum of content of black dye is not specifically limited, It is preferable that it is 0.01 or more by mass ratio with respect to an inorganic pigment.
  • the content of the black dye is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, with respect to the total solid content of the composition. More preferably, it is mass%.
  • the black dye may be used alone or in combination of two or more.
  • the composition of the present invention preferably contains a dispersant.
  • a dispersing agent contributes to the improvement of the dispersibility of pigment components, such as the inorganic pigment mentioned above.
  • a dispersing agent and the binder resin mentioned later are different components.
  • the dispersant for example, 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, naphthalene sulfonic acid formalin condensate and the like], 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 an inorganic pigment and a pigment used in combination as desired, and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are preferable. On the other hand, by modifying the surface of the inorganic pigment, the adsorptivity of the polymer compound can be promoted.
  • the polymer compound preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound having a structural unit having such a graft chain has an affinity with a solvent by the graft chain, the dispersibility of the color pigment such as the above-mentioned inorganic pigment and the dispersion stability after aging are improved. It is excellent. Further, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
  • the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as the above-mentioned inorganic pigments is lowered, and the dispersibility of the pigments and the like tends to be lowered.
  • the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably has a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
  • the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure.
  • the graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
  • the macromonomer having such 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.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is done.
  • the dispersant preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. Among them, it is preferable to have at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester, and polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethacrylic acid. More preferably, it has at least one structure selected from the group consisting of methyl.
  • the dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
  • the polycaprolactone structure means a structure having a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure means a structure having a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • Specific examples of the dispersant having a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
  • Specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
  • dispersant having a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant having a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
  • the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B 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, and the like 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 carbon atoms.
  • alkyl groups or alkoxy groups are preferable, and among them, 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, respectively. Is preferred.
  • the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of dispersion stability and developability of the composition.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.
  • X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of dispersion stability and developability of the composition. .
  • X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
  • the polymer compound 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 above-described inorganic pigment has high dispersibility and good developability when a light-shielding film is formed.
  • 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 (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched chain structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched chain structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon rings such as tricyclo [4.3.1.1 2,5 ] undecane ring, and , 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, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene 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 carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms.
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.
  • Z 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 the above-described colored pigment such as the inorganic pigment.
  • the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the above-described colored pigment such as the inorganic pigment.
  • the functional group capable of forming an interaction with the color pigment such as the above-described inorganic 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.
  • the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, it is possible to impart developability for pattern formation by alkali development to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention is such that the polymer compound as a dispersant that contributes to the dispersion of the color pigment such as the inorganic pigment has alkali solubility. .
  • a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound has a structural unit which has an acid group
  • the acid group in the structural unit having an acid group easily interacts with the above-described colored pigment such as the inorganic pigment, and the polymer compound stably disperses the above-described inorganic pigment or the like, and the above-described inorganic pigment.
  • the viscosity of the polymer compound that disperses colored pigments such as pigments 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 the color pigment such as the inorganic pigment described above include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. It is at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and more preferable is an adsorbing power to a coloring pigment such as the above-mentioned inorganic pigment, and the dispersibility of the coloring pigment In a high point, it is a carboxylic acid group.
  • the polymer compound When the polymer compound has an acid group, 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 the color pigment such as the inorganic pigment described above include a primary amino group, a secondary amino group, a tertiary amino group, and a hetero group including an N atom.
  • a primary amino group a secondary amino group, a tertiary amino group, and a hetero group including an N atom.
  • 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.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with the color pigment such as the inorganic pigment, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride And acid chlorides.
  • Preferable one is an acetylacetoxy group in that the adsorbing power to the color pigment such as the above-mentioned inorganic pigment is good and the dispersibility of the color pigment is high.
  • 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 forming an interaction with a colored pigment such as the above-mentioned inorganic pigment in addition to the graft chain
  • a colored pigment such as the above-mentioned inorganic pigment in addition to the graft chain
  • the above-described various colored pigments such as the above-mentioned inorganic pigments and the like
  • the polymer compounds are 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 the monomer represented by:
  • 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 number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
  • R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched chain structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most 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 forming an interaction with the above-described pigment such as the inorganic pigment in addition to the graft chain, and includes a carboxylic acid group and a tertiary group An amino group is preferable, and 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.), - Z 1, or an L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or 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 1 is a carboxylic acid group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxy Phenyl methacrylamide, and the like.
  • the content of the structural unit having a functional group capable of forming an interaction with the colored pigment such as the above-described inorganic pigment, the interaction with the colored pigment such as the above-described inorganic pigment, the dispersion stability, and the permeability to the developer is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass with respect to the total mass of the polymer compound.
  • the polymer compound is a coloring unit such as a structural unit having a graft chain, a hydrophobic structural unit, and the above-described inorganic pigment, as long as the effects of the present invention are not impaired.
  • a coloring unit such as a structural unit having a graft chain, a hydrophobic structural unit, and the above-described inorganic pigment
  • other structural unit having various functions for example, a structural unit having a functional group having affinity with the dispersion medium used in the dispersion
  • examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. If the acid value of the polymer compound is 50 mgKOH / g or more, precipitation of colored pigments such as the above-mentioned inorganic pigments can be further suppressed, and the number of coarse particles is reduced (in other words, the amount of particles in the liquid is reduced) And the stability over time of the composition can be further improved. Further, from the viewpoint of more effectively suppressing pattern peeling during development when forming a light shielding film, the upper limit is preferably 140 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd. These polymer compounds may be used alone or in combination of two or more.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to columns 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 is preferably in the range of 0.1 to 1 in terms of mass ratio with respect to the above-described inorganic pigment, A range is more preferable.
  • the content of the dispersant is in the range of 0.1 to 0.4 by mass ratio with respect to the above-mentioned inorganic pigment, so that the amount of coarse particles in the composition can be further reduced, and the obtained light-shielding film Excellent shading performance.
  • the content of the dispersant is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the total solid content of the composition. More preferably, the content is 5 to 10% by mass.
  • a dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the composition of the present invention preferably contains a binder resin.
  • a binder resin 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 to enable water development or weak alkaline water development.
  • an alkali-soluble resin a resin having a group that promotes alkali-solubility
  • the binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used.
  • polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferred, and developability From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acryl / (meth) acrylamide copolymer resins are preferred.
  • the group that promotes alkali solubility hereinafter also referred to as an acid group
  • 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.
  • an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable.
  • These acid groups may be used alone or in combination of two or more.
  • binder resin examples include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group Resins in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated by homopolymerizing a monomer having an acid, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride Can be mentioned.
  • radical polymers having a carboxylic acid group in the side chain such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
  • Examples of the monomer having an acid anhydride include And maleic anhydride.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
  • a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.
  • 2001-318463 has a film strength and developability. It is excellent in balance and is suitable.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
  • a known radical polymerization method can be applied.
  • Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, the type and amount of the radical initiator, the type of solvent, and the like when producing the alkali-soluble resin by the radical polymerization method.
  • a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
  • 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. More preferred is a carboxylic acid group.
  • 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 (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, 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, and more preferably Each independently represents a hydrogen atom or a methyl group.
  • R 21 and R 23 are each particularly 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 group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR 41 ′ —
  • R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched chain structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 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, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms. (e.g., 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 resin can be synthesized by the same method as the dispersant having a structural unit having a graft chain described above, and the preferred acid value and weight average molecular weight are the same.
  • the binder resin 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 resin, and more preferably, from the viewpoint of suppressing damage to image strength due to alkali development. 10 to 90%.
  • the content of the binder resin 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.
  • Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, still more preferably 3 or more, and particularly preferably 5 or more.
  • the upper limit is 15 or less, for example.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. Monomers are preferred.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
  • monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, amides, and multimers thereof.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
  • a dehydration condensation reaction product of a carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups or tosyloxy groups
  • a reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
  • the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.
  • the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.
  • the polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.).
  • Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred.
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution property is good, and when it is 40 mgKOH / g or less, it is advantageous in production or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
  • compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” Indicates a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —.
  • Each represents independently an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
  • the total of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40 .
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60 .
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom
  • a form in which the terminal on the side is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a), (B), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, or Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, or JP-B-62-39418 are also suitable. . Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • the polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and preferably 10.60 or more. Further preferred.
  • the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 .
  • the composition also preferably has a polymerizable compound having a cardo skeleton from the viewpoint of improving development residue.
  • a polymerizable compound having a cardo skeleton a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
  • Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line.
  • X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4.
  • R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively.
  • the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.
  • X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • the substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group having a polymerizable group.
  • the aliphatic group having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is still more preferable.
  • aliphatic group having a polymerizable group represented by X 1 to X 4 when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom.
  • R is a substituent
  • the non-adjacent —CH 2 — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is More preferably, it is substituted with an oxygen atom.
  • the aliphatic group having a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar 11 to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line 14 is substituted with a heteroatom.
  • a polymerizable group capable of radical polymerization or cationic polymerization hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively
  • radical polymerizable group a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one.
  • a vinyl group, a (meth) acryloyloxy group, etc. are mentioned. Of these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
  • cationic polymerizable group generally known cationic polymerizable groups can be used.
  • alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
  • the polymerizable group contained in the substituent contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.
  • Two or more of Ar 1 ⁇ Ar 4 includes a substituent having a polymerizable group, preferably contains a substituent 2-4 of Ar 1 ⁇ Ar 4 has a polymerizable group, Ar 1 ⁇ Ar More preferably, 2 or 3 out of 4 contain a substituent having a polymerizable group, and more preferably 2 out of Ar 1 to Ar 4 contain a substituent having a polymerizable group.
  • X 1 to X 4 are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
  • c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
  • R 1 to R 4 each independently represents a substituent.
  • the substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups An aryl group, an alicyclic group, etc. are mentioned.
  • the substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group.
  • R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar 11 to Ar 14 can have.
  • the value obtained by subtracting a, b, c, or d from the number of. e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
  • Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.
  • Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
  • Examples of the polymerizable compound having a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
  • Examples of such a polymerizable compound having a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the composition of the present invention preferably contains a polymerization initiator.
  • a polymerization initiator There is no restriction
  • the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the above-described inorganic pigment and black dye, it is cured by irradiation with actinic rays or radiation. Sometimes called a "composition".
  • 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. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
  • 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, oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like.
  • Examples of the halogenated hydrocarbon compound having a triazine skeleton include 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
  • a compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones
  • examples thereof include at least one compound selected from the group consisting of a compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
  • composition of the present invention when used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is important that From such a viewpoint, it is preferable to use 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-based initiator commercially available IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.
  • the photopolymerization initiator include oxime compounds (oxime initiators).
  • an oxime compound 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.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
  • N-1919 carboxyl ether skeleton-containing photoinitiator
  • 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 into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in 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 Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
  • R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
  • R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
  • halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms
  • X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 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 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is more preferable.
  • a known method can be used for the molar extinction coefficient of the compound.
  • an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use 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 30% by mass relative to the total solid content in the composition, and is preferably 1 to 25% by mass. %, More preferably 1 to 10% by mass.
  • the composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
  • the composition of the present invention preferably contains an organic solvent.
  • organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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 monomethyl ether Ter, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether,
  • composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but the inorganic pigment particles described above are prepared when the composition of the invention is prepared. It is preferable to contain two or more organic solvents from the viewpoint that the diameter variation can be suppressed.
  • the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • the content of the organic solvent is preferably 10 to 90% by mass and more preferably 60 to 90% by mass with respect to the total mass of the composition. preferable.
  • the total amount is preferably within the above range.
  • the composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
  • the water content is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and more preferably 0.1 to 0.00% by mass with respect to 100% by mass of the composition. More preferably, it is 7 mass%.
  • the water content is within the above range, the generation of pinholes when the light shielding film is produced can be suppressed, or the moisture resistance of the light shielding film can be improved.
  • 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), Silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms are It is desirable not to include.
  • 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.
  • Lz represents a divalent linking group
  • the divalent As the linking group an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
  • a group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
  • R 12 represents a hydrogen atom or a methyl group.
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
  • Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group and the like.
  • substituents further include 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, 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 be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
  • examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent.
  • substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
  • the nitrogen atom is couple
  • Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
  • the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
  • the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to 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 various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness or liquid-saving property is 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 in the thickness of the coating film or 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 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, or RS- 72-K and the like.
  • 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 composition preferably contains a polymerization inhibitor.
  • the composition has better temporal stability.
  • the content of the polymerization inhibitor is preferably from 0.00055 to 0.055 mass%, more preferably from 0.0015 to 0.01 mass%, based on the total solid content of the composition.
  • the polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used.
  • the compound used as the polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
  • the said compound may be used individually by 1 type, or may use 2 or more types together.
  • phenol compound examples include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol.
  • phenolic compound a phenolic compound represented by the formula (IH-1) is preferable.
  • R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
  • R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
  • R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group
  • R 2 and R 4 are more preferably a hydrogen atom
  • R 3 is a hydrogen atom
  • an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
  • Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
  • R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
  • R 7 to R 10 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
  • each of the above compounds may be used alone, in combination of two or in combination of three or more.
  • the polymerization inhibitor preferably contains a phenolic compound.
  • a polymerization inhibitor contains a 2 or more types of phenol type compound from a viewpoint of temporal stability.
  • the said polymerization inhibitor contains a phenol type compound and a hindered amine type compound from a viewpoint of temporal stability.
  • the composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
  • an ultraviolet absorber salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the composition.
  • each said compound may be used individually by 1 type, or may use 2 or more types together.
  • the composition may contain an organic pigment.
  • organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24. , 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 Etc.
  • CI Color Index
  • a pigment may be used individually by 1 type, or may use 2 or more types together.
  • ⁇ Chromatic dye> examples 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. Moreover, you may use the chromatic dye polymeric dye which has superposition
  • the colorant may further contain an infrared absorber.
  • the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm).
  • the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
  • Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
  • Examples include compounds, dithiol metal complex compounds, and croconium compounds.
  • the phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound
  • the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated into.
  • 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 content of the colorant is preferably 1 to 10% by mass with respect to the total solid content of the composition. More preferably, it is ⁇ 7% by mass.
  • the following components may be further added to the composition of the present invention.
  • Examples include sensitizers, pigment dispersants other than those described above, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers.
  • Adhesion promoters to the substrate surface and other auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, perfumes, surface tension modifiers, and , Chain transfer agents and the like
  • 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 of the composition of the present invention is preferably 10 to 40% by mass.
  • the light shielding performance of a light shielding film improves more because the solid content of a composition is 10 mass% or more.
  • the solid content of the composition is 40% by mass or less, the amount of particles in the composition can be further reduced, and the temporal stability is improved.
  • the solid content is preferably 12% by mass or more.
  • the composition of the present invention can be produced 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).
  • a known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser.
  • various components constituting the composition may be combined at once, or may be sequentially mixed after the various components are dissolved or dispersed in an organic solvent.
  • the charging order and working conditions when blending are not particularly limited.
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
  • the 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.
  • 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
  • PP polypropylene
  • nylon are preferable.
  • the filter has a pore diameter of 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. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment while suppressing filtration clogging of the pigment.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter 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 cured film of this invention is obtained using the composition mentioned above.
  • the cured film of the present invention mainly contains the above-described inorganic pigment (preferably a black inorganic pigment, more preferably a pigment containing a nitride or oxynitride) and a black dye.
  • the cured film of the present invention is suitably used as a light-shielding film, and specifically, suitably used as a light-shielding film (frame light-shielding film) around an image sensor such as a CCD image sensor or a CMOS image sensor.
  • the image sensor peripheral light shielding film obtained by using the composition of the present invention is excellent in light shielding performance. That is, the light shielding performance does not deteriorate in a specific wavelength region, and the minimum optical density is within a range where sufficient light shielding ability can be provided in a predetermined region (for example, visible light region to 1200 nm).
  • the film thickness of the cured film of the present invention can be appropriately selected depending on the application, and is not particularly limited.
  • the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less, and 0.2 ⁇ m. It is more preferably 30 ⁇ m or less, further preferably 0.2 ⁇ m or more and 25 ⁇ m or less, particularly preferably 0.2 ⁇ m or more and 20 ⁇ m or less, and most preferably 0.2 ⁇ m or more and 10 ⁇ m or less.
  • the size (length of one side) of the light shielding film is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, and further preferably 0.1 mm or more and 3.5 mm or less.
  • the manufacturing method of the cured film (light-shielding film) of the present invention is not particularly limited, and a known method can be adopted.
  • a method for producing a patterned cured film will be described in detail.
  • the method for producing a patterned cured film of the present invention is a process of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter abbreviated as “composition layer forming process” as appropriate). And a step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing the exposed composition layer to form a patterned cured film. (Hereinafter, abbreviated as “development step” as appropriate).
  • composition layer forming step a composition layer
  • exposure process irradiated with light
  • development process developing with a developer
  • composition layer forming step In the composition layer forming step, the composition of the present invention is applied on a substrate to form a composition layer (coating film).
  • the substrate examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and a transparent conductive film attached to these, photoelectric devices used in solid-state imaging devices, and the like.
  • Examples include a conversion element substrate (for example, a silicon substrate), a CCD substrate, and a CMOS substrate.
  • an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
  • composition of the present invention As a method for applying the composition of the present invention on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, or screen printing method can be applied.
  • the coating thickness of the composition is preferably 0.35 ⁇ m or more and 1.5 ⁇ m or less, more preferably 0.40 ⁇ m or more and 1.0 ⁇ m or less from the viewpoint of resolution and developability. preferable.
  • composition coated on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for 2 minutes or longer and 4 minutes or shorter. Thereby, a composition layer can be formed.
  • the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation with actinic rays or radiation, and more preferably ultraviolet rays such as g-line, h-line, or i-line.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
  • the developer an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
  • the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metaoxalate having a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
  • the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.
  • An alkaline aqueous solution in which an alkaline compound such as 0.001 to 10% by mass, preferably 0.01 to 1% by mass is dissolved.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • the developing method for example, a paddle developing method or a shower developing method can be used.
  • the formed cured film of this invention after performing the composition layer formation process, the exposure process, and the image development process which were mentioned above, the formed cured film is hardened
  • a curing step may be included.
  • the cured film formed using the composition of the present invention can be preferably used as a pixel black matrix of a color filter or a light-shielding film applied to various members in an image display device or sensor module described later.
  • the color filter can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels.
  • the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel.
  • Examples of the image pickup device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A. If the color filter of this invention has the said cured film, the form will not be specifically limited.
  • the cured film can be suitably used as, for example, a pixel black matrix of a color filter.
  • the light shielding film is formed on various members in the image display device or the sensor module (for example, an infrared light cut filter, an outer peripheral portion of the solid-state imaging device, an outer peripheral portion of the wafer level lens, or the back surface of the solid-state imaging device). Can be used. Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
  • the thickness of the light shielding film is not particularly limited, but is preferably 0.2 to 25 ⁇ m, and more preferably 0.2 to 10 ⁇ m.
  • the thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light shielding film and arithmetically averaging them.
  • the reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less.
  • the reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation. .
  • the solid-state imaging device of the present invention includes the solid-state imaging element as described above, and includes the cured film (color filter, light-shielding film, etc.) on the outer peripheral portion or the back surface of the solid-state imaging element.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the cured film and the solid-state imaging device, and examples thereof include the following configurations.
  • the substrate has a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and a transfer electrode made of polysilicon, and the photodiodes receive light on the photodiodes and the transfer electrodes.
  • a light-shielding film having an opening only in the part, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, and a color filter on the device protective film It is the composition which has.
  • the light source has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and below the color filter (on the side close to the substrate), and a constitution having a light condensing means on the color filter. May be.
  • a condensing means for example, a microlens, etc., the same shall apply hereinafter
  • the cured film (such as a color filter or a light-shielding film) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.
  • the display device For the definition of the display device or details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., issued in 1990)”, “Display Device (Junsho Ibuki, Industrial Book Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the form is not particularly limited.
  • the color filter of the present invention may be used in 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 color filter of the present invention is a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), or an STN ( Also applicable to Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), or R-OCB (Reflective Bench).
  • the color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.
  • the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above.
  • the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlights SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. It is described in.
  • the cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an office automation (OA) device such as a printer multifunction device or a scanner; a monitoring camera, a barcode reader, and an automatic cash deposit Industrial equipment such as personal identification using payer (ATM) or high-speed camera or face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope or catheter; biosensor , Optical sensors used in space equipment such as biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological or oceanographic observation cameras, land resource exploration cameras, or exploration cameras for space astronomy or deep space targets Or a light shielding member or a light shielding layer of the module; It can be used for anti-reflective member or anti-reflective layer.
  • ATM personal identification using payer
  • ATM high-speed camera or face image authentication
  • in-vehicle camera equipment medical camera equipment such as endoscope, capsule endo
  • the cured film of this invention can be used also for uses, such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode).
  • micro LED Light Emitting Diode
  • micro OLED Organic Light Emitting Diode
  • it does not specifically limit,
  • the optical filter or optical film used for micro LED or micro OLED it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
  • the micro LED or micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
  • curing the composition of this invention can be used also for uses, such as a quantum dot display.
  • a quantum dot display In addition to the optical or optical film used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
  • quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
  • composition ⁇ Composition ⁇
  • each component contained in the composition will be described first.
  • TiN-1 manufactured by Nissin Engineering Co., Ltd.
  • TiN-2 titanium nitride-containing particles, BET specific surface area 55 m 2 / g, average primary particle size 24.2 nm
  • TiN-3 Product name “TiN 20 nm” manufactured by Hefei (titanium nitride-containing particles, average primary particle size 41.7 nm)
  • TiN-3 Product name “13M-T” manufactured by Mitsubishi Materials Corporation (titanium oxynitride-containing particles, average primary particle size 75 nm)
  • Dye A was synthesized based on the following procedure.
  • Binder resin As binder resin, the following resin A which is alkali-soluble resin was used.
  • Resin A ACRYCURE RD-F8 made by Nippon Shokubai, see the following formula
  • Dispersants A to E having the following structures were used as the dispersants.
  • the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
  • the numerical values (a to e) described in each structural unit are intended to be the molar ratio of each structural unit relative to all structural units, and x and y are intended to be the number of linkages.
  • the numerical value described in the coupling group linked to Z intends the number of linkages linked to Z.
  • Polymerizable compound M1 (Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”, see formula below)
  • oxime initiators were used as polymerization initiators.
  • OXE-02 Irgacure OXE02 (trade name, manufactured by BASF Japan)
  • Organic solvent The following organic solvents were used as the organic solvent.
  • PGMEA Propylene glycol monomethyl ether acetate
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of various resins used were calculated by GPC (Gel Permeation Chromatography) measurement.
  • the ratio (mass ratio) of the dispersant to the pigment containing nitride or oxynitride (hereinafter also referred to as “D / P”) is the ratio shown in each example and comparative example in Table 1. Added to.
  • a coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 ⁇ m, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film. The obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the minimum OD at a wavelength of 400 to 1200 nm, the spectroscopic (light shielding property) was evaluated according to the following criteria.
  • each composition of an Example and a comparative example is a negative photosensitive resin composition which an exposure part hardens
  • the silicon wafer substrate on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd.
  • the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center from a jet nozzle.
  • the wafer was rinsed and then spray-dried to form a wafer having a frame-like pattern.
  • the obtained wafer having a frame-like pattern is immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85 ° C. for 5 hours, and immersed in a 2 L DIW (pure water) bath at room temperature for 2 minutes.
  • TMAH tetramethylammonium hydroxide
  • DIW pure water
  • A no pattern is observed
  • B particulate removal residue is observed in 5% or less of the pattern formation region
  • C particulate removal residue is present in more than 5% and 10% or less of the pattern formation area
  • D particulate removal residue is observed in more than 10% of the pattern formation area, or a pattern or a part of the pattern is observed
  • a coating film is formed by applying the composition by spin coating on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 ⁇ m, and on the hot plate, The coating film was heat-treated at 100 ° C. for 2 minutes to obtain a dry film.
  • the obtained dried film was measured for OD (optical density) by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the lowest OD at a wavelength of 400 to 1200 nm, the spectral (light-shielding property) was evaluated and set as the lowest OD before the heat resistance test.
  • the dried film was heat-treated on a hot plate at 265 ° C.
  • a coating film was formed on an image sensor device substrate by a spin coater. Next, the obtained coating film was pre-baked at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film that has been subjected to the pre-baking process is exposed using an i-line exposure apparatus (FPA, manufactured by Canon Inc.), and further developed to cover the outer periphery of the light receiving part on the substrate except for the dicing line and the electrode part. Simultaneously with the formation of the light shielding film, 20 alignment marks having a line width of 20 ⁇ m were formed on the substrate. The resolution was evaluated by observing the number of alignment marks formed using an optical microscope. “A”: 20 marks were formed. “B”: 19 marks were formed. “C”: 18 marks were formed. “D”: 17 or less marks were formed.
  • FPA i-line exposure apparatus
  • the content of the black dye is 0.3 or less (preferably 0.25 or less, more preferably) with respect to the pigment containing nitride or oxynitride. Is 0.2 or less), it was shown that reworkability is further improved.
  • Example 1 When Examples 1, 4 and 5 were compared, it was shown that the reworkability, heat resistance and patterning properties were further improved due to the black dye having a polymerizable group. In Example 5 using an azo dye, it was confirmed that the heat resistance was excellent.
  • Comparison of Examples 1 and 9 to 12 shows that the amount of particles in the liquid can be further reduced by setting the acid value of the dispersant to 50 mgKOH / g or more.
  • the amount of particles in the liquid is smaller and the patterning property is also excellent.
  • Examples 1, 20 and 21 are compared, it is shown that when the pigment content is 30% by mass or more based on the solid content, the light shielding performance of the obtained light shielding film is further improved and the heat resistance is also improved. It was done. On the other hand, it was shown that when the pigment content is 70% by mass or less with respect to the solid content, reworkability and patterning properties are further improved.
  • Example 22 A composition was prepared and evaluated in the same manner except that the polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of using the dye A in Example 1. It was found to have the same performance as in Example 1.
  • the polymerizable black dye “RDW-K01” manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 23 The same as Example 1 except that Dye A and polymerizable black dye “RDW-K01” (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye A, and the mass ratio was 1: 1. When the composition was prepared and evaluated, it was found that it had the same performance as Example 1.
  • Example 24 The same as Example 4 except that Dye B and polymerizable black dye "RDW-K01" (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of Dye B, and the weight ratio was 1: 1.
  • Dye B and polymerizable black dye "RDW-K01" manufactured by Wako Pure Chemical Industries, Ltd.
  • the weight ratio was 1: 1.
  • evaluation superior to that of Example 4 was obtained. Specifically, the reworkability evaluation, the heat resistance evaluation, and the patterning evaluation were all “B”. I understood.
  • Example 25 In Example 1, instead of using TiN-1, TiN-1 and carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, gas black method When the composition was prepared and evaluated in the same manner except that it was used at a mass ratio of 7: 3, it was found that it had the same performance as in Example 1.
  • TiN-1 and carbon black trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, gas black method
  • Example 26 In Example 1, TiN-1 and Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) were used instead of TiN-1, and the mass ratio was 9: 1.
  • the composition was prepared and evaluated in the same manner except that it was used as a light-shielding film, it was found that the composition had the same performance as that of Example 1, and a darker light-shielding film was obtained. From this result, it is presumed that the desired effect of the present application can be obtained even in combination with other organic pigments or chromatic dyes.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
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JP2023130910A (ja) 2022-03-08 2023-09-21 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物、ブラックマトリックス用レジスト組成物、及び、ブラックマトリックス

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JP7494728B2 (ja) 2020-12-23 2024-06-04 Ｔｏｐｐａｎホールディングス株式会社 固体撮像素子および製造方法

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