WO2022158313A1 - Composition, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément d'imagerie solide et unité de phare - Google Patents

Composition, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément d'imagerie solide et unité de phare Download PDF

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WO2022158313A1
WO2022158313A1 PCT/JP2022/000329 JP2022000329W WO2022158313A1 WO 2022158313 A1 WO2022158313 A1 WO 2022158313A1 JP 2022000329 W JP2022000329 W JP 2022000329W WO 2022158313 A1 WO2022158313 A1 WO 2022158313A1
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group
inorganic particles
composition
light
mass
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PCT/JP2022/000329
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English (en)
Japanese (ja)
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宏明 出井
貴規 田口
未紗保 安達
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富士フイルム株式会社
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Publication of WO2022158313A1 publication Critical patent/WO2022158313A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/40—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/08—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters for producing coloured light, e.g. monochromatic; for reducing intensity of light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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

Definitions

  • the present invention relates to compositions, cured films, color filters, light-shielding films, optical elements, solid-state imaging devices, and headlight units.
  • a color filter used in a liquid crystal display device is provided with a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
  • portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units.
  • a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and 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.
  • Patent Document 1 discloses a black resin composition for a light shielding film containing silica or the like surface-treated with a silane coupling agent having a reactive (meth)acryloyl group in the molecule.
  • the present inventors have investigated the surface-treated silica and the like described in Patent Document 1, and have found that the composition containing the silica has a development residue suppressing property when set aside (after standing for a predetermined time), In addition, they have found that at least one of the low reflectivity properties of the cured film obtained using the above composition is inferior.
  • the above-mentioned development residue suppressing property when set aside means that when a composition layer is formed using the composition and the composition layer is left to stand for a predetermined time and then subjected to exposure and development processing, It means that the generated development residue is suppressed.
  • an object of the present invention is to provide a composition that can form a cured film that is excellent in suppressing development residue when left and has excellent low reflectivity.
  • Another object of the present invention is to provide a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
  • modified inorganic particles contain inorganic particles and a coating layer covering part or all of the inorganic particles,
  • the specific group is a carboxylic acid group or a carboxylic anhydride group.
  • modified inorganic particles contain inorganic particles and a coating layer covering part or all of the inorganic particles,
  • the coating layer contains at least one selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, nitric acid groups, phenolic hydroxyl groups, and acid anhydride groups, and a hydrophobic group.
  • Composition [4] The composition according to any one of [1] to [3], wherein the inorganic particles have a particle size of less than 100 nm.
  • [5] The composition according to any one of [1] to [4], further comprising a coloring material.
  • composition of [5], wherein the colorant is a black colorant.
  • [9] further contains a resin, a polymerization initiator, and a coloring material,
  • Any one of [1] to [8], wherein the mass ratio of the total content of the modified inorganic particles, the resin, the polymerization initiator, and the polymerizable compound is 0.01 to 2.00.
  • the hydrophobic group contains at least one selected from the group consisting of fluorine atoms and silicon atoms.
  • the hydrophobic group is a dialkylsiloxane group or a fluoroalkyl group.
  • a color filter comprising the cured film of [14].
  • a light-shielding film comprising the cured film of [14].
  • An optical element comprising the cured film of [14].
  • a solid-state imaging device comprising the cured film of [14].
  • a headlight unit for a vehicle lamp comprising: a light source; and a light shielding part that shields at least part of the light emitted from the light source, A headlight unit, wherein the light shielding part contains the cured film according to [14].
  • the present invention it is possible to provide a composition that can form a cured film that is excellent in suppressing development residue when set aside and has excellent low reflectivity.
  • the present invention can also provide cured films, color filters, light-shielding films, optical elements, solid-state imaging devices, and headlight units.
  • FIG. 2 is a schematic cross-sectional view showing an enlarged imaging unit included in the solid-state imaging device shown in FIG. 1 ; It is a schematic sectional drawing which shows the structural example of an infrared sensor. It is a schematic diagram which shows the structural example of a headlight unit.
  • FIG. 4 is a schematic perspective view showing a configuration example of a light shielding portion of the headlight unit; It is a schematic diagram which shows an example of the light distribution pattern by a headlight unit.
  • FIG. 5 is a schematic diagram showing another example of a light distribution pattern by the headlight unit;
  • the notation that does not describe substitution and unsubstituted includes not only a group that does not contain a substituent but also a group that contains a substituent.
  • the term "alkyl group” includes not only alkyl groups containing no substituents (unsubstituted alkyl groups) but also alkyl groups containing substituents (substituted alkyl groups).
  • actinic rays or “radiation” in this specification means, for example, far ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, electron beams, and the like.
  • light used herein means actinic rays and radiation.
  • exposure in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also writing with particle beams such as electron beams and ion beams.
  • (Meth)acrylate in this specification means acrylate and methacrylate.
  • (Meth)acryl as used herein means acryl and methacryl.
  • (Meth)acryloyl as used herein means acryloyl and methacryloyl.
  • (Meth)acrylamide as used herein means acrylamide and methacrylamide.
  • ppm means “parts-per-million ( 10-6 )
  • ppb means “parts-per-billion ( 10-9 )
  • ppt means “ parts-per-trillion (10 ⁇ 12 )”.
  • the "weight average molecular weight (Mw)" in this specification is a polystyrene conversion value by the GPC (Gel Permeation Chromatography) method.
  • GPC method in the present specification, HLC-8020GPC (manufactured by Tosoh) as a measuring instrument, TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID ⁇ 15 cm) as columns, THF as an eluent. (tetrahydrofuran).
  • the bonding direction of the divalent groups (eg, -COO-) indicated in this specification is not limited.
  • the compound represented by the formula "X-Y-Z” when Y is -COO-, the compound may be "X-O-CO-Z", “X-CO —OZ”.
  • composition contains modified inorganic particles and a polymerizable compound.
  • the modified inorganic particles contain inorganic particles and a coating layer that partially or entirely coats the inorganic particles, and the coating layer contains a group that forms a salt under the action of an alkali (hereinafter also referred to as "specific group A”. ), and a group whose polarity is increased by the action of alkali (hereinafter also referred to as “specific group B”), and at least one specific group selected from the group consisting of a hydrophobic group. .
  • the present inventors presume as follows. Since the modified inorganic particles are covered with a coating layer having a specific group, the modified inorganic particles have excellent affinity for the developer used when forming a cured film from the composition. Therefore, it is speculated that the composition of the present invention is less likely to leave residue derived from the modified inorganic particles after being left behind, and is excellent in suppressing development residue after being left behind. In addition, when a cured film is formed from the composition, the modified inorganic particles having a hydrophobic group tend to be unevenly distributed on the surface of the cured film, and can form appropriate unevenness on the surface of the cured film.
  • the cured film obtained using the composition of the present invention can scatter the light irradiated on the surface and has excellent low reflectivity.
  • the effect of the present invention is that at least one of the effect of excellent suppression of development residue when the composition is left and the effect of excellent low reflectivity of a cured film formed from the composition is obtained. It is also said to be excellent.
  • the components contained in the composition of the present invention are described below.
  • compositions of the invention contain modified inorganic particles.
  • the modified inorganic particles have inorganic particles and a coating layer covering part or all of the inorganic particles.
  • the particle diameter of the inorganic particles is preferably 200 nm or less, more preferably less than 100 nm, still more preferably 10 to 90 nm, particularly preferably 20 to 80 nm, particularly preferably 30 to 70 nm, from the viewpoint of an excellent balance of each performance and handling property of the cured film. is most preferred.
  • particle size means the average primary particle size of particles measured by the following method.
  • the average primary particle size can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • the maximum length of the particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two straight lines parallel to the maximum length
  • Dmax the maximum length at two points on the contour of the particle image
  • DV-max two straight lines parallel to the maximum length
  • the shortest length vertically connecting two straight lines when an image is sandwiched between two straight lines was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the particle diameter.
  • the particle diameters of 100 particles were measured by this method, and the arithmetic average value was taken as the average primary particle diameter of the particles.
  • the shape of the inorganic particles examples include fibrous, needle-like, plate-like, spherical, tetrapod-like, and balloon-like, with spherical being preferred.
  • the inorganic particles may be monodisperse particles or aggregated particles.
  • the inorganic particles may be hollow particles or solid particles. Among them, the inorganic particles are preferably hollow particles because the effects of the present invention are more excellent. Hollow particles refer to particles having cavities inside the particles.
  • a hollow particle may be a structure in which the particle consists of an internal cavity and an outer shell surrounding the cavity. Further, the hollow particles may have a structure in which a plurality of cavities are present inside the particles.
  • the hollow particles preferably have a porosity of 3% or more. Although the upper limit is not particularly limited, it is preferably less than 100%, more preferably 90% or less.
  • Hollow particles have a cavity inside and have a smaller specific gravity than particles without a hollow structure. It is thought that the effect of uneven distribution in In addition, hollow particles have a lower refractive index than inorganic particles having no hollow structure.
  • hollow particles with a low refractive index are unevenly distributed on the surface of the light-shielding film, and an AR (Anti-Reflection) type low-reflection effect is obtained. , it is thought that the low reflectivity of the light shielding film is improved.
  • hollow particles include hollow silica particles described in JP-A-2001-233611 and Japanese Patent No. 3272111, and Sururia 4110 (trade name, manufactured by Nikki Shokubai Kasei Co., Ltd.).
  • Solid particles refer to particles that have substantially no cavities inside the particles. Specifically, the solid particles preferably have a porosity of less than 3%. Examples of solid particles include IPA-ST-L (trade name, manufactured by Nissan Chemical Industries, Ltd.).
  • beaded inorganic particles which are particle aggregates in which a plurality of inorganic particles are linked in a chain
  • the beaded inorganic particles are preferably those in which a plurality of spherical colloidal inorganic particles having a particle diameter of 5 to 50 nm are joined together by metal oxide-containing inorganic particles.
  • beaded inorganic particles include silica sol described in Japanese Patent No. 4328935 and JP-A-2013-253145, and beaded colloidal inorganic particles are preferred.
  • the inorganic particles are preferably other than black.
  • the inorganic particles may have a color such as red, blue, yellow, green, purple, orange, or white, or may be colorless. Among them, the inorganic particles are preferably white or colorless.
  • inorganic particles examples include inorganic oxides, inorganic nitrides, inorganic carbides, carbonates, sulfates, silicates, phosphates, and composites of two or more of these. , inorganic nitrides or carbonates are preferred, and inorganic oxides are more preferred.
  • the inorganic particles preferably contain at least silicon.
  • inorganic particles include silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), mica compounds, zinc oxide, zirconium oxide, tin oxide, potassium titanate, strontium titanate, aluminum borate, and magnesium oxide.
  • magnesium borate aluminum hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, Titanium nitride, aluminum nitride, silicon carbide, titanium carbide, and zinc sulfide.
  • the group consisting of silica, titania, alumina, mica compounds, glass, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, and calcium sulfate It preferably contains at least one selected from, more preferably contains at least one selected from the group consisting of silica, titania, alumina, and calcium carbonate, silica, titania, and alumina It is more preferable to contain at least one selected from the group consisting of, and it is particularly preferable to contain silica.
  • the refractive index of the inorganic particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35.
  • the inorganic particles may be used singly or in combination of two or more.
  • the content of silica (silicon dioxide) is preferably 75 to 100% by mass, more preferably 90 to 100% by mass, more preferably 99% by mass, based on the total mass of the inorganic particles. ⁇ 100% by mass is more preferred.
  • the coating layer has a specific group (at least one group selected from the group consisting of specific group A and specific group B) and a hydrophobic group.
  • a coating layer is a layer which coat
  • the coverage of the inorganic particles by the coating layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more, relative to the total surface area of the inorganic particles.
  • the upper limit is preferably 100% or less, more preferably 80% or less, relative to the total surface area of the inorganic particles.
  • the coating layer may be arranged directly on the surface of the inorganic particles, or may be arranged via another layer between the inorganic particles.
  • the specific group B (a group whose polarity is increased by the action of an alkali) is preferable because the evaluation of storage stability (viscosity) in the Examples section described later is superior. Further, as the specific group, the specific group B (a group whose polarity increases due to the action of alkali), or a group other than a carboxylic acid group, from the viewpoint of better evaluation of storage stability (reflectance) in the Examples section described later. Groups which form salts under the action of alkali are preferred.
  • the hydrophobic group is not particularly limited as long as it is a group exhibiting hydrophobicity.
  • the hydrophobic group include a silicon atom-containing group, a fluorine atom-containing group, an optionally substituted alkyl group, an optionally substituted aryl group, (meth)acryloyl groups, glycidoxy groups, and amino groups.
  • the hydrophobic group preferably contains at least one selected from the group consisting of a fluorine atom and a silicon atom, and more preferably contains a silicon atom.
  • the group containing a silicon atom is preferably a siloxane group or a silyl group, more preferably a siloxane group, and still more preferably a dialkylsiloxane group.
  • the silicon atom-containing group may be chain, branched, or cyclic.
  • a group containing a fluorine atom a fluoroalkyl group is preferred, and a perfluoroalkyl group is more preferred.
  • a fluorine atom-containing group may be chain, branched, or cyclic.
  • the silicon atoms mentioned above do not include silicon derived from hydrolyzable silyl groups directly bonded to the inorganic particles when a silane coupling agent is used to produce the modified inorganic particles.
  • a modified silica having a methacryloyl group is produced by reacting a trimethoxysilyl group of 3-methacryloxypropyltrimethoxysilane with silica, the trimethoxysilyl group reacted with silica
  • the derived silicon atoms do not correspond to the silicon atoms possessed by the coating layer.
  • the hydrophobic group is preferably a group contained in a repeating unit represented by formula (A1) described later (preferably a group represented by SS1 in formula (A1)).
  • the coating layer preferably contains a polymer containing repeating units represented by formula (A1).
  • the coating layer may partially contain the polymer, or may be the polymer itself.
  • the content of the polymer is preferably 10 to 100% by mass, preferably 70 to 100% by mass, more preferably 95 to 100% by mass, relative to the total mass of the coating layer.
  • the repeating unit represented by formula (A1) contained in the polymer is shown below.
  • R S1 represents an optionally substituted alkyl group or a hydrogen atom.
  • the alkyl group may be linear or branched. Moreover, the alkyl group may have a cyclic structure as a whole or may contain a cyclic structure partially.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-3.
  • the preferable number of carbon atoms referred to herein means the number of carbon atoms including the number of carbon atoms that may be present in the substituent when the alkyl group contains a substituent.
  • R S1 is preferably a hydrogen atom or a methyl group.
  • L S1 represents a single bond or a divalent linking group.
  • the divalent linking group may have a substituent, and the substituent of the divalent linking group may be a group represented by S S1 described later, or may be a group represented by S S1 described later. It may be a group partially containing the group represented by S1 .
  • the divalent linking group is preferably a combination of groups selected from the group consisting of an ester group and an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms).
  • the divalent linking group is preferably a group represented by *A-CO-O-*B or *A-CO-O-alkylene group-*B.
  • *B represents the bonding position with S S1 in formula (A1)
  • *A represents the bonding position on the opposite side to *B.
  • the alkylene group may be linear or branched. Moreover, the alkylene group may have a cyclic structure as a whole, or may partially contain a cyclic structure.
  • the alkylene group is preferably linear.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the preferable number of carbon atoms referred to herein means the number of carbon atoms including the number of carbon atoms that may exist in the substituent when the alkylene group contains a substituent.
  • the alkylene group is preferably unsubstituted.
  • S S1 represents a hydrophobic group.
  • the hydrophobic group preferably contains a silicon atom or a fluorine atom.
  • the hydrophobic group is preferably an unsubstituted alkyl group, a fluoroalkyl group, or a group represented by the formula (SS1) described later, and a fluoroalkyl group or a group represented by the formula (SS1) described later. is more preferred, and a dialkylsiloxane group or a fluoroalkyl group is even more preferred.
  • the unsubstituted alkyl group represented by S S1 may be linear or branched. Moreover, the unsubstituted alkyl group may have a cyclic structure as a whole, or may partially contain a cyclic structure.
  • the unsubstituted alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the alkyl group portion of the fluoroalkyl group represented by S S1 may be linear or branched. Moreover, the alkyl group portion may have a cyclic structure as a whole, or may partially contain a cyclic structure.
  • the number of carbon atoms in the alkyl group portion is preferably 1-15, more preferably 1-10. It is also preferable that the alkyl group portion does not contain any substituents other than fluorine atoms.
  • the number of fluorine atoms in the fluoroalkyl group is preferably 1-30, more preferably 5-20. It is also preferable that all or part of the fluoroalkyl group is a perfluoroalkyl group.
  • S S1 is preferably a group represented by formula (SS1). *-L S2 -O-SiR S2 3 (SS1)
  • R 2 S2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a substituent. * represents a binding position.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-20, more preferably 1-10, and even more preferably 1-5.
  • the number of carbon atoms here means the number of carbon atoms including the number of carbon atoms that can exist in the substituents when the above hydrocarbon group contains substituents.
  • the hydrocarbon group is preferably an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group may have a cyclic structure as a whole or may contain a cyclic structure partially.
  • a plurality of R S2 may be the same or different.
  • L S2 represents a single bond or a divalent linking group.
  • the divalent linking group for L S2 include the same groups as the divalent linking groups for L S1 in formula (A1).
  • the divalent linking group in L S2 may contain one or more (eg, 1 to 1000) -SiR S2 2 -O-.
  • R s2 in -SiR S2 2 -O- is the same as R s2 described above.
  • S S1 is more preferably a group represented by formula (A2).
  • * represents a binding position.
  • sa represents an integer from 1 to 1,000.
  • Each R S3 independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (A3) described later.
  • multiple R 3 S3 may be the same or different.
  • the hydrocarbon group that can be represented by R 2 S3 include the hydrocarbon groups that may have a substituent that can be represented by R 2 S2 described above. Among them, it is preferable that each R 3 S3 bonded to Si on the right end in formula (A2) is independently the above hydrocarbon group.
  • each R S3 in “-(-SiR S3 2 -O-) sa -" is independently a group represented by formula (A3) described later. is preferred.
  • the number of R S3 groups represented by formula (A3) among the “2 ⁇ sa” R S3 groups in “—(—SiR S3 2 —O—) sa —” is preferably 0 to 1,000. , more preferably 0 to 10, and even more preferably 0 to 2.
  • Groups represented by formula (A3) are shown below.
  • * represents a binding position.
  • sb represents an integer from 0 to 300;
  • R S4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • multiple R 2 S4 may be the same or different.
  • the hydrocarbon group that can be represented by R 2 S4 include the hydrocarbon groups that may have a substituent that can be represented by R 2 S2 described above.
  • the polymer containing the repeating unit represented by formula (A1) may contain repeating units other than the repeating unit represented by formula (A1).
  • the other repeating units a repeating unit derived from (meth)acryl or a repeating unit containing no silicon atom is preferable.
  • the molecular weight of the other repeating unit is preferably 86-1000, more preferably 100-500.
  • the content of the repeating unit represented by formula (A1) is preferably 10 to 100% by mass with respect to all repeating units, and 60 ⁇ 100% by mass is more preferable, and 90 to 100% by mass is more preferable.
  • the specific group A (group that forms a salt by the action of an alkali) is not particularly limited as long as it is a group that forms a salt with an alkali.
  • Examples of the specific group A include an acid group, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a nitric acid group, or a phenolic hydroxyl group, more preferably a carboxylic acid group or a phenolic hydroxyl group.
  • the specific group B (group whose polarity is increased by the action of an alkali) means a group whose polarity is increased by forming a polar group through decomposition or the like by the action of an alkali.
  • the specific group B include, for example, a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group such as a carboxylic acid anhydride group (-C(O)OC(O)-), an acid imide group (- NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), and sulfonate group (-SO 2 O- ).
  • a carboxylic acid ester group or an acid anhydride group is preferable, and a carboxylic acid anhydride group is more preferable.
  • the carboxylic anhydride group may be linear or cyclic, preferably cyclic.
  • the ring of the cyclic carboxylic acid anhydride group is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 5-membered ring.
  • the specific group B is preferably a group obtained by removing one or two hydrogen atoms from the compound represented by the formula (P-1), and removing one hydrogen atom from the compound represented by the formula (P-1). group is more preferred.
  • R A1a represents a substituent.
  • n1a represents an integer of 0 or more.
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a is preferably an alkylene group, an alkenylene group, or a group combining these, more preferably an alkylene group or an alkenylene group.
  • the number of carbon atoms in the alkylene group or alkenyl group is preferably 1-10, more preferably 2-5, and even more preferably 2-3.
  • n1a represents an integer of 0 or more.
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0 to 1.
  • R A1a may be the same or different.
  • two or more RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.
  • each R independently represents a hydrogen atom or a substituent.
  • Each R p independently represents a substituent, and each p independently represents an integer of 0-9. * represents a binding position.
  • the coating layer may contain a polymer containing a repeating unit having a specific group.
  • the repeating unit having a specific group preferably contains at least one selected from the group consisting of repeating units represented by formulas (D) to (F), represented by formula (E) or (F) It is more preferable to contain repeating units having
  • cylic represents a cyclic group into which an acid anhydride group has been introduced.
  • the acid anhydride group the acid anhydride group possessed by the specific group B is preferable.
  • the number of atoms contained in the cyclic group is not particularly limited.
  • Repeating units represented by formula (D) are preferably repeating units represented by formulas (d-1) to (d-4).
  • Each R p independently represents a substituent, and each p independently represents an integer of 0-4.
  • each Re independently represents a hydrogen atom or an organic group.
  • Organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may contain substituents.
  • "cylic” represents a cyclic group into which an acid anhydride group has been introduced.
  • the acid anhydride group the acid anhydride group possessed by the specific group B is preferable.
  • the number of atoms contained in the cyclic group is not particularly limited.
  • R represents a hydrogen atom or a substituent.
  • R p independently represents a substituent, and each p independently represents an integer of 0 to 8.
  • Each Re independently represents a hydrogen atom or an organic group.
  • RF represents an optionally substituted alkyl group or a hydrogen atom.
  • the alkyl group may be linear or branched. Moreover, the alkyl group may have a cyclic structure as a whole or may contain a cyclic structure partially.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-3.
  • the preferable number of carbon atoms referred to herein means the number of carbon atoms including the number of carbon atoms that may be present in the substituent when the alkyl group contains a substituent.
  • RF is preferably a hydrogen atom or a methyl group.
  • LF represents a single bond or a divalent linking group.
  • the divalent linking group is preferably a combination of groups selected from the group consisting of an alkylene group, an ester group, and an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms).
  • the alkylene group may be linear or branched. Moreover, the alkylene group may have a cyclic structure as a whole, or may partially contain a cyclic structure.
  • the alkylene group is preferably linear.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the preferable number of carbon atoms referred to herein means the number of carbon atoms including the number of carbon atoms that may exist in the substituent when the alkylene group contains a substituent.
  • the alkylene group is preferably unsubstituted.
  • SF represents an acid anhydride group.
  • the acid anhydride group the acid anhydride group possessed by the specific group B is preferable.
  • R F each independently represents an optionally substituted alkyl group or a hydrogen atom.
  • R p independently represents a substituent, and each p independently represents an integer of 0 to 8.
  • Each Re independently represents a hydrogen atom or an organic group.
  • LF represents a single bond or a divalent linking group.
  • R represents a hydrogen atom or a substituent.
  • Examples of monomers for forming repeating units having a specific group include itaconic anhydride, maleic anhydride, allylsuccinic anhydride, (2-methyl-2-propenyl)succinic anhydride, and 2-octenylsuccinic acid.
  • anhydride 2,3-dimethylmaleic anhydride, 2-dodecen-1-ylsuccinic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Acid anhydrides, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 2-butene-1-ylsuccinic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride , citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phenylmaleic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride.
  • itaconic anhydride, maleic anhydride, or allylsuccinic anhydride is preferable as the monomer.
  • the polymer contained in the coating layer preferably does not substantially contain repeating units having a hydrolyzable silyl group.
  • substantially free of repeating units means that the content of repeating units having a hydrolyzable silyl group in the polymer contained in the coating layer is 1.0% by mass or less with respect to all repeating units. However, 0.1% by mass or less is preferable. The upper limit is preferably 0% by mass.
  • the particle diameter (number average particle diameter) of the modified inorganic particles is preferably 1 to 500 nm, more preferably 20 to 200 nm, still more preferably 30 to 160 nm, and particularly preferably 30 to 100 nm, from the viewpoint that the effects of the present invention are more excellent.
  • the particle diameter of the modified inorganic particles can be measured by the same method as the particle diameter (number average particle diameter) of the inorganic particles described above, which is measured using a TEM or the like.
  • the content of the coating layer is preferably 2% by mass or more, more preferably 6% by mass or more, more preferably 8% by mass, based on the total mass of the modified inorganic particles, from the viewpoint that the effects of the present invention are more excellent.
  • the above is more preferable.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the total mass of the modified inorganic particles.
  • Modified inorganic particles may be used singly or in combination of two or more. Among them, the modified inorganic particles are preferably used singly or in combination of two. When using two or more modified inorganic particles, the total content is preferably within the following range.
  • the content of the modified inorganic particles is preferably 0.1 to 30.0% by mass, more preferably 0.5 to 20.0% by mass, relative to the total solid content of the composition, and the effects of the present invention are more excellent. From the point of view, 1.0 to 20.0% by mass is more preferable, and 2.5 to 16.0% by mass is particularly preferable.
  • the "solid content" of the composition herein means a component that forms a cured film, and when the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. .
  • a liquid component is also regarded as a solid content.
  • the method for producing the modified inorganic particles is not particularly limited, and for example, the following production method A can be mentioned.
  • the ethylenically unsaturated group of the coating precursor layer in the modified inorganic particle precursor containing the inorganic particles and the coating precursor layer containing the ethylenically unsaturated group by coating the inorganic particles, and the formula (1b) described later Ethylenically unsaturated group in the represented compound and a compound containing the above-described specific group and having an ethylenically unsaturated group (preferably the compound represented by formula (P-1)) in the ethylenically unsaturated group is polymerized to form a coating layer containing the polymer on the surfaces of the inorganic particles to coat the inorganic particles (coating layer forming step).
  • the modified inorganic particle precursor in the modified inorganic particle manufacturing method A contains inorganic particles and a coating precursor layer that coats the inorganic particles.
  • the inorganic particles in the modified inorganic particle precursor include, for example, the inorganic particles exemplified as the inorganic particles of the modified inorganic particles.
  • the coating precursor layer in the modified inorganic particle precursor contains ethylenically unsaturated groups (eg, (meth)acryloyl groups, vinyl groups, styryl groups, etc.).
  • the modified inorganic particle precursor may be used after purchasing a commercially available product, or may be used after being manufactured.
  • inorganic particles are reacted with a silane coupling agent containing an ethylenically unsaturated group (e.g., 3-methacryloxypropyltrimethoxysilane, etc.) to obtain inorganic particles. and forming a coating precursor layer on the surface of to produce a modified inorganic particle precursor.
  • a silane coupling agent containing an ethylenically unsaturated group e.g., 3-methacryloxypropyltrimethoxysilane, etc.
  • R S1 represents an optionally substituted alkyl group or a hydrogen atom.
  • L S1 represents a single bond or a divalent linking group.
  • S S1 represents a group containing -SiR S2 2 -O-.
  • R S2 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • a plurality of R S2 may be the same or different.
  • Each group represented by each symbol in formula (1b) is the same as the group represented by the corresponding symbol in formula (A1). That is, the compound represented by formula (1b) is a monomer corresponding to the repeating unit represented by formula (A1).
  • the ethylenically unsaturated groups in the coating precursor layer of the modified inorganic particle precursor and the ethylenically unsaturated groups in the compound represented by formula (1b) (preferably represented by formula (1b) Ethylenically unsaturated group specified in the formula (1b) in the compound obtained) and a compound containing a specific group and containing an ethylenically unsaturated group (preferably represented by formula (P-1)
  • a polymer-containing coating layer is formed on the surfaces of the inorganic particles by polymerizing (generally, radically polymerizing) the ethylenically unsaturated groups in the compound) to cover the inorganic particles.
  • the polymerization system contains a compound represented by the formula (1b), and a compound containing a specific group A and an ethylenically unsaturated group (preferably, the formula (P -1), other compounds containing ethylenically unsaturated groups (hereinafter also referred to as "other compounds") may be present.
  • the above other compounds are preferably compounds containing no silicon atoms.
  • (Meth)acrylic compounds are preferable as the other compounds.
  • the molecular weight of the other compound is preferably 86-1000, more preferably 100-700.
  • the compound represented by formula (1b) and a compound containing a specific group and containing an ethylenically unsaturated group (preferably, formula (P-1).
  • the total content of the compound represented by ) is the compound represented by formula (1b), a compound containing a specific group and an ethylenically unsaturated group (preferably, formula (P-1) compound represented), and other compounds (preferably silicon-free compounds), relative to the total content, preferably 10 to 100% by mass, more preferably 60 to 100% by mass, 90 to 100 % by mass is more preferred.
  • a purification treatment is performed to separate part or all of the polymerized product polymerized without being incorporated into the polymer of the coating layer in the coating layer forming step and the resulting modified inorganic particles.
  • the purification treatment include a treatment of filtering (preferably microfiltration) the solution subjected to the coating layer forming step, obtaining modified inorganic particles as a filter cake, and separating the polymerization product into the filtrate.
  • Other purification treatments include centrifugation of the solution subjected to the coating layer forming step to separate the supernatant containing the polymerization product and the sediment containing the modified inorganic particles. In carrying out the filtration and / or the centrifugation, the solution that has undergone the coating layer forming step is treated for efficient purification treatment (for example, addition of a suitable solvent and / or partial distillation of the solvent etc.) may be implemented.
  • the modified inorganic particles with the polymerization product adhered on the surface may be obtained by evaporating the solvent of the solution subjected to the coating layer forming step without performing the purification treatment.
  • the modified inorganic particles thus obtained may be directly mixed with other raw materials and used to produce a composition.
  • the modified inorganic particles may be redispersed in another solvent and the resulting dispersion used to prepare the composition and mixed with other raw materials.
  • the solution containing the modified inorganic particles subjected to the coating layer forming step may be mixed with other raw materials as it is for use in the production of the composition.
  • the following manufacturing method B is also mentioned as a manufacturing method of a modified inorganic particle.
  • the inorganic particles are reacted with a silane coupling agent containing a hydrophobic group and a silane coupling agent containing a specific group to form a coating layer on the surface of the inorganic particles to cover the inorganic particles.
  • a method B for producing modified inorganic particles which includes a step (coating layer forming step B), is also included.
  • the modified inorganic particles obtained by the production method B are surface-modified with a silane coupling agent containing at least a silane coupling agent containing a hydrophobic group and a silane coupling agent containing a specific group. It corresponds to inorganic particles.
  • Examples of the inorganic particles include the inorganic particles exemplified as the inorganic particles of the modified inorganic particles.
  • Silane coupling agents containing a hydrophobic group include, for example, silane coupling agents containing a group represented by SS1 in formula (A1) described above.
  • a compound represented by Formula (2b) is preferred.
  • X represents a hydroxyl group or -OR S3 .
  • R S3 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • Y represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • L S2 represents a single bond or a divalent linking group.
  • SS2 represents a specific group.
  • a represents an integer of 1 to 3;
  • b represents an integer of 0 to 2; However, a+b is 3.
  • R S3 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • R S3 is preferably a hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent, more preferably an unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and an unsubstituted hydrocarbon group having 1 to 5 carbon atoms.
  • a hydrocarbon group is more preferred, and a methyl group or an ethyl group is particularly preferred.
  • a plurality of R S3 may be the same or different.
  • Y represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • Y has the same definition as R S3 , and the preferred range is also the same.
  • L S2 represents a single bond or a divalent linking group.
  • L S2 is preferably an optionally substituted alkylene group.
  • the number of carbon atoms in the alkylene group which may contain a substituent is preferably 1-20, more preferably 1-10, and even more preferably 1-5.
  • the alkylene group may be linear, branched, or cyclic.
  • SS2 represents a specific group.
  • the specific group represented by SS2 has the same meaning as the specific group possessed by the coating layer described above, and the preferred range is also the same.
  • a represents an integer of 1 to 3; As a, 2 to 3 are preferable, and 3 is more preferable.
  • b represents an integer of 0 to 2; b is preferably 0 to 1, more preferably 0. However, a+b is 3.
  • silane coupling agents include silane coupling agents that do not contain a hydrophobic group and the specific group A or the specific group B and that contain an amino group, an aryl group, or an epoxy group.
  • composition of the present invention may contain other modified inorganic particles or other inorganic particles in addition to the above modified inorganic particles.
  • modified inorganic particles include, but are not limited to, modified inorganic particles other than the modified inorganic particles described above.
  • Inorganic particles contained in other modified inorganic particles include inorganic particles possessed by the modified inorganic particles described above.
  • composition of the invention contains a polymerizable compound.
  • polymerizable compound means an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized under the action of a polymerization initiator or the like, which will be described later.
  • the composition of the present invention contains a solvent, the polymerizable compound is preferably dissolved in the solvent.
  • the polymerizable compound may be a low-molecular-weight polymerizable compound or a high-molecular-weight polymerizable compound.
  • low-molecular-weight polymerizable compounds include polymerizable low-molecular-weight compounds described later.
  • high-molecular-weight polymerizable compound include resins described later that contain groups (ethylenically unsaturated groups, etc.) that polymerize under the action of a polymerization initiator.
  • the content of the polymerizable compound (the total content of the low-molecular-weight polymerizable compound and the high-molecular-weight polymerizable compound) is preferably 10 to 90% by mass based on the total solid content of the composition.
  • the content of the polymerizable compound is preferably 50 to 90% by mass, based on the total solid content of the composition, and 65 to 85% by mass. more preferred. Further, when the composition of the present invention contains a coloring material to be described later, the content of the polymerizable compound is preferably 15 to 55% by mass, based on the total solid content of the composition, and 20 to 50% by mass. more preferred. The content of the polymerizable compound is preferably 20 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 88% by mass, based on the total non-colored organic solid content of the composition.
  • a non-coloring organic solid content is a solid content and refers to a non-coloring organic component.
  • inorganic particles discussed above, do not fall under the organic component and are not included in non-colored organic solids.
  • a component used as a coloring material or a coloring agent organic pigment, etc.
  • Non-colored organic solids include, for example, a polymerizable compound, a resin described later that does not contain a group that polymerizes under the action of a polymerization initiator (ethylenically unsaturated group, etc.), a polymerization initiator, a surfactant agents and polymerization inhibitors.
  • a polymerization initiator ethylenically unsaturated group, etc.
  • a surfactant agents ethylenically unsaturated group, etc.
  • a polymerizable low-molecular-weight compound is one form of a polymerizable compound.
  • the content of the polymerizable low-molecular-weight compound in the composition is preferably 5-60% by mass based on the total solid content of the composition.
  • the content of the polymerizable low-molecular-weight compound is preferably 20 to 50% by mass, more preferably 25 to 40% by mass, based on the total solid content of the composition. % is more preferred.
  • the content of the polymerizable low-molecular-weight compound is preferably 7 to 30% by mass, more preferably 10 to 20% by mass, based on the total solid content of the composition. % is more preferred.
  • the content of the polymerizable low-molecular-weight compound is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total non-colored organic solid content of the composition. .
  • the polymerizable low-molecular-weight compounds may be used singly or in combination of two or more. When two or more polymerizable low-molecular-weight compounds are used, the total content is preferably within the above range.
  • the molecular weight (or weight-average molecular weight) of the polymerizable low-molecular-weight compound is not particularly limited, but is preferably 2500 or less. The lower limit is preferably 100 or more.
  • the polymerizable low-molecular-weight compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond). That is, the composition of the present invention preferably contains an ethylenically unsaturated group-containing low-molecular-weight compound as a polymerizable low-molecular-weight compound.
  • the polymerizable low-molecular-weight compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, still more preferably a compound containing three or more, and particularly a compound containing four or more. preferable.
  • the upper limit is, for example, 15 or less.
  • Ethylenically unsaturated groups include, for example, vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • polymerizable low-molecular-weight compound for example, the compounds described in paragraph [0050] of JP-A-2008-260927 and paragraph [0040] of JP-A-2015-68893 can be used. is incorporated herein.
  • Polymerizable low-molecular-weight compounds may be in any chemical form such as monomers, prepolymers, oligomers, mixtures thereof, and polymers thereof.
  • the polymerizable low-molecular compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • the polymerizable low-molecular-weight compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100°C or higher under normal pressure.
  • a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100°C or higher under normal pressure.
  • the compounds described in paragraph [0227] of JP-A-2013-29760 and paragraphs [0254] to [0257] of JP-A-2008-292970 can be used, and the contents thereof are incorporated herein.
  • Polymerizable low-molecular-weight compounds include dipentaerythritol triacrylate (commercially available, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available, for example, KAYARAD D-320 Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available, for example, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available , for example, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are via ethylene glycol residues or propylene glycol residues (eg, SR454, SR499, commercial
  • oligomeric types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD DPEA-12LT KAYARAD DPHA LT
  • KAYARAD RP-3060 KAYARAD DPEA-12
  • the polymerizable low-molecular-weight compound may be a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond in the compound. manufactured by Nippon Kayaku Co., Ltd.) may be used.
  • Preferred embodiments of the polymerizable low-molecular compound are shown below.
  • the polymerizable low-molecular-weight compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups.
  • the polymerizable low-molecular-weight compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid.
  • a polymerizable low-molecular-weight compound having an acid group is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is more preferable.
  • Commercially available products include, for example, Aronix TO-2349, M-305, M-510 and M-520 manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable low-molecular compound containing an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g.
  • the acid value of the polymerizable low-molecular-weight compound is 0.1 mgKOH/g or more, the development dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • a preferred embodiment of the polymerizable low-molecular-weight compound is a compound containing a caprolactone structure.
  • Examples of compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure in the molecule.
  • Examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol,
  • Examples include ⁇ -caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ⁇ -caprolactone. be done.
  • a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents the number of 1 or 2
  • * represents a bonding position
  • R 1 represents a hydrogen atom or a methyl group
  • "*" represents a bonding position
  • Commercially available polymerizable low-molecular-weight compounds containing a caprolactone structure include, for example, M-350 (trade name) (trimethylolpropane tri
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used as the polymerizable low-molecular compound.
  • E represents -((CH 2 ) y CH 2 O)- or ((CH 2 ) y CH(CH 3 )O)-, and y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of (meth)acryloyl groups is 3 or 4
  • m represents an integer of 0-10, and the sum of m is an integer of 0-40.
  • formula (Z-5) the total number of (meth)acryloyl groups is 5 or 6
  • n represents an integer of 0-10, and the sum of each n is an integer of 0-60.
  • m is preferably an integer of 0-6, more preferably an integer of 0-4.
  • the sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
  • n is preferably an integer of 0-6, more preferably an integer of 0-4.
  • the sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and even more preferably an integer of 6-12.
  • -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is on the oxygen atom side is preferably bound to X.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used singly or in combination of two or more.
  • formula (Z-5) a form in which all six X are acryloyl groups, a compound in which all six X are acryloyl groups in formula (Z-5), and among six X,
  • a preferred embodiment is a mixture with a compound having at least one hydrogen atom. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable low-molecular-weight compound is preferably 20% by mass or more, more preferably 50% by mass or more.
  • pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.
  • the polymerizable low-molecular-weight compound may contain a cardo skeleton.
  • a polymerizable low-molecular-weight compound containing a cardo skeleton is preferably a polymerizable low-molecular-weight compound containing a 9,9-bisarylfluorene skeleton.
  • Examples of polymerizable low-molecular-weight compounds containing a cardo skeleton include Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).
  • the polymerizable low-molecular-weight compound is also preferably a compound containing an isocyanuric acid skeleton as a central nucleus.
  • examples of such polymerizable low-molecular-weight compounds include NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the content of ethylenically unsaturated groups in the polymerizable low-molecular-weight compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable low-molecular-weight compound by the molecular weight (g/mol) of the polymerizable low-molecular-weight compound ) is preferably 5.0 mmol/g or more.
  • the upper limit is preferably 20.0 mmol/g or less.
  • the composition of the invention preferably contains a coloring material.
  • the coloring material is a material different from the inorganic particles described above.
  • Colorants include, for example, chromatic colorants, achromatic colorants, and infrared absorbers.
  • a chromatic colorant means a colorant other than a white colorant and a black colorant.
  • the chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.
  • the colorant preferably contains at least one selected from the group consisting of chromatic colorants and achromatic colorants, and contains at least one selected from the group consisting of chromatic colorants and black colorants.
  • the pattern shape when placed is more excellent, it is more preferable to contain at least one selected from the group consisting of a chromatic colorant of an organic pigment and a black colorant of an inorganic pigment, and carbon black It is particularly preferred to include black colorants other than inorganic pigments.
  • the content of the coloring material is preferably 30 to 80% by mass based on the total solid content of the composition.
  • the lower limit is more preferably 40% by mass or more, still more preferably 44% by mass or more, and particularly preferably 48% by mass or more, from the viewpoint of better color separation.
  • the upper limit is more preferably less than 70% by mass, and even more preferably 65% by mass or less, from the viewpoint of further improving the accuracy of the pattern shape. When two or more coloring materials are included, the total amount thereof preferably falls within the above range.
  • the lower limit of the mass ratio of the content of the coloring material to the content of the modified inorganic particles is 1 or more from the viewpoint of better color separation. It is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more.
  • the upper limit is preferably 16 or less, more preferably 14 or less, even more preferably 13 or less, and particularly preferably 12 or less, from the viewpoint of better transmittance. In particular, if the mass ratio is in the range of 2 to 14, the occurrence of peeling after the moisture resistance test can be further suppressed.
  • Mass ratio of the total content of modified inorganic particles, resin, polymerization initiator and polymerizable compound to the content of coloring material is preferably 0.01 to 2.00, more preferably 0.10 to 1.80, even more preferably 0.20 to 1.00.
  • Chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, violet colorants and orange colorants.
  • a chromatic colorant may be a pigment or a dye.
  • a pigment and a dye may be used in combination.
  • the pigment may be either an inorganic pigment or an organic pigment, and an inorganic pigment is preferable.
  • an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing an inorganic pigment or an organic-inorganic pigment with an organic chromophore, hue design can be facilitated.
  • the average primary particle size of the pigment is preferably 1 to 200 nm.
  • the lower limit is more preferably 5 nm or more, and even more preferably 10 nm or more.
  • the upper limit is more preferably 180 nm or less, still more preferably 150 nm or less, and particularly preferably 100 nm or less.
  • the primary particle diameter of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment.
  • the primary particles of the pigment refer to independent particles without agglomeration.
  • the chromatic colorant preferably contains a pigment.
  • the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. is particularly preferred.
  • the upper limit is preferably 100% by mass or less. Examples of pigments include those shown below.
  • a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule.
  • Specific examples include compounds described in International Publication No. 2015/118720.
  • compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds having phosphoric acid esters as ligands described in WO 2012/102395, and the like can also be used.
  • An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraphs [0022] to [0030] of JP-A-2012-247591 and paragraph [0047] of JP-A-2011-157478.
  • JP-A-6443711 pigments, quinophthalone-based yellow pigments described in JP-A-2018-155881, compounds described in JP-A-2018-062644, quinophthalone compounds described in JP 6432077, and patents Pigments described in JP-A-6443711 can also be used.
  • JP-A-2018-062644 can also be used as the yellow pigment.
  • This compound can also be used as a pigment derivative.
  • a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolo described in paragraphs [0016] to [0022] of Japanese Patent No. 6248838 Pyrrole compounds, diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, naphthol azo compounds described in JP 2012-229344, etc. can also be used.
  • a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may also be used. can.
  • the compounds described in Japanese Patent Nos. 6516119 and 6525101 can also be used as red pigments.
  • This compound can also be used as a pigment derivative.
  • dyes can also be used as chromatic colorants.
  • the dye is not particularly limited, and known dyes can be used.
  • thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be preferably used.
  • yellow dyes for example, quinophthalone compounds described in paragraphs [0011] to [0034] of JP-A-2013-054339 and quinophthalones described in paragraphs [0013] to [0058] of JP-A-2014-026228 Compounds can also be used.
  • achromatic colorant examples include black colorants and white colorants, with black colorants being preferred.
  • black colorant examples include one or more selected from the group consisting of black pigments and black dyes.
  • a plurality of coloring agents that cannot be used alone as a black coloring agent may be combined and adjusted so as to be black as a whole, and used as a black coloring agent.
  • a plurality of pigments having a color other than black alone may be used in combination as a black pigment.
  • a plurality of dyes having a color other than black alone may be used in combination as a black dye
  • a pigment having a color alone other than black and a dye alone having a color other than black may be combined to form a black dye.
  • a black colorant means a colorant that absorbs over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black colorant that meets the evaluation criteria Z described below is preferred.
  • a composition containing a coloring material, a transparent resin matrix (acrylic resin or the like), and a solvent, and having a coloring material content of 60% by mass relative to the total solid content is prepared.
  • the resulting composition is applied onto a glass substrate so that the thickness of the cured film after drying is 1 ⁇ m to form a cured film.
  • the light-shielding property of the cured film after drying is evaluated using a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd., etc.).
  • the coloring material can be judged to be a black coloring material that meets the evaluation criteria Z.
  • the maximum value of the transmittance of the cured film after drying at a wavelength of 400 to 700 nm is more preferably less than 8%, more preferably less than 5%, in the evaluation criteria Z.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • the black colorant is preferably a black pigment, more preferably an inorganic pigment, from the viewpoint that the light resistance of the light shielding film is more excellent.
  • the black pigment a pigment that expresses black color by itself is preferable, and a pigment that expresses black color by itself and absorbs infrared rays is more preferable.
  • the black pigment that absorbs infrared rays has absorption in, for example, the wavelength region of the infrared region (preferably wavelength of 650 to 1300 nm).
  • a black pigment having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is also preferred.
  • the particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, from the viewpoint of better balance between handling properties and the stability of the composition over time (black pigment does not settle). 5 to 30 nm is more preferred.
  • the particle size of the black pigment means the average primary particle size of particles measured by the following method.
  • the average primary particle size can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • the maximum length of the particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two straight lines parallel to the maximum length
  • Dmax the maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the shortest length vertically connecting two straight lines when an image is sandwiched between two straight lines was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the particle diameter.
  • the particle diameters of 100 particles were measured by this method, and the arithmetic average value was taken as the average primary particle diameter of the particles.
  • Inorganic pigment used as black colorant is not particularly limited as long as it has a light-shielding property and contains an inorganic compound, but known inorganic pigments can be used. . Inorganic pigments are preferable as the black colorant because the light-shielding film has better low reflectivity and light-shielding properties.
  • inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), and aluminum (Al).
  • Group 4 metal elements such as titanium (Ti) and zirconium (Zr)
  • Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), and aluminum (Al).
  • the inorganic pigment may contain two or more metal atoms.
  • metal oxides metal nitrides and metal oxynitrides, particles in which other metal atoms are mixed may be used.
  • metal nitride-containing particles further containing atoms (preferably oxygen atoms and/or sulfur atoms) selected from elements of groups 13 to 17 of the periodic table can be used.
  • the metal oxide, metal nitride and metal oxynitride may be coated with an inorganic substance and/or an organic substance.
  • the inorganic substance include metal atoms contained in the inorganic pigment.
  • organic substance include organic substances having the hydrophobic group described above, and silane compounds are preferable.
  • the method for producing the above metal nitride, metal oxide or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained. You can use the method.
  • the vapor phase reaction method includes an electric furnace method, a thermal plasma method, and the like, but the thermal plasma method is preferable from the viewpoints of less impurity contamination, easier particle diameter uniformity, and higher productivity.
  • the metal nitride, metal oxide or metal oxynitride may be subjected to a surface modification treatment.
  • the surface may be modified with a surface treating agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Inorganic pigments also include, for example, zirconium nitride containing yttrium.
  • zirconium nitride containing yttrium When the composition contains yttrium-containing zirconium nitride, it is possible to improve the visible light shielding property while maintaining the i-line transmittance.
  • the particle size (average primary particle size) of the yttrium-containing zirconium nitride is preferably 10 to 100 nm from the viewpoint of suppressing a decrease in light shielding properties at a wavelength of 550 nm (visible light).
  • the average primary particle size of the yttrium-containing zirconium nitride powder can be measured by converting the measured specific surface area into spheres.
  • yttrium is contained in a solid solution state in the zirconium nitride powder.
  • X1 is the light transmittance at a wavelength of 550 nm
  • X2 is the light transmittance at a wavelength of 365 nm. 5% or less is preferable, and 6.5% or less is more preferable.
  • X2 is preferably 25% or more, more preferably 26% or more.
  • the ratio of X2 to X1 (X2/X1) is preferably 3.5 or more, more preferably 4.0 or more.
  • the content of yttrium is preferably 1.0 to 12.0% by mass, relative to the total mass of zirconium nitride and yttrium, from the viewpoint of suppressing a decrease in light shielding properties at a wavelength of 550 nm (visible light), and 2.0 to 2.0%. 11.0% by mass is more preferable.
  • the above content can be measured by ICP emission spectrometry.
  • Yttrium-containing zirconium nitride and its production method include, for example, those described in JP-A-2020-180036, the contents of which are incorporated herein.
  • Inorganic pigments also include, for example, zirconium nitride containing aluminum.
  • Zirconium containing aluminum is preferably zirconium nitride coated with alumina.
  • Moisture resistance is improved by coating zirconium nitride with alumina.
  • the zirconium nitride coated with alumina preferably has a volume resistivity of 1 ⁇ 10 6 ⁇ cm or more, more preferably 1 ⁇ 10 7 ⁇ cm or more.
  • the volume resistivity of zirconium nitride coated with alumina is obtained as follows.
  • Alumina-coated zirconium nitride is placed in a pressure vessel and compressed at 5 to 10 MPa to form a compact, and the resistance value of the compact is measured with a digital multimeter. Then, the obtained resistance value is multiplied by a resistivity correction factor (RCF) that is referred to based on the thickness of the green compact, the shape of the apparatus, and the thickness of the green compact, to obtain the volume resistivity of the powder ( ⁇ cm) is obtained.
  • RCF resistivity correction factor
  • the coating amount of alumina is preferably 1.5 to 9% by mass, more preferably 3 to 7% by mass with respect to 100% by mass of zirconium nitride.
  • the isoelectric point of zirconium nitride coated with alumina is preferably 5.7 or higher, more preferably 5.8 or higher.
  • the “isoelectric point of alumina-coated zirconium nitride” means that when the pH of a dispersion liquid in which alumina-coated zirconium nitride is dispersed, the charge per piece becomes zero as a whole, and the dispersion liquid means the pH at which the powder does not move even if a voltage is applied to .
  • an inorganic nitride powder such as a zirconium nitride powder, exhibits a large change in zeta potential when the pH changes, and at a certain pH, the surface potential (zeta potential) becomes zero, and the isoelectric potential does not exhibit any electrophoresis. have a point.
  • zeta potential is an electric double layer, which is an electric double structure formed by attracting ions with opposite polar charges around powder with a certain polar charge in a dispersion liquid. , means the potential of the sliding surface at which liquid flow begins to occur. This zeta potential is measured as follows using, for example, a zeta potential meter (model: DT1202) manufactured by Dispersion Technology.
  • the device is measured using the colloidal oscillating current method.
  • the above dispersion is placed in a container and sandwiched between a pair of electrodes, and a predetermined voltage is applied to these electrodes to move the powder in the dispersion.
  • a predetermined voltage is applied to these electrodes to move the powder in the dispersion.
  • the charged particles and their surrounding counter ions are polarized, generating an electric field called the colloidal oscillation potential, which can be detected as a current.
  • This current becomes a colloidal oscillation current.
  • the zeta potential is determined from the measured colloidal oscillatory currents using Smoluchowski's equation and coupling theory.
  • the pH at which the zeta potential becomes zero is the isoelectric point of the powder.
  • the L * value of zirconium nitride coated with alumina is preferably 13 or less.
  • the “L * value of zirconium nitride coated with alumina” is the lightness index in the CIE1976 L * a * b * color space (measurement light source C: color temperature 6774K).
  • the above CIE1976L * a * b * color space was converted from the CIEXYZ color system by the International Commission on Illumination (CIE) in 1976, and a constant distance in the color system is almost perceptually uniform in any color region. It is a color space defined to have a difference.
  • L * value, a * value, and b * value are quantities determined by an orthogonal coordinate system in the CIE1976L * a * b * color space, and are expressed by equations (1) to (3).
  • L * 116(Y/Y0) 1/ 3-16 ( 1 )
  • a * 500 [(X/X 0 ) 1/3 - (Y/Y 0 ) 1/3 ]
  • b * 200 [(Y/Y 0 ) 1/3 - (Z/Z 0 ) 1/3 ] (3)
  • X/X 0 , Y/Y 0 , Z/Z 0 >0.008856
  • X, Y, and Z are the tristimulus values of the object color.
  • the lightness index L * value of zirconium nitride coated with alumina is determined using, for example, a spectral color difference meter (model: SE7700) manufactured by Nippon Denshoku Industries Co., Ltd. When the L * value is 13 or less, the blackness is sufficient and a predetermined color tone can be obtained as a black pigment.
  • the BET specific surface area of zirconium nitride coated with alumina is preferably 20 m 2 /g or more.
  • the upper limit is preferably 1000 m 2 /g or less.
  • the BET specific surface area is measured by using, for example, a specific surface area measuring device (model: SA1100) manufactured by Shibata Kagaku Co., Ltd., on the surface of the powder (black pigment), a gas molecule (for example, nitrogen gas, etc.) whose adsorption area is known. is adsorbed and calculated from the adsorption amount.
  • the BET equation when adsorption is in equilibrium at a constant temperature, adsorption
  • the amount of gas molecules in only one layer is measured, making it possible to measure the exact specific surface area.
  • the BET specific surface area is 20 m 2 /g or more, a decrease in coloring power (color development power) can be suppressed.
  • Alumina-coated zirconium nitride and its manufacturing method include, for example, those described in JP-A-2020-158377, the contents of which are incorporated herein.
  • nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are more preferable because they can suppress the occurrence of undercuts when forming a light-shielding film.
  • one or more metal oxynitrides selected from the group consisting of titanium, vanadium, zirconium and iron are more preferable, and zirconium oxynitride or titanium oxynitride (titanium black ) is particularly preferred.
  • Titanium black is black particles containing titanium oxynitride. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing cohesion, and the like. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. can also be processed.
  • Titanium black can be produced by heating a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (JP-A-49-5432), and ultra-fine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method of reducing titanium in a reducing atmosphere containing hydrogen JP-A-57-205322
  • a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia JP-A-60-65069, Japanese Patent Application Laid-Open No. 61-201610
  • a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide and subjecting it to high-temperature reduction in the presence of ammonia Japanese Patent Application Laid-Open No. 61-201610.
  • the particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm.
  • the specific surface area of titanium black is not particularly limited, but since the water repellency after surface treatment with a water repellent agent has a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method is 5 to 5. It is preferably 150 m 2 /g, more preferably 20 to 100 m 2 /g.
  • titanium black for example, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilac D (trade name) , manufactured by Ako Kasei Co., Ltd.), and MT-150A (trade name, manufactured by Teika Co., Ltd.).
  • the composition also preferably contains titanium black as a dispersant containing titanium black and Si atoms.
  • titanium black is contained as a dispersant in the composition.
  • the content ratio (Si/Ti) of Si atoms and Ti atoms in the material to be dispersed is preferably 0.05 to 0.5, more preferably 0.07 to 0.4 in terms of mass.
  • the material to be dispersed includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles).
  • the Si/Ti ratio of the substance to be dispersed is at least a predetermined value, when a composition layer using the substance to be dispersed is patterned by photolithography or the like, it is difficult for a residue to remain in the removed portion. If /Ti is equal to or less than a predetermined value, the light shielding ability tends to be good.
  • the following means can be used. First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this mixture is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C.), so that titanium black particles are the main component. Then, a dispersed material containing Si and Ti can be obtained. Titanium black in which Si/Ti is adjusted can be produced, for example, by the method described in paragraphs [0005] and [0016] to [0021] of JP-A-2008-266045.
  • the content ratio (Si/Ti) of Si atoms and Ti atoms in the object to be dispersed is, for example, the method described in paragraphs [0054] to [0056] of WO 2011/049090 (2-1 ) or method (2-3).
  • the above titanium black can be used.
  • a composite oxide of a plurality of metals selected from Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, and aniline black may be used singly or in combination of two or more as an object to be dispersed.
  • the dispersed material comprising titanium black accounts for 50% by mass or more of the total dispersed material.
  • Inorganic pigments also include carbon black.
  • Carbon blacks include, for example, furnace black, channel black, thermal black, acetylene black and lamp black.
  • carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used.
  • Specific examples of commercial products of carbon black include C.I. I. Pigment Black 1 and other organic pigments, and C.I. I. Inorganic pigments such as Pigment Black 7 can be used.
  • Carbon black that has undergone surface treatment is preferable as the carbon black.
  • the surface treatment can modify the surface state of the carbon black particles and improve the dispersion stability in the composition.
  • Examples of the surface treatment include coating treatment with a resin, surface treatment for introducing an acidic group, and surface treatment with a silane coupling agent.
  • the carbon black carbon black coated with a resin is preferable.
  • the light shielding properties and insulating properties of the light shielding film can be improved.
  • the reliability of the image display device can be improved by reducing leakage current. Therefore, the light shielding film is suitable for applications that require insulation.
  • Coating resins include epoxy resins, polyamides, polyamideimides, novolac resins, phenolic resins, urea resins, melamine resins, polyurethanes, diallyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonates, polybutylene terephthalate, and modified polyphenylene oxides.
  • the content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total amount of the carbon black and the coating resin, from the viewpoint that the light shielding film has better light shielding properties and insulating properties. more preferred.
  • the crystallite size of the inorganic pigment is preferably 10 nm or more, more preferably 20 nm or more.
  • the upper limit is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.
  • the crystallite size is less than 10 nm, the particle surface is likely to be oxidized, resulting in a decrease in light shielding properties. If the crystallite size is more than 60 nm, the transmission peak of the colored film shifts to longer wavelengths, resulting in lower light transmittance in the ultraviolet region and lower light shielding properties in the visible region.
  • the crystallite size is determined, for example, by the following method. It can be calculated from the half width of the X-ray diffraction peak derived from the (111) plane in the X-ray diffraction spectrum when CuK ⁇ rays are used as the X-ray source.
  • K represents a constant of 0.9.
  • ⁇ represents 0.15406 (nm).
  • ⁇ is a value represented by the above formula (5).
  • ⁇ is as described above.
  • Equation (5) ⁇ e represents the half width of the diffraction peak.
  • ⁇ O represents the half width correction value (0.12°).
  • ⁇ , ⁇ e and ⁇ O are calculated in radians.
  • the X-ray diffraction spectrum is measured by a wide-angle X-ray diffraction method using CuK ⁇ rays as an X-ray source.
  • the X-ray diffractometer for example, RU-200R manufactured by Rigakusha can be used.
  • the measurement conditions are an output of 50 kV/200 mA, a slit system of 1°-1°-0.15 mm-0.45 mm, a measurement step (2 ⁇ ) of 0.02°, and a scan speed of 2°/min.
  • the value of the X-diffraction peak includes, for example, paragraphs [0027] to [0028] of JP-A-2009-091205, the contents of which are incorporated herein.
  • a method of adjusting the crystallite size within the above range includes, for example, a method of adjusting crystal growth conditions during particle synthesis by gas phase reaction.
  • the crystallite size can be easily adjusted within the above range by adjusting the cooling time and cooling rate after the particles are vaporized.
  • inorganic pigments used as black colorants include, for example, JP-A-2017-222559, WO-A-2019/130772, WO-A-2019/059359 and JP-A-2009-091205. , the contents of which are incorporated herein.
  • Organic pigment used as a black colorant is not particularly limited as long as it has a light-shielding property and contains an organic compound, but known organic pigments can be used. .
  • organic pigments include, for example, bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • Examples of the bisbenzofuranone compound include compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234.
  • a bisbenzofuranone compound is available as “Irgaphor Black” (trade name) manufactured by BASF.
  • Perylene compounds include those described in JP-A-62-001753 and JP-B-63-026784. The perylene compound is C.I. I. Pigment Black 21, 30, 31, 32, 33, and 34.
  • black dye a dye that expresses black color by itself can be used.
  • pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds can be used.
  • black dyes include dyes defined by the Color Index (C.I.) of Solvent Black 27 to 47, and Solvent Black 27, 29 or 34 C.I. I.
  • Commercially available products of these black dyes include Spiron Black MH, Black BH (manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (manufactured by Orient Chemical Industry Co., Ltd.), Dyes such as Savinyl Black RLSN (manufactured by Clariant Co., Ltd.), KAYASET Black KR, K-BL (manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • a pigment multimer as a black dye.
  • dye multimers include compounds described in JP-A-2011-213925 and JP-A-2013-041097.
  • a polymerizable dye having polymerizability in the molecule may be used, and commercially available products thereof include, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd.
  • a plurality of dyes having a color other than black alone may be used in combination as a black dye. Examples of such colored dyes include, for example, R (red), G (green), and B (blue) chromatic dyes (chromatic dyes), and paragraph [0027 ] to [0200] can also be used.
  • white colorant As the white colorant, one or more selected from the group consisting of white pigments and white dyes can be mentioned, and white pigments are preferable from the viewpoint of weather resistance and the like.
  • white pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, and aluminum silicate. , hollow resin particles, and zinc sulfide.
  • the white pigment is preferably particles containing titanium atoms, more preferably titanium oxide. Titanium oxide described in "Titanium Oxide, Physical Properties and Applied Techniques, Manabu Seino, Jun. 25, 1991, published by Gihodo Publishing" can also be suitably used as titanium oxide.
  • C.I. I. Pigment White 1 C.I. I. Pigment White 1, 3, 6, 16, 18, 21 can be used as a white pigment.
  • An infrared absorbing agent means a compound having absorption in the wavelength region of the infrared region (preferably wavelength of 650 to 1300 nm).
  • a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferred.
  • Colorants having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, and quatarylene. compounds, dithiol metal complex compounds, and croconium compounds.
  • Phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, cyanine compounds, squarylium compounds, and croconium compounds may use compounds disclosed in paragraphs [0010] to [0081] of JP-A-2010-111750. The contents are incorporated herein.
  • cyanine compound for example, "Functional Dyes, Shin Okawara/Ken Matsuoka/Teijiro Kitao/Tsunesuke Hirashima, Kodansha Scientific" can be referred to, the contents of which are incorporated herein.
  • the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
  • the infrared absorber is preferably a compound that dissolves in water at 25°C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25°C in an amount of 10% by mass or more. Solvent resistance is improved by using such a compound.
  • Pyrrolopyrrole compounds can be referred to paragraphs [0049] to [0062] of JP-A-2010-222557, the contents of which are incorporated herein.
  • JP 2014-063144 Paragraphs [0053] to [0099] of JP-A-2014-052431, paragraphs [0085]-[0150] of JP-A-2014-052431, paragraphs [0076]-[0124] of JP-A-2014-044301, JP-A-2012- 008532, paragraphs [0045] to [0078], JP 2015-172102, paragraphs [0027] to [0067], JP 2015-172004, paragraphs [0029] to [0067], JP 2015 -040895, paragraphs [0029] to [0085], JP 2014-126642, paragraphs [0022] to [0036], JP 2014-148567, paragraphs [0011] to [0017], JP Paragraphs [0010] to [0025] of 2015-157893, paragraphs [0013] to [0026] of JP 2014
  • the composition of the invention may contain a resin.
  • the resin is blended, for example, for use as a binder and for dispersing particles such as pigments in the composition.
  • a resin that is mainly used to disperse particles such as pigments is also called a dispersant.
  • the above dispersant does not contain either fluorine atoms or silicon atoms.
  • the use of the resin is only an example, and the resin can be used for purposes other than such uses.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is more preferably 1,000,000 or less, and even more preferably 500,000 or less.
  • the lower limit is more preferably 3000 or more, and even more preferably 5000 or more.
  • resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins can be used. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance.
  • norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520).
  • epoxy resins include epoxy resins that are glycidyl etherified compounds of phenolic compounds, epoxy resins that are glycidyl etherified compounds of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester-based Epoxy resins, glycidylamine-based epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensation products of silicon compounds containing epoxy groups and other silicon compounds, polymerizable unsaturated compounds having epoxy groups and others with other polymerizable unsaturated compounds.
  • Epoxy resins include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (NOF). Co., Ltd., epoxy group-containing polymer) and the like can also be used. Also, resins described in Examples of International Publication No. 2016/088645 can be used as the resin. When the resin contains an ethylenically unsaturated group, particularly a (meth)acryloyl group, in the side chain, the main chain and the ethylenically unsaturated group are linked via a divalent linking group containing an alicyclic structure. It is also preferred that
  • the curable composition of the invention preferably contains an alkali-soluble resin.
  • the curable composition of the present invention contains an alkali-soluble resin
  • the acid group includes a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferred.
  • the number of acid groups that the alkali-soluble resin has may be one, or two or more.
  • the alkali-soluble resin can also be used as a dispersant.
  • the alkali-soluble resin preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin.
  • the upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less.
  • the lower limit of the content of repeating units having an acid group in the side chain is preferably 10 mol % or more, more preferably 20 mol % or more.
  • the alkali-soluble resin is also preferably an alkali-soluble resin having a polymerizable group.
  • Polymerizable groups include (meth)allyl groups (meaning both allyl groups and methallyl groups), (meth)acryloyl groups, and the like.
  • the alkali-soluble resin having a polymerizable group is preferably a resin containing a repeating unit having a polymerizable group in its side chain and a repeating unit having an acid group in its side chain.
  • the alkali-soluble resin is a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferred to include repeating units derived from
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • ED2 the description in JP-A-2010-168539 can be referred to, the contents of which are incorporated herein.
  • the alkali-soluble resin preferably contains a repeating unit derived from the compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
  • represents an alkyl group of n represents an integer of 1-15.
  • JP 2012-208494 paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 can be referred to, and the contents thereof are incorporated herein.
  • the acid value of the resin is preferably 10 to 500 mgKOH/g.
  • the lower limit is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less.
  • the ethylenically unsaturated bond equivalent of the resin (especially the alkali-soluble resin) (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is 0.4 to 2.5 mmol/g is preferred.
  • the lower limit is preferably 1.0 mmol/g, more preferably 1.2 mmol/g.
  • the upper limit is preferably 2.3 mmol/g, more preferably 2.0 mmol/g.
  • the curable composition of the present invention contains a resin having an acid value of 10 to 100 mgKOH/g and an ethylenically unsaturated bond equivalent of 1.0 to 2.0 mmol/g, after the moisture resistance test It is possible to further suppress the occurrence of peeling.
  • alkali-soluble resins include resins with the following structures.
  • Me represents a methyl group.
  • the curable composition of the present invention also preferably contains a resin having a basic group.
  • Basic groups include amino groups and ammonium bases.
  • the resin having a basic group may further have an acid group in addition to the basic group.
  • such a resin is also an alkali-soluble resin.
  • Resins having a basic group include resins having a tertiary amino group and a quaternary ammonium base.
  • the resin having a tertiary amino group and a quaternary ammonium base is preferably a resin having a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium base.
  • the resin having a tertiary amino group and a quaternary ammonium base may further have a repeating unit having an acid group.
  • the resin having a tertiary amino group and a quaternary ammonium base also preferably has a block structure.
  • the resin having a tertiary amino group and a quaternary ammonium base preferably has an amine value of 10 to 250 mgKOH/g and a quaternary ammonium salt value of 10 to 90 mgKOH/g, and an amine value of 50 to 200 mgKOH. /g, and a quaternary ammonium salt value of 10 to 50 mgKOH/g.
  • the weight average molecular weight (Mw) of the resin having a tertiary amino group and a quaternary ammonium base is preferably 3,000 to 300,000, more preferably 5,000 to 30,000.
  • a resin having a tertiary amino group and a quaternary ammonium group is an ethylenically unsaturated monomer having a tertiary amino group, an ethylenically unsaturated monomer having a quaternary ammonium group, and optionally other ethylenic It can be produced by copolymerizing unsaturated monomers.
  • ethylenically unsaturated monomers having a tertiary amino group and ethylenically unsaturated monomers having a quaternary ammonium base include those described in paragraphs 0150 to 0170 of WO 2018/230486. , the contents of which are incorporated herein.
  • a resin having an acidic group described in paragraphs 0079 to 0160 of JP-A-2018-87939 may be used in combination.
  • the resin having a basic group is preferably a resin containing a nitrogen atom in its main chain.
  • Resins containing nitrogen atoms in the main chain include poly(lower alkyleneimine)-based repeating units, polyallylamine-based repeating units, polydiallylamine-based repeating units, metaxylenediamine-epichlorohydrin polycondensate-based It preferably contains a repeating unit having at least one nitrogen atom selected from repeating units and polyvinylamine-based repeating units.
  • the oligoimine resin is a resin having a repeating unit having a partial structure X having a functional group with a pKa of 14 or less and a repeating unit having a side chain containing an oligomer chain or polymer chain Y having 40 to 10000 atoms. is preferred.
  • the oligoimine resin may further have a repeating unit having an acid group.
  • the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the curable composition of the present invention can also contain a resin as a dispersant, and preferably contains a resin as a dispersant.
  • Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. A resin consisting only of groups is more preferred.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of acid groups and basic groups is 100 mol %.
  • the dispersant is preferably a resin having a basic group, more preferably a basic dispersant.
  • the resin used as the dispersant examples include the resin having a tertiary amino group and a quaternary ammonium base, the oligoimine resin, and the like. Also, the resin used as the dispersant is preferably a graft resin. Grafted resins include resins having repeating units with grafted chains. The graft resin may further have repeating units with acid groups. Details of the graft resin can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the graft chain is selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the coloring material and the like. It is preferably a graft chain containing at least one kind of polyether structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
  • the resin used as the dispersant is preferably a resin containing a repeating unit having an acid group. It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion.
  • Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962. Moreover, the alkali-soluble resin mentioned above can also be used as a dispersing agent.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie) and Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.). Dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
  • the resin content is preferably 1 to 50% by mass based on the total solid content of the curable composition.
  • the lower limit is preferably 5% by mass or more, more preferably 7% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the alkali-soluble resin is preferably 1 to 50% by mass based on the total solid content of the curable composition.
  • the lower limit is preferably 5% by mass or more, more preferably 7% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the alkali-soluble resin in the resin contained in the curable composition is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and 90 to 100% by mass. is more preferred.
  • the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the curable composition.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the curable composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.
  • the composition includes, as a resin other than the resins described above, for example, a polymerized product (resin) polymerized without being incorporated into the polymer of the coating layer in the coating layer forming step described in the manufacturing method of the modified inorganic particles. may contain.
  • the polymerization product is the same as the polymer described as the polymer contained in the coating layer of the modified inorganic particles, except that it is not incorporated as the polymer in the coating layer.
  • the content of the polymerization product in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass, based on the total solid content of the composition.
  • the composition of the invention may contain a polymerization initiator.
  • a polymerization initiator for example, a known polymerization initiator can be used.
  • examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred.
  • the content of the polymerization initiator is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, even more preferably 1.5 to 8% by mass, based on the total solid content of the composition.
  • a polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.
  • thermal polymerization initiators examples include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl-(2,2′)-azobis(2 -methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • thermal polymerization initiators include polymerization initiators described in Kiyomi Kato, "Ultraviolet Curing System” (published by Sogo Gijutsu Center Co., Ltd.: 1989), pp. 65-148.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet range to the visible range are preferred.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds.
  • ketone compounds aromatic onium salts
  • ⁇ -hydroxyketone compounds ⁇ -aminoketone compounds.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles.
  • oxime compounds dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, or 3-aryl-substituted coumarin compounds, oxime compounds, ⁇ -hydroxy A compound selected from a ketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound is more preferred, and an oxime compound is even more preferred.
  • the photopolymerization initiator include compounds described in paragraphs [0065] to [0111] of JP-A-2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated herein.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins BV) and the like (former BASF, Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 2959, Irgacure in that order).
  • Examples of commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (manufactured by IGM Resins B.V.), etc. ).
  • acylphosphine compounds include Omnirad 819 and Omnirad TPO (manufactured by IGM Resins B.V.) and the like (former BASF, Irgacure 819 and Irgacure TPO in this order).
  • Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2000-080068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, Patent No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), and Adeka Optomer N-1919.
  • ADEKA Corporation photopolymerization initiator 2 described in JP-A-2012-014052.
  • the oxime compound it is also preferable to use a compound having no coloring property and a compound having high transparency and resistance to discoloration.
  • Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).
  • an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
  • Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of
  • an oxime compound having a nitro group can be used as a photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include paragraphs [0031] to [0047] of JP-A-2013-114249, paragraphs [0008]-[0012] and [0070]- of JP-A-2014-137466. [0079], compounds described in paragraphs [0007] to [0025] of Japanese Patent No. 4223071, and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation).
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator in the present invention.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used as the photopolymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include, for example, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the photopolymerization initiator preferably contains an oxime compound and an ⁇ -aminoketone compound. By using both together, the developability is improved, and it is easy to form a pattern excellent in rectangularity.
  • the ⁇ -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass, per 100 parts by mass of the oxime compound.
  • the content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the composition.
  • the composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.
  • the composition may contain a polymerization inhibitor.
  • a polymerization inhibitor for example, a known polymerization inhibitor can be used.
  • polymerization inhibitors include phenol-based polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (e.g.
  • hydroquinone, 2,6-di-tert-butyl hydroquinone, etc. hydroquinone, 2,6-di-tert-butyl hydroquinone, etc.); quinone polymerization inhibitors (e.g., benzoquinone, etc.); free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (eg, phenothiazine, 2-methoxyphenothiazine, etc.); Among them, a phenol-based polymerization inhibitor or a free-radical polymerization inhibitor is preferable because the effects of the present invention are more excellent.
  • quinone polymerization inhibitors e
  • the content of the polymerization inhibitor is preferably 0.0001 to 0.5 mass%, more preferably 0.001 to 0.2 mass%, and 0.008 to 0.05, based on the total solid content of the composition. % by mass is more preferred.
  • a polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition is 0.00005 to 0.02. is preferred, and 0.0001 to 0.005 is more preferred.
  • the composition of the invention preferably contains a solvent.
  • An organic solvent is preferable as the solvent.
  • Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
  • Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 - heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be reduced for environmental reasons (for example, 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a ppt (parts per trillion) mass level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the lower limit is preferably 1 nm or more.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
  • the content of the solvent is preferably 10-97% by mass with respect to the total amount of the composition.
  • the lower limit is more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, even more preferably 60% by mass or more, and most preferably 70% by mass or more.
  • the upper limit is more preferably 96% by mass or less, and even more preferably 95% by mass or less.
  • the composition may contain only one type of solvent, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.
  • composition may further contain other optional ingredients than those mentioned above.
  • optional ingredients include particulate components other than those mentioned above, ultraviolet absorbers, silane coupling agents, surfactants, sensitizers, co-sensitizers, cross-linking agents, curing accelerators, thermosetting accelerators, plasticizers, diluents, and oil sensitizers, etc., and adhesion promoters to the substrate surface and other aids (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, Antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be added as necessary.
  • aids e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, Antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.
  • composition of the present invention contains modified inorganic particles and a polymerizable compound, and the modified inorganic particles contain inorganic particles and a coating layer covering part or all of the inorganic particles. and the coating layer contains at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a nitric acid group, a phenolic hydroxyl group, and an acid anhydride group, and a hydrophobic group. Things are mentioned.
  • Each component contained in the above composition is synonymous with each component described above, and the preferred ranges are also the same.
  • the composition is preferably prepared by preparing a dispersion liquid of the modified inorganic particles and further mixing the obtained composition with other components to form a composition.
  • the composition contains a coloring material
  • the composition is preferably prepared by mixing a coloring material, a resin and a solvent.
  • the composition further contains a polymerization inhibitor.
  • the above composition can be prepared by mixing each of the above components by a known mixing method (for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, or wet disperser).
  • a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, or wet disperser.
  • each component When preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. In addition, there are no particular restrictions on the order of addition and working conditions when blending.
  • the composition is preferably filtered with a filter for purposes such as removing foreign substances and reducing defects.
  • a filter for example, any filter that has been used for filtering purposes can be used without particular limitation.
  • filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • nylon polyamide resins
  • polyolefin resins including high density and ultrahigh molecular weight
  • PP polypropylene
  • nylon is preferred.
  • the pore size of the filter is preferably 0.1-7.0 ⁇ m, more preferably 0.2-2.5 ⁇ m, even more preferably 0.2-1.5 ⁇ m, and particularly preferably 0.3-0.7 ⁇ m. Within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter clogging of the pigment (including black pigment).
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore size of the second and subsequent filtering is the same as or larger than the pore size of the first filtering.
  • the first filters having different pore diameters within the range described above may be combined.
  • the pore size here can refer to the nominal value of the filter manufacturer.
  • Commercially available filters can be selected from various filters provided by Nihon Pall Co., Ltd., Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nihon Microlith Co., Ltd.), and Kitz Micro Filter Co., Ltd., for example.
  • the second filter a filter made of the same material as the first filter described above can be used.
  • the pore size of the second filter is preferably 0.2-10.0 ⁇ m, more preferably 0.2-7.0 ⁇ m, even more preferably 0.3-6.0 ⁇ m.
  • the composition preferably does not contain impurities such as metals, halogen-containing metal salts, acids and alkalis.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, and particularly preferably 10 mass ppt or less. below the detection limit of the instrument) is most preferred.
  • the above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs).
  • a composition layer formed using the composition of the present invention is cured to obtain a cured film (including a patterned cured film).
  • a method for producing a cured film is not particularly limited, but preferably includes the following steps. - Composition layer formation process - exposure process - development process Hereinafter, each process is demonstrated.
  • composition layer forming step In the composition layer forming step, prior to exposure, the composition is applied onto a support or the like to form a composition layer (composition layer).
  • a support for example, a substrate for a solid-state imaging device provided with an imaging device (light receiving device) such as CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) on a substrate (eg, silicon substrate) is used.
  • an undercoat layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, flattening the surface of the substrate, and the like.
  • composition layer coated on the support for example, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied.
  • the film thickness of the composition layer is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, even more preferably 0.2 to 3 ⁇ m. Drying (pre-baking) of the composition layer coated on the support can be carried out, for example, by using a hot plate, an oven or the like at a temperature of 50 to 140° C. for 10 to 300 seconds.
  • the composition layer formed in the composition layer forming step is exposed to actinic rays or radiation, and the irradiated composition layer is cured.
  • light irradiation is preferably performed through a photomask having patterned openings.
  • Exposure is preferably carried out by irradiation with radiation. Radiation that can be used for exposure is preferably ultraviolet such as g-line, h-line or i-line, and the light source is preferably a high-pressure mercury lamp.
  • the irradiation intensity is preferably 5-1500 mJ/cm 2 , more preferably 10-1000 mJ/cm 2 .
  • the composition layer may be heated in the exposure step.
  • the heating temperature is not particularly limited, it is preferably 80 to 250°C.
  • the heating time is preferably 30 to 300 seconds.
  • the post-heating step described below may also be performed. In other words, when the composition layer is heated in the exposure step, the method for producing a cured film does not need to include a post-heating step.
  • the developing step is a step of developing the exposed composition layer to form a cured film.
  • the composition layer in the portion not irradiated with light in the exposure step is eluted, leaving only the photocured portion to obtain a patterned cured film.
  • the type of developer used in the development process is not particularly limited, but an alkaline developer that does not cause damage to the underlying imaging device, circuits, and the like is desirable.
  • the developing temperature is, for example, 20 to 30.degree.
  • the development time is, for example, 20 to 90 seconds. In order to remove the residue better, in recent years, it may be carried out for 120 to 180 seconds. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
  • Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (of which organic alkali is preferred). .).
  • it is generally washed with water after development.
  • Post-bake Heat treatment (post-baking) is preferably performed after the exposure step.
  • a post-bake is a heat treatment after development to complete curing.
  • the heating temperature is preferably 240° C. or lower, more preferably 220° C. or lower. Although there is no lower limit, it is preferably 50° C. or higher, more preferably 100° C. or higher, in consideration of efficient and effective treatment.
  • Post-baking can be performed continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater.
  • the above post-baking is preferably performed in an atmosphere with a low oxygen concentration.
  • the oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. Although there is no particular lower limit, 10 ppm by volume or more is preferable.
  • Curing may be completed by UV (ultraviolet) irradiation instead of post-baking by heating.
  • the composition described above preferably further contains a UV curing agent.
  • the UV curing agent is preferably a UV curing agent capable of curing at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process by ordinary i-line exposure.
  • Examples of UV curing agents include Ciba Irgacure 2959 (trade name).
  • the composition layer is preferably made of a material that cures at a wavelength of 340 nm or less. Although the lower limit of the wavelength is not particularly limited, it is preferably 220 nm or more.
  • the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, even more preferably 800 to 3500 mJ.
  • This UV curing step is preferably performed after the exposure step in order to perform low-temperature curing more effectively. It is preferable to use an ozoneless mercury lamp as an exposure light source.
  • a cured film formed using the composition of the present invention (particularly, the composition of the present invention containing a black colorant) has excellent light-shielding properties, and the film thickness in the wavelength region of 400 to 1100 nm is 1.5.
  • the optical density (OD) per 5 ⁇ m is preferably 2.5 or more, more preferably 3.0 or more. Although the upper limit is not particularly limited, generally 10 or less is preferable.
  • the above cured film can be preferably used as a light shielding film.
  • the optical density per 1.5 ⁇ m film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more, which means that the optical density per 1.5 ⁇ m film thickness is 2.5 or more in the entire wavelength range of 400 to 1100 nm. is 2.5 or more.
  • a method for measuring the optical density of a cured film first, a cured film is formed on a glass substrate, and a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corporation) integrating sphere type light receiving unit. is used to measure the film thickness at the measurement point, and the optical density per predetermined film thickness is calculated.
  • the thickness of the cured film is, for example, preferably 0.1 to 4.0 ⁇ m, more preferably 1.0 to 2.5 ⁇ m.
  • the cured film may be thinner or thicker than this range depending on the application.
  • the light shielding property may be adjusted by making the film thinner than the above range (for example, 0.1 to 0.5 ⁇ m).
  • the optical density per 1.0 ⁇ m film thickness in the wavelength range of 400 to 1200 nm is preferably 0.1 to 1.5, more preferably 0.2 to 1.0.
  • the reflectance of the cured film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%.
  • the lower limit is preferably 0% or more.
  • the reflectance is determined from the reflectance spectrum obtained by using a spectroscope V7200 (trade name) VAR unit manufactured by JASCO Corporation to irradiate light with a wavelength of 400 to 1100 nm at an incident angle of 5°.
  • the reflectance of the cured film is defined as the reflectance of the light having the maximum reflectance in the wavelength range of 400 to 1100 nm.
  • the above cured film can be used for personal computers, tablets, mobile phones, smartphones, portable devices such as digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, cash Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and equipment with personal authentication functions that use face image authentication or biometric authentication; vehicle-mounted camera equipment; endoscopes, capsules Medical camera equipment such as scopes and catheters; and biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy and deep space. It is suitable for light-shielding members and light-shielding films of optical filters and modules used in space equipment such as target search cameras, etc., as well as anti-reflection members and anti-reflection films.
  • the cured film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).
  • the cured film is suitable for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members imparting a light shielding function or an antireflection function.
  • Micro LEDs and micro OLEDs include, for example, examples described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.
  • the above cured film is also suitable as an optical and optical film used in quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member that imparts a light shielding function and an antireflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313.
  • the cured film of the present invention is excellent in light-shielding properties and low reflectivity.
  • a light-shielding film is one of the preferred applications of the cured film of the present invention, and the light-shielding film of the present invention can be produced in the same manner as described above as the method for producing the cured film.
  • the composition can be applied to a substrate to form a composition layer, exposed to light, and developed to produce a light-shielding film.
  • the present invention also includes the invention of optical elements.
  • the optical element of the present invention is an optical element having the cured film (light shielding film).
  • optical elements include optical elements used in optical equipment such as cameras, binoculars, microscopes, and semiconductor exposure apparatuses. Above all, as the optical element, for example, a solid-state imaging element mounted on a camera or the like is preferable.
  • the solid-state imaging device of the present invention is a solid-state imaging device containing the cured film (light-shielding film) of the present invention described above.
  • a cured film for example, a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and Examples include a form having a light receiving element made of polysilicon or the like and having a cured film on the side of the support on which the light receiving element is formed (for example, a portion other than the light receiving portion and/or the pixels for color adjustment, etc.) or on the opposite side of the formation surface.
  • a solid-state imaging device includes the above solid-state imaging device.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging device of the present invention.
  • a solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 held above the solid-state imaging element 101 and sealing the solid-state imaging element 101.
  • a lens layer 111 is provided over the cover glass 103 with spacers 104 interposed therebetween.
  • the lens layer 111 is composed of a support 113 and a lens material 112 .
  • the lens layer 111 may have a structure in which the support 113 and the lens material 112 are integrally molded.
  • light diffusion weakens the light-condensing effect of the lens material 112 , thereby reducing the amount of light reaching the imaging unit 102 .
  • noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is provided with a light shielding film 114 to shield the light.
  • the cured film of the present invention can also be used as the light shielding film 114 described above.
  • the solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102 serving as its light-receiving surface, and outputs it as an image signal.
  • This solid-state imaging device 101 has a laminated substrate 105 in which two substrates are laminated.
  • the laminated board 105 is composed of a rectangular chip board 106 and a circuit board 107 of the same size.
  • the substrate material used as the chip substrate 106 for example, known materials can be used.
  • An imaging unit 102 is provided in the central portion of the surface of the chip substrate 106 .
  • a light shielding film 115 is provided in the peripheral area of the imaging unit 102 .
  • the shielding film 115 shields the stray light incident on the peripheral region, thereby preventing generation of dark current (noise) from circuits in the peripheral region. It is preferable to use the cured film of the present invention as the light shielding film 115 .
  • a plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106 .
  • the electrode pads 108 are electrically connected to the imaging section 102 via signal lines (not shown) (bonding wires are also possible) provided on the surface of the chip substrate 106 .
  • External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions substantially below the electrode pads 108 .
  • Each external connection terminal 109 is connected to an electrode pad 108 via a penetrating electrode 110 vertically penetrating through the laminated substrate 105 . Further, each external connection terminal 109 is connected to a control circuit for controlling driving of the solid-state imaging device 101 and an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging device 101 via wiring (not shown). It is
  • FIG. 2 A schematic cross-sectional view of the imaging unit 102 is shown in FIG.
  • the imaging unit 102 is composed of units provided on a substrate 204, such as a light receiving element 201, a color filter 202, a microlens 203, and the like.
  • the color filter 202 has blue pixels 205b, red pixels 205r, green pixels 205g, and a black matrix 205bm.
  • the cured film of the present invention may be used as the black matrix 205bm.
  • a p-well layer 206 is formed on the surface layer of the substrate 204 .
  • light receiving elements 201 which are made of an n-type layer and generate and store signal charges by photoelectric conversion are arranged in a square lattice.
  • a vertical transfer path 208 made of an n-type layer is formed on one side of the light receiving element 201 via a readout gate portion 207 on the surface layer of the p-well layer 206 .
  • a vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element isolation region 209 made of a p-type layer.
  • the read gate portion 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208 .
  • a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204 .
  • a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208 , the readout gate portion 207 and the element isolation region 209 .
  • the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges, and a readout electrode that drives the readout gate section 207 to read out signal charges.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output section (floating diffusion amplifier), and then output as a voltage signal.
  • a light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof.
  • the light shielding film 212 has an opening directly above the light receiving element 201 and shields the other region from light.
  • the cured film of the present invention may be used as the light shielding film 212 .
  • On the light shielding film 212 there is provided a transparent intermediate layer consisting of an insulating film 213 made of BPSG (borophospho silicate glass), an insulating film (passivation film) 214 made of P—SiN, and a flattening film 215 made of a transparent resin or the like. ing.
  • a color filter 202 is formed on the intermediate layer.
  • the image display device of the present invention comprises the cured film of the present invention.
  • Examples of the mode in which the image display device has a cured film include a mode in which the cured film is contained in a black matrix and a color filter containing such a black matrix is used in the image display device.
  • a black matrix and a color filter containing the black matrix will be described, and further, a liquid crystal display containing such a color filter will be described as a specific example of the image display device.
  • the cured film of the present invention is also preferably contained in a black matrix.
  • a black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • As the black matrix for example, those already described above; a black edge provided at the periphery of an image display device such as a liquid crystal display device; a grid pattern between red, blue, and green pixels, and/or , striped black portions; dot-shaped and/or linear black patterns for TFT (thin film transistor) light shielding;
  • TFT thin film transistor
  • the black matrix has a high light shielding property (optical density OD is 3 or more).
  • the black matrix As a method for producing the black matrix, for example, it can be produced by the same method as the method for producing the cured film. Specifically, the composition can be applied to a substrate to form a composition layer, exposed to light, and developed to produce a patterned cured film (black matrix). The thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 ⁇ m.
  • the substrate material preferably has a transmittance of 80% or more for visible light (wavelength 400 to 800 nm).
  • examples of such materials include glasses such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; And, from the viewpoint of heat resistance, alkali-free glass, quartz glass, or the like is preferable.
  • the cured film of the invention is also preferably contained in a color filter.
  • a color filter including a substrate and the black matrix. That is, a color filter having red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
  • a color filter containing a black matrix can be produced, for example, by the following method.
  • a composition layer of a composition containing a pigment corresponding to each colored pixel of a color filter is formed in the openings of a patterned black matrix formed on a substrate.
  • a composition for each color for example, a known composition can be used, but in the composition described in this specification, a composition in which the black colorant is replaced with a colorant corresponding to each pixel is used. is preferred.
  • the composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix.
  • the substrate can be baked to form colored pixels in the openings of the black matrix.
  • the cured film of the present invention is contained in a liquid crystal display device.
  • a form in which the liquid crystal display device contains a cured film for example, a form in which a color filter containing the black matrix (cured film) already described is included.
  • a liquid crystal display device includes, for example, a mode comprising a pair of substrates arranged facing each other and a liquid crystal compound sealed between the substrates.
  • the substrate for example, the substrate for the black matrix has already been described.
  • liquid crystal display device for example, from the user side, polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor) A laminate containing an element/substrate/polarizing plate/backlight unit in this order is mentioned.
  • liquid crystal display device for example, “Electronic display device (written by Akio Sasaki, published by Industrial Research Institute Co., Ltd. in 1990)", “Display device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)", etc.
  • the disclosed liquid crystal display device can be mentioned.
  • FIG. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with the cured film of the present invention.
  • An infrared sensor 300 shown in FIG. 3 includes a solid-state imaging device 310 .
  • the imaging area provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to the embodiment of the present invention.
  • the infrared absorption filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm). It is preferably a film that shields light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbing agent (the form of the infrared absorbing agent is as described above) as a coloring agent can be used.
  • the color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region.
  • pixels of red (R), green (G), and blue (B) are formed.
  • a color filter or the like is used, and its form is as already explained.
  • a resin film 314 (for example, a transparent resin film or the like) that can transmit light having a wavelength that has passed through the infrared transmission filter 313 is arranged.
  • the infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and/or a bisbenzoate Furanone compounds, etc.) and infrared absorbers (eg, pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, polymethine compounds, etc.) can be used in the cured film of the present invention.
  • the infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.
  • a microlens 315 is arranged on the incident light h ⁇ side of the color filter 312 and the infrared transmission filter 313 .
  • a planarization film 316 is formed to cover the microlenses 315 .
  • the resin film 314 is arranged in the form shown in FIG. That is, the infrared transmission filter 313 may be formed on the solid-state imaging device 310 .
  • the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of both may be different.
  • the color filter 312 is provided closer to the incident light hv than the infrared absorption filter 311.
  • the infrared absorption filter 311 may be provided on the incident light h ⁇ side of the color filter 312 .
  • the infrared absorption filter 311 and the color filter 312 are laminated adjacent to each other. good.
  • the cured film of the present invention can be used as a light shielding film such as the edge and / or side of the surface of the infrared absorption filter 311, and if it is used for the inner wall of the infrared sensor device, it can be used for internal reflection and / or meaningless light to the light receiving part. can be prevented from entering, and the sensitivity can be improved.
  • this infrared sensor since image information can be captured at the same time, it is possible to perform motion sensing, etc., by recognizing an object whose motion is to be detected. In addition, since distance information can be obtained with this infrared sensor, it is possible to take an image including 3D information. Furthermore, this infrared sensor can also be used as a biometric sensor.
  • the solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like.
  • paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983 can be referred to, and the contents thereof are incorporated into the specification of the present application.
  • the cured film of the present invention is contained as a light-shielding film in a headlight unit of a vehicle lighting device such as an automobile.
  • the cured film of the present invention contained in the headlight unit as a light shielding film is preferably formed in a pattern so as to block at least part of the light emitted from the light source.
  • FIGS. 4 and 5 A headlight unit according to the above embodiment will be described with reference to FIGS. 4 and 5.
  • FIG. FIG. 4 is a schematic diagram showing a configuration example of a headlight unit
  • FIG. 5 is a schematic perspective view showing a configuration example of a light blocking portion of the headlight unit. As shown in FIG.
  • the headlight unit 10 has a light source 12, a light shielding section 14, and a lens 16, and the light source 12, the light shielding section 14, and the lens 16 are arranged in this order.
  • the light shielding part 14 has a base 20 and a light shielding film 22 as shown in FIG.
  • the light shielding film 22 is formed with a patterned opening 23 for irradiating the light emitted from the light source 12 in a specific shape.
  • the light distribution pattern irradiated from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22 .
  • the lens 16 projects the light L from the light source 12 that has passed through the light blocking portion 14 . If a specific light distribution pattern can be emitted from the light source 12, the lens 16 is not necessarily required.
  • the lens 16 is appropriately determined according to the irradiation distance of the light L and the irradiation range.
  • the structure of the substrate 20 is not particularly limited as long as it can hold the light shielding film 22. However, it is preferable that the substrate 20 is not deformed by the heat of the light source 12. For example, it is made of glass. be. Although an example of the light distribution pattern is shown in FIG. 5, it is not limited to this. Also, the light source 12 is not limited to one, and may be arranged in a row or in a matrix, for example. When a plurality of light sources are provided, for example, one light shielding section 14 may be provided for one light source 12 . In this case, the light shielding films 22 of the plurality of light shielding portions 14 may all have the same pattern or different patterns.
  • FIG. 6 is a schematic diagram showing an example of the light distribution pattern by the headlight unit
  • FIG. 7 is a schematic diagram showing another example of the light distribution pattern by the headlight unit.
  • the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 both indicate areas irradiated with light.
  • a region 31 shown in FIG. 6 and a region 31 shown in FIG. 7 both indicate irradiation regions irradiated by the light source 12 (see FIG. 4) when the light shielding film 22 is not provided. Due to the pattern of the light shielding film 22, the intensity of the light sharply drops at the edge 30a, as in the light distribution pattern 30 shown in FIG. 6, for example.
  • the light distribution pattern 30 shown in FIG. 6 is, for example, a pattern that does not illuminate an oncoming vehicle in left-hand traffic. Also, like a light distribution pattern 32 shown in FIG. 7, a pattern obtained by cutting out a part of the light distribution pattern 30 shown in FIG. 6 may be used. In this case as well, the intensity of the light sharply drops at the edge 32a, as in the light distribution pattern 30 shown in FIG. Furthermore, the intensity of the light is sharply reduced at the notch 33 as well. For this reason, in the area corresponding to the notch 33, for example, it is possible to display a mark indicating the state of the road, such as a curved road, an upward slope, a downward slope, or the like. As a result, safety during night driving can be improved.
  • the light shielding portion 14 is not limited to being fixed between the light source 12 and the lens 16, and may be placed between the light source 12 and the lens 16 by a drive mechanism (not shown) as necessary. It is also possible to adopt a configuration in which a specific light distribution pattern is obtained by allowing the light to enter. Further, the light shielding portion 14 may constitute a shade member capable of shielding the light from the light source 12 . In this case, a driving mechanism (not shown) may be used to enter between the light source 12 and the lens 16 as necessary to obtain a specific light distribution pattern.
  • the present invention will be described in more detail below based on examples.
  • the materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.
  • the particle diameter of the inorganic particles was measured by the method using the TEM described above.
  • an inorganic particle dispersion liquid PS-1 (hollow silica surface-modified with a methacrylic group) having a solid content of 20% by mass was obtained. dispersion) was obtained.
  • the inorganic particle dispersion PS-1 (30.0 g) obtained above, X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., one end methacrylic modified silicone oil, 1.8 g), Itaconic anhydride (0.4 g) and PGMEA (propylene glycol monomethyl ether acetate, 28.2 g) were added, and the contents of the flask were heated to 80° C. under a nitrogen atmosphere.
  • a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 0.01 g) was added to the resulting flask and stirred for 3 hours.
  • V-601 (0.02 g) was added to the flask and stirred for 2 hours. After that, the contents of the flask were subjected to microfiltration, and 1-methoxy-2-propanol was added to the obtained filter cake so that the solid content was 20% by mass, thereby obtaining S-1 (solid content: 20% by mass). , 31.5 g).
  • S-2 (solid content: 20% by mass) was obtained in the same manner as S-1, except that itaconic anhydride was changed to methacrylic acid in the above [Production of S-1].
  • S-3 (solid content: 20% by mass) was obtained in the same manner as S-1, except that vinylphenol was used instead of itaconic anhydride in the above [Production of S-1].
  • ⁇ resin ⁇ ⁇ B-1 the following resin (weight average molecular weight 11,000, acid value 32 mgKOH / g (where Me represents a methyl group))
  • ⁇ B-4 the following resin (weight average molecular weight 21,000, acid value 36 mgKOH / g)
  • ⁇ B-6 Solsperse 36000 (manufactured by Lubrizol)
  • ⁇ B-7 B-10 described in paragraph [0352] of WO 2020/203080
  • ⁇ B-8 SOLSPERSE20000 (manufactured by Lubrizol, amine value 32 mgKOH / g)
  • ⁇ X-2 the following compound (wherein Ph represents a phenyl group and Me represents a methyl group.)
  • compositions of Examples and Comparative Examples were prepared by using the following raw materials and mixing them according to the formulations shown in Tables 2 to 7.
  • ⁇ M-1 NK ester A-TMMT (tetrafunctional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • ⁇ M-2 Aronix TO-2349 (acid-modified polyfunctional acrylate, manufactured by Toagosei Co., Ltd.)
  • ⁇ M-3 Ogsol EA-0300 (fluorene-containing acrylate, manufactured by Osaka Gas Chemicals Co., Ltd.)
  • ⁇ M-6 KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.)
  • ⁇ W-2 the following surfactant (weight average molecular weight 3000, where n represents an integer of 1 or more.)
  • ⁇ W-3 KF6000 (manufactured by Shin-Etsu Silicone Co., Ltd.)
  • W-4 FZ-2122 (manufactured by Dow Toray Chemical Co., Ltd.)
  • EHPE 3150 compound containing an epoxy group, manufactured by Daicel Corporation
  • Example 1 [Evaluation of reflectance (low reflectivity)] ⁇ Preparation of a substrate with a light-shielding film using the composition>
  • the composition of Example 1 obtained above was applied onto a glass substrate by spin coating to prepare a composition layer having a thickness of 1.5 ⁇ m. After pre-baking at 100° C. for 120 seconds, the entire surface of the substrate was exposed to light of 500 mJ/cm 2 with a high pressure mercury lamp (lamp power 50 mW/cm 2 ) using UX-1000SM-EH04 (manufactured by Ushio Inc.). exposed with The exposed substrate was post-baked at 220° C. for 300 seconds to obtain a substrate with a light-shielding film using the composition of Example 1. Further, a substrate with a light-shielding film was produced in the same manner as in Example 1, except that the composition was changed according to Tables 2-7.
  • a silicon oxide layer was formed on a silicon wafer by plasma CVD (chemical vapor deposition).
  • this silicon oxide layer was patterned by a dry etching method to form barrier ribs (width 100 nm, thickness 500 nm) made of silicon oxide in a grid pattern at intervals of 1.0 ⁇ m.
  • the dimensions of the opening of the partition on the silicon wafer (the area partitioned by the partition on the silicon wafer) were 1.0 ⁇ m long and 1.0 ⁇ m wide.
  • the composition of each example and each comparative example was applied by a spin coating method so that the film thickness after film formation was 0.8 ⁇ m, and then a hot plate was applied. After heating at 90° C.
  • a focused ion beam (FIB) was used to prepare a cross-sectional sample of the portion where the color filters were embedded in the barrier ribs, and a scanning electron microscope ( SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) was used to measure the taper angle of the cross section of the color filter, and the accuracy of the pattern shape was evaluated according to the following criteria. The closer the taper angle of the color filter cross section to 90 degrees, the higher the accuracy of the pattern shape. If the evaluation was A to C, it was determined that there was no practical problem.
  • the taper angle of the color filter cross section is 88 degrees or more and 90 degrees or less
  • ⁇ Vis is 0.5 mPa s or less
  • a substrate with a light-shielding film was prepared using the composition before the standing treatment in the same manner as ⁇ Preparation of a substrate with a light-shielding film using the composition>, and the reflectance was measured.
  • the composition was allowed to stand (stationary treatment) under the conditions of 45° C. and light shielding for 3 days, and the upper layer liquid of the composition after the stationary treatment was used to prepare a substrate with a light-shielding film.
  • the absolute value ⁇ R of the difference in reflectance before and after the standing was calculated and evaluated according to the following evaluation criteria. The smaller the ⁇ R, the less the change in reflectance occurs, which is preferable. If the evaluation was A to C, it was determined that there was no practical problem. (Evaluation criteria) A: ⁇ R is 0.5% or less B: ⁇ R is more than 0.5% and 1% or less C: ⁇ R is more than 1% and 3% or less D: ⁇ R is more than 3%
  • Tables 2 to 7 show the evaluation results.
  • each description shows the following.
  • “Content of modified inorganic particles (% by mass)” indicates the content of modified inorganic particles relative to the total solid content of the composition.
  • the description of "A” or “B” in the “hydrophobic group” indicates that the hydrophobic group is a group containing a silicon atom when it is “A”, and when it is "B", the hydrophobic group is Indicates a group containing a fluorine atom.
  • the colorant is at least one selected from the group consisting of chromatic colorants and black colorants of inorganic pigments. If it contains, it is confirmed that the pattern shape is more excellent when placed, and from the comparison of Examples 8 and 23 and Examples 19, 20 and 45 to 52, the colorant is an inorganic pigment other than carbon black. When the black colorant is contained, it was confirmed that the pattern shape when placed was further excellent.

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Abstract

La présente invention aborde le problème consistant à fournir : une composition qui, après avoir été étalée et laissée au repos, est hautement inhibée de laisser des résidus de développement et qui peut former des films durcis ayant des propriétés réfléchissantes extrêmement faibles ; un film durci ; un filtre coloré ; un film de protection contre la lumière ; un élément optique ; un élément d'imagerie solide ; et une unité de phare. Cette composition comprend des particules inorganiques modifiées et un composé polymérisable, les particules inorganiques modifiées comprenant des particules inorganiques et une couche de revêtement avec laquelle une partie ou la totalité des particules inorganiques sont revêtues, la couche de revêtement contenant un groupe hydrophobe et au moins un groupe spécifique choisi dans le groupe constitué par les groupes qui forment chacun un sel par l'action d'un alcali et de groupes qui augmentent chacun en polarité par l'action d'un alcali.
PCT/JP2022/000329 2021-01-20 2022-01-07 Composition, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément d'imagerie solide et unité de phare WO2022158313A1 (fr)

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JP2021-007037 2021-01-20
JP2021007037 2021-01-20

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CN116674279A (zh) * 2023-05-29 2023-09-01 珠海市凯拓塑料制品有限公司 一种用于线路板保护的抗摔包装盒及其制备工艺
WO2023190455A1 (fr) * 2022-03-29 2023-10-05 太陽ホールディングス株式会社 Composition de résine photosensible, produit durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé
WO2024043110A1 (fr) * 2022-08-22 2024-02-29 富士フイルム株式会社 Composition photosensible, film et capteur optique

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WO2019176409A1 (fr) * 2018-03-13 2019-09-19 富士フイルム株式会社 Procédé de fabrication de film durci et procédé de fabrication d'élément d'imagerie à semi-conducteurs
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WO2023190455A1 (fr) * 2022-03-29 2023-10-05 太陽ホールディングス株式会社 Composition de résine photosensible, produit durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé
WO2024043110A1 (fr) * 2022-08-22 2024-02-29 富士フイルム株式会社 Composition photosensible, film et capteur optique
CN116674279A (zh) * 2023-05-29 2023-09-01 珠海市凯拓塑料制品有限公司 一种用于线路板保护的抗摔包装盒及其制备工艺
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