WO2015005310A1 - Composition et film bloquant la lumière et leur procédé de production - Google Patents

Composition et film bloquant la lumière et leur procédé de production Download PDF

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Publication number
WO2015005310A1
WO2015005310A1 PCT/JP2014/068122 JP2014068122W WO2015005310A1 WO 2015005310 A1 WO2015005310 A1 WO 2015005310A1 JP 2014068122 W JP2014068122 W JP 2014068122W WO 2015005310 A1 WO2015005310 A1 WO 2015005310A1
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Prior art keywords
light
group
composition
shielding
mass
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PCT/JP2014/068122
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English (en)
Japanese (ja)
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浜田　大輔
久保田　誠
哲 村山
嶋田　和人
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富士フイルム株式会社
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Publication of WO2015005310A1 publication Critical patent/WO2015005310A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/14618—Containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14623—Optical shielding

Definitions

  • the present invention relates to a light-shielding composition, a light-shielding film, and a method for producing the same.
  • a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor is provided with a light shielding film for the purpose of preventing noise generation and improving image quality.
  • a composition for forming a light-shielding film for a solid-state imaging device a light-shielding composition containing a black color material such as carbon black or titanium black is known (Patent Document 1).
  • Patent Document 1 it is disclosed that when the disclosed light-shielding composition is used, a light-shielding film having good coating uniformity and step followability and good high-temperature and high-humidity durability can be formed. .
  • a low-reflective light-shielding film as described above can be formed by a spin coating method having excellent productivity.
  • the inventors of the present invention have studied the reflection characteristics using the light-shielding composition specifically disclosed in Patent Document 1, and satisfy the level that has been conventionally required, but more recently than required. It has been found that it does not meet the high level and needs further improvement.
  • An object of this invention is to provide the light-shielding composition which can form the light-shielding film which shows low reflectivity simply in view of the said situation.
  • Another object of the present invention is to provide a light-shielding film formed using the light-shielding composition and a method for producing the same.
  • the present inventors have found that the above-mentioned problems can be solved by using a composition containing a predetermined component, and have completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a light-shielding composition comprising at least one of light-shielding particles and a light-shielding dye, and (B) a filler having a particle diameter in the range of 100 to 3000 nm, A light-shielding composition having a filler (B) content of 3 to 30% by mass relative to the total solid content in the light-shielding composition.
  • the light-shielding composition according to (1) or (2) further comprising a binder polymer having an acid value of 50 mgKOH / g or less and a weight average molecular weight of 8000 to 50,000.
  • a method for producing a light shielding film comprising a step of spin-coating the light shielding composition according to any one of (1) to (4) to form a light shielding film.
  • (A) contains at least one kind of light-shielding particles and a light-shielding dye, and (B) a filler having a particle diameter in the range of 100 to 3000 nm, A light-shielding film having a filler (B) content of 3 to 30% by mass.
  • (B) contains at least one kind of light-shielding particles and a light-shielding dye, and (B) a filler having a particle diameter in the range of 100 to 3000 nm, A light-shielding film having a filler (B) content of 3 to 30% by mass.
  • the light-shielding film according to (6) wherein the reflectance at a wavelength of 400 to 700 nm is 4% or less.
  • (9) (A) Any one of light-shielding particles and light-shielding dyes, and (C) a light-shielding material containing at least a binder polymer having an acid value of 50 mgKOH / g or less and a weight average molecular weight of 8,000 to 50,000.
  • a sex composition A light-shielding composition having a binder polymer content of 4 to 30% by mass relative to the total solid content in the light-shielding composition.
  • the light-shielding composition which can form easily the light-shielding film which shows low reflectivity by methods, such as a spin coat method, can be provided.
  • the light shielding film formed using this light-shielding composition and its manufacturing method can also be provided.
  • FIG. 1 It is a perspective view which shows the solid-state imaging device of 1st Embodiment. It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.
  • one of the features of the present invention is that it includes a predetermined amount of a filler having a predetermined size.
  • a filler having a predetermined size By including a filler having a predetermined size, the surface of the light shielding film can be easily formed even by a simpler method such as spin coating, and a light shielding film having desired reflection characteristics can be obtained.
  • Another feature of the present invention is that a binder polymer exhibiting a predetermined acid value and weight average molecular weight is used. When the binder polymer is used, layer separation is likely to occur between the light-shielding particles and the light-shielding dye, and as a result, a light-shielding film having excellent reflection characteristics can be obtained.
  • a solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic substrate 5 made of ceramic that holds the circuit board 4. And.
  • the solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) toward the CMOS sensor 3, a photographing lens 7, and a lens holder 8 that holds the photographing lens 7.
  • a holding cylinder 9 that holds the lens holder 8 movably.
  • a CCD sensor or an organic CMOS sensor may be provided instead of the CMOS sensor 3.
  • the ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds the side surface of the CMOS sensor 3.
  • the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy adhesive, the same applies hereinafter).
  • an adhesive for example, an epoxy adhesive, the same applies hereinafter.
  • Various circuit patterns are formed on the circuit board 4.
  • a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a.
  • the IR cut filter 6 is formed in a size slightly larger than the opening 5a, and is fixed to the ceramic substrate 5 with an adhesive so as to cover the opening 5a.
  • a CMOS sensor 3 is disposed behind the photographing lens 7 (downward in FIGS. 2 and 3), and an IR cut filter 6 is disposed between the photographing lens 7 and the CMOS sensor 3. The subject light enters the light receiving surface of the CMOS sensor 3 through the photographing lens 7 and the IR cut filter 6. At this time, the infrared light is cut by the IR cut filter 6.
  • the circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2.
  • an electronic device for example, a digital camera
  • CMOS sensor 3 a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.
  • a light-shielding film (light-shielding layer) 11 that shields visible light is formed at the end of the incident surface 6a of the IR cut filter 6 over the entire circumference.
  • reflected light (visible light) R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 2 and 3) of the ceramic substrate 5 enters the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus.
  • the reflected light (visible light) R2 reflected from the inner wall surface of the lens holder 8 emitted from the photographing lens 7 enters the CMOS sensor 3, it causes flare and ghost in the photographed image.
  • the light shielding film 11 shields harmful light such as reflected light R ⁇ b> 1 and R ⁇ b> 2 toward the CMOS sensor 3.
  • the light shielding film 11 is applied by, for example, spin coating or spray coating. 2 and 3, the thickness of the light shielding film 11 is exaggerated.
  • the above is one aspect of the solid-state imaging device including the light-shielding film of the present invention, and may be another aspect.
  • composition each component that can be contained in the light-shielding composition (hereinafter also simply referred to as “composition”) used when forming the light-shielding film 11 will be described in detail.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • radiation in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
  • the description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • monomer and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a mass 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 first embodiment of the light-shielding composition includes (A) any one of light-shielding particles and light-shielding dyes, and (B) at least a filler having a particle diameter in the range of 100 nm to 3000 nm.
  • the said component is explained in full detail.
  • the light-shielding particles and light-shielding dyes used in the present invention (hereinafter collectively referred to as “light-shielding material”) mainly absorb light at 800 to 1200 nm and are used for exposure. It is preferable that the permeability is good.
  • the light-shielding particles and light-shielding dyes in the present invention any of light-shielding particles and light-shielding dyes having absorption at 800 to 1200 nm can be used, but light-shielding particles are preferable from the viewpoint of heat resistance.
  • the light-shielding particles are preferably fine particles, and the particle size showing the maximum value in the particle size distribution is preferably in the range of 5 to 100 nm, more preferably in the range of 5 to 50 nm, and more preferably in the range of 5 to 30 nm. More preferably, it is in the range.
  • the particle diameter is in such a range, the light-shielding particles are less likely to settle due to aging or the like, and the aging stability of the composition of the present invention becomes better.
  • the total content of the light-shielding material in the composition is not particularly limited, but is preferably 30 to 70% by mass, and preferably 40 to 60% by mass with respect to the total solid content in the composition in terms of more excellent reflection characteristics of the light-shielding film. % Is more preferable, and 45 to 55% by mass is even more preferable.
  • the total solid content intends the total mass of components (for example, a light shielding material, a binder polymer, a polymerizable compound, etc.) that can constitute a light shielding film described later, and does not include components that do not constitute a film such as a solvent.
  • the dye that can be used as the light-shielding dye examples include cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, imonium dyes, aminonium dyes, quinolium dyes, pyrylium dyes, and metal complex dyes such as Ni complex dyes. it can.
  • the light-shielding particles are preferably pigments selected from organic pigments and inorganic pigments from the viewpoint of heat resistance, and inorganic pigments are particularly preferable.
  • inorganic pigments that can be used as light-shielding particles include carbon black, titanium black, tungsten compounds, 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, bitumen (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, ceramic red, salmon pink, etc., and black pigments such as Co, Cr, Cu, Mn, Ru, Fe, Ni, Gold containing one or more metal elements selected from the group consisting of Sn, Ti and Ag Oxides, metal nitrogen compound or a mixture thereof can be used.
  • carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite and the like are preferable from the viewpoint of infrared light shielding properties.
  • at least one of carbon black and titanium black is preferable. It is preferable to contain, especially titanium black.
  • the carbon black As the carbon black, those disclosed in paragraphs [0020] to [0024] of JP-A-2006-301101 can be used.
  • the titanium black is black particles having titanium atoms. Black particles such as low-order titanium oxide and titanium oxynitride are preferred.
  • the surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. is there.
  • Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), or ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method of reducing titanium in a reducing atmosphere containing hydrogen Japanese Patent Laid-Open No. 57-205322
  • a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No.
  • the titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
  • the average primary particle diameter is preferably in the range of 10 nm to 45 nm, and more preferably in the range of 12 nm to 20 nm.
  • the particle diameter that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle.
  • the projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
  • the specific surface area of titanium black is not particularly limited. However, since the water repellency after surface treatment of such titanium black with a water repellent becomes a predetermined performance, the value measured by the BET method is usually 5 to 150 m. it is preferably 2 / g, and more preferably in particular 20 ⁇ 100m 2 / g.
  • titanium black examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
  • Titanium black can modify the particle surface as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • coating treatment with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like is possible, and repellent properties as disclosed in JP-A-2007-302836 are also possible. Treatment with an aqueous material is also possible.
  • the composition of the present invention contains titanium black as a dispersion containing titanium black and Si atoms.
  • 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 to 5 in terms of mass. 0.5 is preferable, and 0.07 to 0.4 is 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).
  • the Si / Ti of the dispersion is too small, when the light-shielding film using the dispersion is patterned by photolithography or the like, a residue is likely to remain in the removed portion, and the Si / Ti of the dispersion is large. If it is too much, the light shielding ability tends to decrease.
  • the following means can be used. First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly contained.
  • Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraph Nos. [0005] and (6) and paragraph Nos. [0016] to [0021] of JP-A-2008-266045.
  • the present invention 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), this coverage is achieved.
  • a suitable range for example, 0.05 or more
  • the residue derived from the composition outside the region where the light-shielding film is formed is reduced.
  • a residue contains the component derived from compositions, such as titanium black and a resin component.
  • titanium black is excellent in light shielding properties for light in a wide wavelength range from ultraviolet to infrared, the above-described light shielding film formed using a dispersion containing titanium black and Si atoms is excellent.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011 / 049090t. ).
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline
  • other colorants an organic pigment, dye, etc.
  • the filler contained in the composition is preferably 100 to 1000 nm, more preferably 100 to 800 nm, and even more preferably 100 to 600 nm in that the particle diameter is 100 to 3000 nm and the reflection characteristics of the light shielding film are more excellent.
  • the particle diameter means an average particle diameter (D50).
  • the particle size (average particle size (D50)) is defined as a particle size having an integrated value of 50% when expressed as an integrated (cumulative) volume percentage. More specifically, in the graph (volume-based particle size distribution) in which the horizontal axis represents the particle diameter and the vertical axis represents the cumulative frequency from the small diameter side, the cumulative value of all particles (100%) from the small diameter side.
  • the particle diameter corresponding to the cumulative value of 50% by volume corresponds to D50.
  • the particle diameter (average particle diameter (D50)) is measured using a dynamic light scattering photometer (trade name DLS7000, manufactured by Otsuka Electronics Co., Ltd.) with the measurement principle being the dynamic light scattering method and the size distribution analysis method being the cumulant method. And / or as a histogram method.
  • the content of the filler in the composition is 3 to 30% by mass with respect to the total solid content in the composition, and is preferably 4 to 16% by mass in terms of more excellent reflection characteristics of the light-shielding film. More preferably, it is ⁇ 16% by mass.
  • the light-shielding film When the filler content is less than 3% by mass, the light-shielding film has poor reflection characteristics, and when it exceeds 30% by mass, the light-shielding film has poor light-shielding characteristics.
  • the total solid content means the total mass of components constituting a light shielding film described later, and does not include a solvent. Further, different materials are used for the filler and the light shielding particles.
  • any of an organic filler, an inorganic filler, an inorganic-organic composite filler, and the like may be used, and two or more of these may be mixed and used.
  • the organic filler include synthetic resin particles, natural polymer particles, and the like, and preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide, Resin particles such as carboxymethyl cellulose, gelatin, starch, chitin, and chitosan, and more preferably resin particles such as acrylic resin, polyethylene, polypropylene, and polystyrene.
  • Inorganic fillers include metals and metal compounds such as oxides, composite oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides and at least two of these.
  • Specific examples of the composites include silica, mica compound, glass, zinc oxide, alumina, zircon oxide, tin oxide, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, magnesium borate, water
  • Two or more composite products, such as Kutomo like such as Kutomo like.
  • silica mica compound, glass, alumina, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, calcium sulfate and the like can be mentioned.
  • inorganic fillers silica is preferred.
  • Specific examples of the inorganic filler include SO-C1 (particle diameter 250 nm) manufactured by Admatechs Co., Ltd., silica filler (SO-C2 manufactured by Admatechs Co., Ltd.) (particle diameter 500 nm), silica filler (Admatechs).
  • silica filler manufactured by Admatechs Corporation, SO-C5 (particle diameter 1600 nm), and the like.
  • the shape of the filler include a fiber shape, a needle shape, a plate shape, a spherical shape, a tetrapot shape, and a balloon shape. Of these, the preferable one is spherical.
  • components other than the light-shielding material and the filler may be contained.
  • Polymerization inhibitors, adhesion improvers, surfactants and the like will be described in detail.
  • the composition of the present invention may further contain a binder polymer as necessary for the purpose of improving the film properties.
  • the acid value of the binder polymer used is preferably 50 mgKOH / g or less, more preferably 20 to 50 mgKOH / g, still more preferably 20 to 40 mgKOH / g. If it is the said range, the reflective characteristic of a light shielding film will be more excellent.
  • the lower limit of the acid value is not particularly limited, but is preferably 20 mgKOH / g or more from the viewpoint of lithography performance.
  • the acid value of a binder polymer 30 mgKOH / g or less is also preferable.
  • the acid value (unit: mg KOH / g) of the binder polymer is the amount (mg) of potassium hydroxide (KOH) necessary to neutralize 1 g of the binder polymer.
  • the acid value in the present invention refers to a value measured by the method of Section 11.1 of JIS K 5407 (1990).
  • the weight average molecular weight of the binder polymer is preferably 8000 to 50000, and more preferably 8000 to 30000. If it is the said range, the reflective characteristic of a light shielding film will be more excellent.
  • a weight average molecular weight of a binder polymer 20000 or less is preferable and 15000 or less is more preferable.
  • the measurement method of the weight average molecular weight of the binder polymer is, for example, HPC-8220GPC (manufactured by Tosoh Corporation), guard column: TSKguardcolumn SuperHZ-L, column: TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ2000, TSKgel Super 10 ⁇ l of a tetrahydrofuran solution having a sample concentration of 0.1% by mass is injected at 40 ° C., tetrahydrofuran is flowed at a flow rate of 0.35 ml per minute as an elution solvent, and the sample peak is detected by an RI detector.
  • the weight average molecular weight is calculated using a calibration curve prepared using standard polystyrene.
  • the binder polymer may have a polymerizable group (for example, (meth
  • a linear organic polymer is preferably used as the binder polymer.
  • a linear organic polymer a known one can be arbitrarily used.
  • a linear organic polymer that is soluble or swellable in water or alkaline water is selected in order to enable water development or alkaline water (preferably weak alkaline water) development.
  • the linear organic polymer is selected and used not only as a film forming agent but also according to a developer (developer) made of water, alkaline water, or an organic solvent. For example, when a water-soluble organic polymer is used, water development becomes possible.
  • linear organic polymers 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, and JP-B-54. No. 25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. Is mentioned.
  • Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and examples of monomers having an acid anhydride include maleic anhydride.
  • An acid etc. are mentioned.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • Japanese Patent Publication No. 7-2004 Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No.
  • Urethane binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and advantageous in terms of suitability for low exposure.
  • the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
  • binder polymers may be any of random polymers, block polymers, graft polymers and the like.
  • the binder polymer can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more. Examples of the radical polymerization initiator used when the binder polymer is synthesized include known compounds such as an azo initiator and a peroxide initiator.
  • an alkali-soluble resin having a double bond in the side chain as the binder polymer, both the curability of the exposed area and the alkali developability of the unexposed area can be improved.
  • the alkali-soluble resin having a double bond in the side chain has a non-image area removability by having an acid group for making the resin alkali-soluble in the structure and at least one unsaturated double bond. Improve various performances.
  • a resin having such a structure is described in detail in JP-A No. 2003-262958, and the resin described therein can be used as a binder polymer.
  • a cardo resin can be used, which is selected from the group consisting of epoxy resin, polyester resin, polycarbonate resin, acrylic resin, polyether resin, polyamide resin, polyurea resin, and polyimide resin, and a fluorene skeleton.
  • a cardo resin having is preferred.
  • the cardo resin refers to a resin having a cardo structure (a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure) in the molecule. More specifically, compounds described in paragraphs [0046] to [0057] of JP2011-170334A can be used.
  • the content of the binder polymer in the composition is 4 to 30% by mass with respect to the total solid content in the composition in that the reflection characteristics of the light shielding film are more excellent. It is preferably 7 to 30% by mass, more preferably 15 to 25% by mass.
  • the composition may contain a dispersant in order to improve the dispersion stability of the light-shielding material (particularly, light-shielding particles) and filler (hereinafter, both are also collectively referred to as “dispersoid”).
  • the dispersant is preferably a polymer compound dispersant, more preferably a polymer compound having a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having a graft chain.
  • the dispersant examples include a polymer dispersant [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 copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, and pigment derivatives.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • the dispersant acts to adsorb on the surface of the dispersoid and prevent reagglomeration. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to these surfaces can be cited as preferred structures. On the other hand, the adsorptivity of the dispersant to these can be promoted by modifying the surface of titanium black or the above-described dispersion material containing titanium black and Si atoms.
  • the dispersant preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • a dispersant having such a structural unit having a graft chain has excellent dispersibility of the dispersoid and dispersion stability after the lapse of time because it has an affinity for the solvent by the graft chain.
  • the composition since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably has a polymer structure, and examples of such a polymer structure include a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and Examples thereof include a polyether structure.
  • the graft chain has at least one selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure in order to improve the interaction between the graft site and the solvent and thereby increase the dispersibility.
  • a graft chain having at least one of a polyester structure and a polyether structure is more preferable.
  • the structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain, but preferably a reactive double bond group is formed.
  • the macromonomer which has can be used conveniently.
  • AA-6 (trade name, manufactured by 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, manufactured 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.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation), and the like.
  • the dispersant preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any one of the formula (3A), the following formula (3B), and the following formula (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 preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represents hydrogen.
  • An atom or a methyl group is more preferable, and a methyl group is particularly preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the 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, and an amino group Etc.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable.
  • n, m, p, and q are each an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
  • p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the structural units represented by the formulas (1) to (4) are preferably contained in a range of 10% to 90%, in terms of mass, with respect to the total mass of the dispersant, 30% to 70%. It is more preferable that it is contained in the range of%.
  • the structural units represented by the formulas (1) to (4) are included within this range, the dispersoid has high dispersibility and good developability when forming the light-shielding film.
  • a dispersing agent can have the structural unit which has a graft chain from which 2 or more types of structures differ. That is, the dispersing agent molecule may contain structural units represented by the formulas (1) to (4) having different structures, and in the formulas (1) to (4), n, m, When p and q each represent an integer of 2 or more, in the formula (1) and the formula (2), j and k may contain different structures in the side chain, and the formula (3) and the formula In (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
  • X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoints of dispersion stability and developability.
  • the dispersant has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain is preferably contained in a range of 10% to 90%, more preferably in a range of 30% to 70% with respect to the total mass of the dispersant in terms of mass. preferable.
  • the structural unit having a graft chain is contained within this range, the dispersoid has high dispersibility, and the developability when forming the light-shielding film is good.
  • the dispersant preferably has a hydrophobic structural unit that is different from the structural unit having a graft chain (that is, does not correspond 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.
  • the dispersant 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 represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1 to 6
  • An alkyl group for example, a methyl group, an ethyl group, a propyl group; the same shall apply hereinafter).
  • R 1 , R 2 , and R 3 are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are particularly preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • the 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 groups), divalent heterocyclic groups, and oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR 31 —, R 31 is an aliphatic group, aromatic group or heterocyclic group) or a combination with a carbonyl group (—CO—).
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent.
  • the substituent examples 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.
  • 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 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 includes aliphatic groups (eg, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (eg, arylene groups, substituted arylene groups), heterocyclic groups, and Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 is an aliphatic group, aromatic group or heterocyclic group) Or a combination with a carbonyl group (—CO—) and the like can be mentioned.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group are included.
  • the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, and a biphenyl. Group, 4-cyclohexylphenyl group and the like.
  • bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
  • Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.02,6] decane, tricyclo [4.3.1.12,5] undecane ring, tetracyclo [4 4.0.12, 5.17,10] dodecane, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like.
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent.
  • the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • 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.
  • the heterocyclic group may have a substituent.
  • 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, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms, Z or -LZ is represented.
  • 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 includes an alkylene group or an oxyalkylene structure 2
  • 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.
  • a compound in which Y is a methine 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 monomers represented by the formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. Specific examples of the radical polymerizable compound include the definitions described in paragraphs 0069 to 0071 of JP2010-106268A (paragraphs 0113 to 0114 of the corresponding US Patent Application Publication No. 2011-0124824). The contents of which are incorporated herein.
  • methacrylic acid esters and styrenes are preferably used, and benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate are particularly preferably used.
  • the following compounds are exemplified as the compound containing a heterocyclic group.
  • the hydrophobic structural unit is preferably contained in a range of 10% to 90% and more preferably in a range of 20% to 80% with respect to the total mass of the dispersant in terms of mass.
  • the dispersant can introduce functional groups that can interact with the dispersoid.
  • the dispersant preferably further includes a structural unit having a functional group capable of forming an interaction with the dispersoid. Examples of the functional group capable of forming an interaction with the dispersoid include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the dispersant has an acid group, a basic group, a coordinating group, or a reactive functional group
  • a structural unit having an acid group, a structural unit having a basic group, and a coordinating group respectively. It is preferable to have a structural unit having or a reactive structural unit.
  • the dispersant further has an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the dispersant. That is, by introducing an alkali-soluble group into the dispersant, the dispersant has alkali solubility.
  • a polymerizable composition containing such a composition has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • 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).
  • the acid group that is a functional group capable of forming an interaction with the dispersoid examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • the carboxylic acid group, the sulfonic acid group, Among the phosphoric acid groups at least one kind, and particularly preferred is a carboxylic acid group that has good adsorbability on the dispersoid and has high dispersibility. That is, the dispersant 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 dispersant may have one or more structural units having an acid group.
  • the dispersant 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 preferably in terms of mass with respect to the total mass of the dispersant. Is from 5 to 80%, more preferably from 10 to 60% from the viewpoint of suppressing damage to the image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with the dispersoid include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Among them, particularly preferred is a tertiary amino group which has good adsorption power to titanium black and high dispersibility.
  • the dispersant may have one or more of these basic groups.
  • the dispersant 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 based on the total mass of the dispersant in terms of mass. Preferably, the content is 0.01 to 50%, and more preferably 0.01 to 30% from the viewpoint of inhibiting the developability inhibition.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with the dispersoid, and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride. Is mentioned. Particularly preferred is an acetylacetoxy group having good adsorbing power to the dispersoid and high dispersibility.
  • the dispersant may have one or more of these groups.
  • the dispersant 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 the mass. In terms of conversion, it is preferably 10 to 80% with respect to the total mass of the dispersing agent, and more preferably 20 to 60% from the viewpoint of inhibiting developability inhibition.
  • the manner in which these functional groups are introduced is not particularly limited. It is preferable to have one or more structural units selected from structural units derived from monomers represented by the following general formulas (iv) to (vi).
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having a number of 1-6.
  • R 11 , R 12 and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, most preferably Are each independently a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group ( For example, an arylene group and a substituted arylene group), a divalent heterocyclic group and an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR) 31′- , where R 31 ′ is an aliphatic group, aromatic group or heterocyclic group) or a combination with one or more of carbonyl bonds (—CO—).
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an
  • a bivalent aliphatic group a bivalent aromatic group, and a bivalent heterocyclic group is synonymous with the definition of each group represented by L mentioned above.
  • a preferred embodiment of the L 1 has the same meaning as the preferred embodiment of L as described above.
  • Z 1 represents a functional group capable of forming an interaction with the dispersoid other than the graft site, and is preferably a carboxylic acid group or a tertiary amino group.
  • a carboxylic acid group is more preferable.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms, — Z 1 or -L 1 -Z 1 is represented.
  • 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 is an oxygen atom or an imino group and Z 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, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid group is preferred.
  • the monomer represented by the general formula (iv) to the general formula (vi)
  • the monomer include a reaction product of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride, a molecule
  • a reaction product of a compound having an addition polymerizable double bond and hydroxyl group and trimellitic anhydride a reaction product of a compound having an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic Acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenyl methacrylate And the like.
  • the content of the functional group capable of forming an interaction with the dispersoid is 0.05 mass with respect to the total mass of the dispersant from the viewpoint of interaction with the dispersoid, dispersion stability, and permeability to the developer. % To 90% by mass, preferably 1.0% to 80% by mass, more preferably 10% to 70% by mass.
  • the dispersant forms an interaction with the structural unit having a graft chain, the hydrophobic structural unit, and the dispersoid as long as the effects of the present invention are not impaired.
  • other structural units having various functions for example, structural units having functional groups 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 content thereof is preferably 0 to 80% based on the total mass of the dispersant in terms of mass, in particular. Preferably, it is 10 to 60%. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the dispersant is preferably in the range of 0 to 160 mgKOH / g, more preferably in the range of 10 to 140 mgKOH / g, and still more preferably in the range of 20 to 120 mgKOH / g.
  • the acid value of the dispersant is preferably more than 30 mgKOH / g. If the acid value of the dispersant is 160 mgKOH / g or less, pattern peeling during development when forming the light-shielding film can be more effectively suppressed. Moreover, if the acid value of a dispersing agent is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the dispersant is 20 mgKOH / g or more, the sedimentation of the dispersion containing titanium black or titanium black and Si atoms can be further suppressed, and the number of coarse particles can be further reduced. The stability over time can be further improved.
  • the acid value of the dispersant can be calculated, for example, from the average content of acid groups in the dispersant.
  • resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group in a dispersing agent.
  • the weight average molecular weight of the dispersant is preferably 4,000 or more and 300,000 or less as a polystyrene conversion value by GPC method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less.
  • the weight average molecular weight of the dispersant is preferably more than 15000, more preferably more than 20000.
  • 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 numerical value written together with each structural unit represents the content of the structural unit [described as mass%: (wt%)].
  • the numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.
  • dispersant examples include, in addition to the above, “Disperbyk-161, 162, 163, 164, 165, 166, 170 (trade name, polymer copolymer)” manufactured by BYK Chemie, “EFKA4047” manufactured by EFKA. , 4050, 4010, 4165 (trade name, polyurethane-based), EFKA4330, 4340 (trade name, block copolymer). These dispersants may be used alone or in combination of two or more.
  • the content of the dispersant in the composition is 1 to 90% by mass with respect to the total solid content in the composition in that the dispersion stability such as dispersoid is better. Preferably, it is 3 to 70% by mass.
  • the composition of the present invention may contain a solvent.
  • the type of solvent is not particularly limited, but is preferably an organic solvent.
  • organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • Acetylacetone, cyclohexanone, 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 Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, ethyl lactate and the like, but are not limited thereto.
  • Solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the content of the solvent contained in the composition is not particularly limited, but is preferably 10 to 80% by mass, and preferably 20 to 70% by mass with respect to the total mass of the composition. More preferred is 30 to 65% by mass.
  • the composition of the present invention may contain a polymerizable compound.
  • the polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure. Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C.
  • polyethylene glycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth)
  • compounds described in JP-A-10-62986 as general formula (1) and general formula (2) together with specific examples thereof, and (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol can also be used.
  • dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and structures in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferred.
  • bifunctional compounds include NK ester A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd., and light acrylate DCP-A manufactured by Kyoei Chemical Co., Ltd.
  • a trifunctional and tetrafunctional mixture examples include Aronix M-305 and M-510 manufactured by Toagosei Co., Ltd., and four functional groups include KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd. and NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., and KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd. are used as the mixture of the isomer and hexafunctional compound .
  • urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained.
  • Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name) , Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
  • ethylenically unsaturated compounds having an acid group are also suitable.
  • examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate.
  • TO-1382 and the like can be mentioned.
  • the polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination aspect can be suitably set according to the physical property etc. which are requested
  • a suitable combination mode of the polymerizable compound for example, a mode in which two or more polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
  • the content of the polymerizable compound in the composition is preferably 3 to 55% by mass, more preferably 10 to 50% by mass with respect to the total solid content in the composition. is there.
  • the composition of the present invention may contain a polymerization initiator (preferably a photopolymerization initiator).
  • the polymerization initiator is a compound that is decomposed by light or heat to initiate and accelerate the polymerization of the above-described polymerizable compound, and preferably has absorption with respect to light in the wavelength region of 300 to 500 nm.
  • Specific examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid.
  • Examples thereof include compounds, disulfonic acid compounds, oxime compounds (particularly oxime ester compounds), onium salt compounds, and acylphosphine (oxide) compounds. More specific examples include polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749. Among the above polymerization initiators, an oxime compound (particularly an oxime ester compound) is more preferable from the viewpoint that the shape of the pattern to be obtained can be improved. As the oxime compound, IRGACURE OXE01 and OXE02 manufactured by BASF are preferable. Similar effects can be obtained with OXE01 and OXE02.
  • the content of the polymerization initiator in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content in the composition. Preferably, 2 to 20% by mass is more preferable.
  • the composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength.
  • a sensitizer what sensitizes the polymerization initiator used by an electron transfer mechanism or an energy transfer mechanism is preferable.
  • the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
  • the content of the sensitizer is preferably 0.1 to 30% by mass, based on the total solid content of the composition, from the viewpoint of sensitivity and storage stability. More preferably, it is more preferably 2 to 15% by mass.
  • the composition of the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition.
  • a polymerization inhibitor known thermal polymerization inhibitors can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
  • the content of the polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the composition.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and a higher fatty acid derivative is applied to the surface of the coating film during the drying process after coating. Etc. may be unevenly distributed.
  • the amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% by weight of the total composition.
  • the composition of the present invention may contain an adhesion improver in order to improve adhesion to a hard surface such as a support.
  • the adhesion improver include a silane coupling agent and a titanium coupling agent.
  • Silane coupling agents include ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, and ⁇ -mercaptopropyltrimethoxy.
  • the adhesion improver is contained in the composition, the content of the adhesion improver is preferably 0.5 to 30% by mass, more preferably 0.7 to 20% by mass, based on the total solid content in the composition. .
  • (K) surfactant Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) 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, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
  • 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 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactants include Toray Dow Corning (Toray Silicone DC3PA, Toray Silicone SH7PA, Tore Silicone DC11P).
  • A "Torre silicone SH21PA”, “Torre silicone SH28PA”, “Torre silicone SH29PA”, “Torre silicone SH30PA”, “Torre silicone SH8400”, “TSF-4440”, “TSF-” manufactured by Momentive Performance Materials “4300”, “TSF-4445”, “TSF-4460”, “TSF-4442”, "KP341", “KF6001", “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., "BYK307”, “BYK323”, “BYK323”, “BYK330 "etc. are mentioned.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.005 to 1.0% by mass with respect to the total mass of the composition. More preferred.
  • the preparation mode of the composition of the present invention is not particularly limited.
  • the light-shielding material, the filler, and the solvent are dispersed using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser.
  • the method is not limited to these.
  • the dispersion process may be performed by two or more dispersion processes (multistage dispersion).
  • the light-shielding composition is 4 to 30% by mass (preferably 7 to 30% by mass) with respect to the minute. If it is this composition, the light shielding film excellent in a reflective characteristic will be obtained.
  • the light shielding film of the present invention is formed using the above-described composition. That is, the light shielding composition is used for forming a light shielding film.
  • the thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 50 ⁇ m, more preferably 0.5 to 30 ⁇ m in terms of the film thickness after drying in terms of more excellent reflection characteristics of the light-shielding film. 7 to 20 ⁇ m is more preferable.
  • the size (length of one side) is preferably 0.001 to 5 mm, more preferably 0.05 to 4 mm, in order to obtain the effect of the present invention more effectively. More preferably, it is 0.1 to 3.5 mm.
  • the reflectance of the light shielding film is not particularly limited, but is preferably 4% or less, and more preferably 2% or less from the viewpoint of the effect of the present invention. Although a minimum in particular is not restrict
  • the method for measuring the reflectance of the light shielding film is such that light having a wavelength of 400 to 700 nm is incident on the light shielding film as an object to be measured at an incident angle of 5 °, and the reflectance is measured by a spectrometer UV4100 manufactured by Hitachi High Technology (product) Name).
  • the surface roughness (Ra) of the light shielding film is not particularly limited, but is preferably 0.07 to 1.55 ⁇ m and more preferably 0.08 to 1.3 ⁇ m from the viewpoint that the reflection characteristics of the light shielding film are more excellent.
  • the surface roughness of the light shielding film is measured using a stylus type film thickness meter DEKTAK150 (manufactured by VEECO).
  • the method for producing the light-shielding film of the present invention is not particularly limited, and preferably includes a step of applying the above-described composition onto a predetermined support, performing a curing treatment as necessary, and forming a light-shielding film.
  • the method for applying the composition is not particularly limited, and various coating methods such as spin coating, spray coating, slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.
  • the spin coating method (spin coating) is preferable from the viewpoint of productivity and excellent productivity.
  • the method for the curing treatment is not particularly limited, and usually a light irradiation treatment or a heat treatment is performed.
  • composition layer formation step a step of forming a composition layer
  • exposure step a step of exposing the composition layer through a mask
  • development step a step of developing the exposed composition layer to form a colored pattern
  • composition of the present invention is applied to the incident surface 6a of the IR cut filter 6 directly or via another layer to form a composition layer (composition layer forming step), It is possible to form a patterned light-shielding film by exposing through a mask pattern, curing only the coating film portion irradiated with light (exposure process), and developing with a developer (development process).
  • exposure process curing only the coating film portion irradiated with light
  • development process developing with a developer
  • composition layer forming step the light shielding film 11 that is a polymerizable composition layer is formed by applying the composition of the present invention to the incident surface 6 a of the IR cut filter 6.
  • the incident surface 6a of the IR cut filter 6 may be provided with an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • Examples of the method for applying the composition of the present invention to the incident surface 6a of the IR cut filter 6 include the methods described above.
  • the composition applied to the incident surface 6a of the IR cut filter 6 is preferably dried at 70 to 110 ° C. for about 2 to 4 minutes to form a composition layer.
  • the composition layer 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 of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2, and most preferably 10 ⁇ 800mJ / cm 2.
  • an alkali development treatment (development step) is performed to elute the light non-irradiated portion in the exposure step into the alkaline aqueous solution. Thereby, only the photocured part remains.
  • an organic alkali developer is desirable.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • alkaline aqueous solution examples include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as an inorganic developer, ammonia water, ethylamine, An alkaline compound such as diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and a concentration of 0.
  • a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like 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 formed light shielding film 11 of this invention after performing the composition layer formation process, the exposure process, and the image development process which were mentioned above, the formed light shielding film is hardened
  • a curing step may be included. In the case of curing by heating, after washing with pure water, a curing treatment is performed at 200 ° C. for 5 minutes on a hot plate.
  • the solid-state imaging device provided with the light-shielding film of the present invention is not limited to the embodiment shown in FIG.
  • FIG. 4 shows a solid-state imaging device 20 according to the second embodiment.
  • symbol is attached
  • the solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • a light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference.
  • the light shielding film 21 shields harmful light such as reflected light R ⁇ b> 3 directed toward the COMS sensor 3.
  • FIG. 5 shows a solid-state imaging device 30 according to the third embodiment.
  • the solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • a light-shielding film (light-shielding layer) 31 is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare and ghost is reliably suppressed.
  • FIG. 6 shows a solid-state imaging device 40 of the fourth embodiment.
  • the solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9.
  • a light-shielding film (light-shielding layer) 31 is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
  • a light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5.
  • Precursor M1 (50.0 g), NK ester CB-1 (2-methacryloyloxyethylphthalic acid, Shin-Nakamura Chemical Co., Ltd.) (30.0 g), benzyl methacrylate (20.0 g), dodecyl mercaptan (2 .3 g) and propylene glycol monomethyl ether acetate (233.3 g) are introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature was raised to 75 ° C.
  • V-65 2,2-azobis (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.
  • V-65 2,2-azobis (2,4-dimethylvaleronitrile)
  • Titanium Black A-1 100 g of titanium oxide MT-150A having an average particle diameter of 15 nm (trade name: manufactured by Teika Co., Ltd.), 25 g of silica particles AROPERL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m 2 / g, and dispersion 100 g of the agent Disperbyk190 (trade name: manufactured by Big Chemie), add 71 g of ion-exchange water, and use MURASTAR KK-400W manufactured by KURABO for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm.
  • Gave a homogeneous aqueous mixture.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing. After the completion, the collected powder was pulverized in a mortar to obtain titanium black A-1 [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
  • composition 1 -Titanium black (A-1) obtained as described above-25 parts-30% by weight propylene glycol monomethyl ether acetate solution of specific resin 1-25 parts-Propylene glycol monomethyl ether acetate (PGMEA) ( solvent) ... 50 copies
  • the obtained dispersion a was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a titanium black dispersion 1.
  • silica particle dispersion 2a ⁇ Preparation of silica particle dispersion 2a> Silica filler (manufactured by Admatechs Co., Ltd., SO-C1) (particle diameter 250 nm) 31 parts by mass, cyclomer P (ACA) 230AA (Daicel Cytec Co., Ltd.), solid content 54%, acid value (mgKOH / g ): 21.0, weight average molecular weight: 14000) 58 parts by mass and 11 parts by mass of hexamethoxymethylmelamine were mixed in advance, and then zirconia beads having a diameter of 1.0 mm were used with a motor mill M-50 (manufactured by Eiger).
  • the silica particle dispersion 2a was prepared by dispersing for 1.5 hours at a peripheral speed of 9 m / s.
  • silica particle dispersion 2b ⁇ Preparation of silica particle dispersion 2b>
  • the silica filler manufactured by Admatechs, SO-C1 (particle diameter 250 nm) was replaced with the silica filler (manufactured by Admatechs, SO-C2) (particle diameter 500 nm). Except for this, silica particle dispersion 2b was obtained in the same manner as in the preparation of silica particle dispersion 2a.
  • silica particle dispersion 2c ⁇ Preparation of silica particle dispersion 2c>
  • the silica filler manufactured by Admatechs Co., Ltd., SO-C1 (particle diameter 250 nm) was replaced with the silica filler (manufactured by Admatechs Co., Ltd., SO-C3) (particle diameter 900 nm).
  • a silica particle dispersion 2c was obtained in the same manner as in the preparation of the silica particle dispersion 2a.
  • silica particle dispersion 2d ⁇ Preparation of silica particle dispersion 2d>
  • the silica filler manufactured by Admatechs Co., Ltd., SO-C1 (particle diameter 250 nm) was replaced with the silica filler (manufactured by Admatechs Co., Ltd., SO-C5) (particle diameter 1600 nm).
  • a silica particle dispersion 2d was obtained in the same manner as in the preparation of the silica particle dispersion 2a.
  • Comparative Example 1 The following components were mixed with a stirrer to prepare Comparative Composition 1.
  • the comparative composition 1 does not contain a predetermined filler and a binder polymer having an acid value of 50 mgKOH / g or less.
  • Cyclomer P (ACA) 230AA (binder polymer; solid content 54%, acid value (mgKOH / g): 21.0, weight average molecular weight: 14000) 7.1 parts by mass Nippon Kayaku KAYARAD DPHA (polymerizable compound) manufactured by Nihon Kayaku Co., Ltd.
  • KAYARAD RP-1040 polymerizable compound 2.5 parts by mass IRGACURE OXE01 (polymerization initiator) manufactured by BASF 1.4 parts by mass 4-methoxy Phenol (polymerization inhibitor) 0.003 parts by mass Megafac F781 (surfactant) manufactured by DIC Corporation 0.02 parts by mass Propylene glycol monomethyl ether acetate (solvent) 4.5 parts by mass
  • Titanium Black Dispersion 1 75.1 parts by mass Cyclomer P (ACA) 230AA (binder polymer; solid content 54%, acid value (mgKOH / g): 21.0, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight: 14000) 10.7 parts by mass Nippon Kayaku Co., Ltd.
  • KAYARAD DPHA polymerizable compound 2.5 parts by mass Nippon Kayaku Co., Ltd.
  • KAYARAD RP-1040 polymerizable compound
  • BASF IRGACURE OXE01 polymerization start
  • Agent 1.4 parts by mass 4-methoxyphenol (polymerization inhibitor) 0.003 parts by mass Megafac F781 (surfactant) manufactured by DIC Corporation 0.02 parts by mass Propylene glycol monomethyl ether acetate (solvent) 5.7 parts by mass
  • the light-shielding composition 3 was prepared by further adding 3.4 parts by mass of the cyclomer P (ACA) 230AA (binder polymer; solid content 54%) manufactured by Daicel Chemical Industries, Ltd. to the light-shielding composition 2. .
  • Comparative example 2 The following components were mixed with a stirrer to prepare Comparative Composition 2.
  • the comparative composition 2 does not contain a predetermined filler and a binder polymer having an acid value of 50 mgKOH / g or less.
  • KAYARAD DPHA polymerizable compound manufactured by Nippon Kayaku Co., Ltd.
  • 2.5 parts by mass KAYARAD RP-1040 polymerizable compound manufactured by Nippon Kayaku Co., Ltd.
  • IRGACURE OXE01 polymerization initiator manufactured by BASF 1.44 parts by mass 4-methoxyphenol (polymerization inhibitor) 0.003 parts by mass Megafac F781 (surfactant) manufactured by DIC Corporation 0.02 parts by mass Propylene glycol monomethyl ether acetate (solvent) 1.9 parts by mass
  • the light-shielding composition 4 was prepared by adding 5.6 mass parts of silica particle dispersions 2a to the said comparative composition 2.
  • the light-shielding composition 5 was prepared by adding 11.3 mass parts of the silica particle dispersion 2a to the comparative composition 2.
  • the light-shielding composition 6 was prepared by adding 19.2 parts by mass of the silica particle dispersion 2a to the comparative composition 2.
  • the light-shielding composition 7 was prepared by adding 29.6 parts by mass of the silica particle dispersion 2a to the comparative composition 2.
  • the light-shielding composition 8 was prepared by adding 29.6 parts by mass of the silica particle dispersion 2b to the comparative composition 2.
  • the light-shielding composition 9 was prepared by adding 29.6 parts by mass of the silica particle dispersion 2c to the comparative composition 2.
  • the light-shielding composition 10 was prepared by adding 29.6 parts by mass of the silica particle dispersion 2d to the comparative composition 2.
  • the IR cut filter 6 on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and tetramethylammonium hydroxide. Paddle development was performed for 90 seconds at 23 ° C. using a 0.3% aqueous solution.
  • the IR cut filter 6 on which the coating film is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is ejected from above the rotation center while rotating the IR cut filter 6 at a rotation speed of 50 rpm by a rotating device.
  • Particle size in Table 1 intends the size of the filler.
  • the content of the binder polymer and filler in Table 1 corresponds to the content (% by mass) relative to the total solid content in the light-shielding composition.
  • those content is synonymous with content in a light shielding film.
  • Solid-state imaging device 2
  • CMOS sensor 3
  • Circuit board 4
  • Holding substrate for solid-state imaging device 5a Opening 5b
  • Inner wall surface 6
  • IR cut filter 7
  • Shooting lens 8
  • Lens holder 9
  • Holding cylinder 11 21, 31, 31, 41
  • Light-shielding film Light shielding layer

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Ceramic Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

La présente invention concerne : une composition bloquant la lumière, capable de former facilement un film bloquant la lumière, qui présente une faible réflectivité ; un film bloquant la lumière ; et un procédé de production d'un film bloquant la lumière. Une composition bloquant la lumière, conforme à la présente invention, contient au moins (A) des particules bloquant la lumière ou une teinte bloquant la lumière et (B) une charge ayant un diamètre de particule compris dans la plage entre 100 nm et 3 000 nm. La teneur de la charge (B) est comprise entre 3 % et 30 % en masse par rapport à la teneur totale en solide de la composition bloquant la lumière.
PCT/JP2014/068122 2013-07-10 2014-07-08 Composition et film bloquant la lumière et leur procédé de production WO2015005310A1 (fr)

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JP2013144578 2013-07-10

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WO2016129381A1 (fr) * 2015-02-09 2016-08-18 富士フイルム株式会社 Film de protection contre la lumière, filtre coupe-infrarouge équipé d'un film de protection contre la lumière, et dispositif d'imagerie à semi-conducteurs
KR102352740B1 (ko) * 2015-04-30 2022-01-18 삼성디스플레이 주식회사 마스크의 제조 방법 및 표시 장치의 제조 방법
JP6694513B2 (ja) * 2016-08-22 2020-05-13 富士フイルム株式会社 遮光性組成物、遮光膜、固体撮像素子、カラーフィルタ、及び、液晶表示装置
JP6726317B2 (ja) 2017-02-09 2020-07-22 富士フイルム株式会社 感光性組成物、硬化膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP6504299B1 (ja) * 2017-12-07 2019-04-24 東洋インキＳｃホールディングス株式会社 黒色低反射膜、および積層体の製造方法
JP2019191447A (ja) * 2018-04-27 2019-10-31 東洋インキＳｃホールディングス株式会社 ブラックマトリクス基板、その製造方法、及び該基板を有する画像表示装置
US20200201180A1 (en) * 2018-12-21 2020-06-25 Rohm And Haas Electronic Materials Korea Ltd. Colored photosensitive resin composition and black matrix prepared therefrom
TWI778829B (zh) * 2021-05-05 2022-09-21 勝麗國際股份有限公司 非迴焊式感測鏡頭
CN113740950B (zh) * 2021-11-04 2022-03-18 巨玻固能(苏州)薄膜材料有限公司 镀膜组合物、其制备方法、消光膜及镜头模组、终端

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