WO2022210175A1 - 黒色感光性組成物、黒色感光性組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、光学素子、固体撮像素子、ヘッドライトユニット - Google Patents
黒色感光性組成物、黒色感光性組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、光学素子、固体撮像素子、ヘッドライトユニット Download PDFInfo
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- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1462—Coatings
- H01L27/14623—Optical shielding
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0018—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means for preventing ghost images
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/003—Light absorbing elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Definitions
- the present invention relates to a black photosensitive composition, a method for producing a black photosensitive composition, a cured film, a color filter, a light shielding film, an optical element, a solid-state imaging device, and a headlight unit.
- 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 describes "a black coloring agent (A), a binder resin (B), an addition-polymerizable compound (C) having an ethylenically unsaturated bond, and one or more photopolymerization initiators. (D), a black photosensitive resin composition containing (E) an aliphatic monocarboxylic acid having 12 to 24 carbon atoms and a solvent (F)."
- the present inventors have investigated the black photosensitive resin composition described in Patent Document 1, and found that the black photosensitive composition is used to suppress residue when forming a pattern, and the base material of the pattern to be formed. It was found that it is difficult to achieve both adhesion to the In particular, with respect to adhesion, it is preferable that a pattern having excellent adhesion is formed with a smaller amount of exposure.
- an object of the present invention is to provide a black photosensitive composition that is excellent in suppressing residue when a pattern is formed and that can form a pattern with excellent adhesion with a smaller amount of exposure.
- Another object of the present invention is to provide a method for producing a black photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
- a black photosensitive composition containing a black pigment, a resin, a carboxylic anhydride, and a polymerizable compound The carboxylic anhydride has a molecular weight of 50 to 550, The content of the carboxylic anhydride is 0.30 to 10.0% by mass with respect to the total solid content of the black photosensitive composition, A black photosensitive composition, wherein the black pigment has an average particle size of 250 nm or less.
- the carboxylic anhydride is a cyclic carboxylic anhydride, The black photosensitive composition according to (1), wherein the compound formed by ring-opening a cyclic carboxylic acid anhydride has a pKa of -1.20 to 4.50.
- the carboxylic anhydride is selected from the group consisting of a carboxylic anhydride represented by formula (P1) described below and a carboxylic anhydride represented by formula (P2) described below.
- P1 carboxylic anhydride represented by formula (P2) described below.
- the divalent organic group represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted arylene group, —CH 2 — group in the alkylene group may be substituted with —NH— group,
- the alkylene group has multiple substituents, the substituents may combine to form a ring, and when the alkenylene group has multiple substituents, the substituents may combine to form a ring.
- the tetravalent organic group includes a tetravalent aromatic ring group which may have a substituent, a tetravalent aliphatic group which may have a substituent, and 4 represented by the formula (Q1) described later.
- the black photosensitive composition according to (5) which represents a valent group or a tetravalent group represented by formula (Q2) described later.
- the black photosensitive composition according to any one of (1) to (7) which contains inorganic particles different from the black pigment and modified inorganic particles having a coating layer covering at least part of the inorganic particles.
- An optical element comprising the cured film according to (10).
- a solid-state imaging device containing the cured film according to (10).
- 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 (10).
- the black photosensitive composition which is excellent in the residue suppression property at the time of forming a pattern, and can form a pattern excellent in adhesiveness by a smaller amount of exposure can be provided.
- the present invention can also provide a method for producing a black photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
- 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;
- a description that does not describe substitution or 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).
- an organic group is a group containing at least one carbon atom.
- actinic rays or “radiation” in this specification mean, 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 drawing 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”.
- halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
- the black photosensitive composition of the present invention (hereinafter also simply referred to as "composition”) is a composition containing a black pigment, a resin, a carboxylic anhydride, and a polymerizable compound, wherein the carboxylic acid
- the molecular weight of the acid anhydride is 50 to 550
- the content of the carboxylic anhydride is 0.3 to 10% by mass with respect to the total solid content of the composition
- the average particle size of the black pigment is 250 nm or less.
- the composition contains a predetermined amount or more of a predetermined carboxylic anhydride
- the acidity of the coating film formed using the composition increases, and an appropriate amount of the carboxylic anhydride in the composition increases. It interacts with the black pigment surface. Therefore, the non-exposed portion of the composition of the present invention has good affinity with the developer, and the residue is suppressed when the pattern is formed by development.
- the amount of carboxylic acid anhydride contained in the composition is equal to or less than a predetermined amount, the adhesion of the pattern to the substrate is maintained well.
- the black photosensitive composition contains a black pigment having an average particle size of a predetermined value or less, and the black pigment has an average particle size that is not too large. It is speculated that the composition of the present invention can also suppress undercutting of the formed pattern. Hereinafter, it is possible to form a pattern exhibiting superior adhesion with a smaller amount of exposure, and that the pattern formed using the composition has a superior residue suppressing property when a pattern is formed using the composition. Obtaining at least one or more of the effects of better undercut suppression is also referred to as more excellent effects of the present invention.
- the components contained in the composition of the present invention are described below.
- Carboxylic anhydride (specific acid anhydride)
- the composition of the invention contains a carboxylic anhydride.
- the molecular weight of the carboxylic acid anhydride is in the range of 50 to 550, and acid anhydrides satisfying the above molecular weight requirements are also referred to as specific acid anhydrides.
- a carboxylic anhydride is a compound having a carboxylic anhydride group (a group represented by --CO--O--CO--).
- the number of carboxylic acid anhydride groups possessed by the specific acid anhydride is 1 or more, preferably 1 to 5, more preferably 1 or 2.
- the specific acid anhydride is also preferably a cyclic carboxylic acid anhydride.
- a cyclic carboxylic anhydride is a compound having a ring (acid anhydride ring) containing a carboxylic anhydride group as a constituent element forming a cyclic structure.
- the cyclic carboxylic acid anhydride has a plurality of carboxylic acid anhydride groups, only some of the carboxylic acid anhydride groups may be contained in the acid anhydride ring, or all the carboxylic acid anhydride groups may be contained in the acid anhydride ring. may be included.
- a cyclic carboxylic acid anhydride is usually contacted with an alkali (such as an alkaline developer described later) to open (hydrolyze) the acid anhydride ring.
- the number of ring member atoms of the acid anhydride ring that the specific acid anhydride can have is preferably 4 to 20, more preferably 5 to 6.
- the preferred number of ring members of the acid anhydride ring referred to here is the number of ring members of only the ring containing the acid anhydride group, even when the acid anhydride ring is condensed with another ring. Intend. For example, when a group represented by -CO-O-CO- is bonded at both ends to adjacent carbon atoms in a benzene ring group, the acid anhydride ring formed has 5 ring member atoms. be.
- the molecular weight of the specific acid anhydride is 50-550, preferably 74-450, more preferably 90-358.
- the specific acid anhydride preferably has 1 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 4 to 20 carbon atoms.
- the ClogP value of the specific acid anhydride is preferably 8.00 or less, more preferably 6.00 or less, even more preferably 5.00 or less, and particularly preferably 3.00 or less, from the viewpoint that the effects of the present invention are more excellent.
- the ClogP value of the specific acid anhydride is preferably ⁇ 6.00 or more, more preferably ⁇ 3.00 or more.
- the ClogP value of the compound obtained by ring-opening the specific acid anhydride by contacting with an alkali is preferably 8.00 or less, and 6.00 The following is more preferable, 5.00 or less is still more preferable, and 3.00 or less is particularly preferable.
- the ClogP value of the ring-opened compound is preferably ⁇ 6.00 or more, more preferably ⁇ 3.00 or more.
- ClogP values were obtained from Daylight Chemical Information System, Inc. It is a value calculated with the program "CLOGP” available from This program provides "calculated logP” values calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. ClogP values calculated by the program CLOGP v4.82 are used herein. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.; G. Sammnens, J.; B. Taylor and C.I. A. Ramsden, Eds.
- log P means the common logarithm of the partition coefficient P (Partition Coefficient), and is a quantitative measure of how an organic compound is partitioned in a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is shown by the following formula.
- log P log (coil/water)
- Coil represents the molar concentration of the compound in the oil phase
- Cwater represents the molar concentration of the compound in the water phase. If the value of logP is larger than 0, the oil solubility increases, and if the absolute value becomes negative, the water solubility increases, and there is a negative correlation with the water solubility of the organic compound. widely used as.
- the pKa of the specific acid anhydride is preferably -3.00 to 8.00, more preferably -2.00 to 6.00, and -1.40 to 4.50 from the viewpoint that the effect of the present invention can be more excellent. is more preferred. Further, when the specific acid anhydride is a cyclic acid anhydride, the pKa of the compound obtained by ring-opening the specific acid anhydride by contacting with an alkali or the like is preferably -3.00 to 8.00, - 2.00 to 6.00 is more preferred, and -1.20 to 4.50 is even more preferred.
- the acid dissociation constant (pKa) represents the pKa in an aqueous solution. , is a calculated value. All pKa values described herein are calculated using this software package.
- the carboxylic acid anhydride represented by the formula (P1) or the carboxylic acid anhydride represented by the formula (P2) is preferable because the effects of the present invention are more excellent.
- L 1 represents a divalent organic group.
- a divalent hydrocarbon group which may have a substituent and a divalent hydrocarbon group which may have a substituent and -O-, -S-, -NR a -, -CO-, or a group combined with a divalent heterocyclic group.
- Ra represents a hydrogen atom or an alkyl group. Examples of the combined groups include -NR a -divalent hydrocarbon group--, -divalent hydrocarbon group -CO-divalent hydrocarbon group-, and the like.
- a divalent hydrocarbon group may have one substituent or may have a plurality of (two or more) substituents.
- the substituent may be a monovalent substituent or a divalent substituent.
- Monovalent substituents are not particularly limited, and examples thereof include alkyl groups, carboxyl groups, amino groups, alkoxy groups, aryloxy groups, aromatic heterocyclic oxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyloxy groups.
- acylamino group alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, aromatic heterocyclicthio group, ureido group, halogen atom, cyano group, hydrazino group, heterocyclic group (e.g., heteroaryl group) , a silyl group, and groups in which these are combined (eg, *—NH—CO—O-alkylene group—aryl group. * represents a bonding position).
- the said substituent may be further substituted by the substituent.
- the substituents may combine to form a ring.
- the ring formed may be an aromatic ring or an aliphatic ring.
- the ring formed may be monocyclic or polycyclic.
- Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.
- Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, and pyrene rings.
- Aromatic heterocycles include furan, pyrrole, pyrazole, imidazole, thiophene, oxazole, and thiazole rings.
- the aromatic ring constituting the aromatic ring is polycyclic, the polycyclic ring may be a combination of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
- Divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups such as alkylene groups, alkenylene groups, and alkynylene groups, divalent aromatic hydrocarbon groups such as arylene groups, and groups in which these are combined. are mentioned. Groups in combination include -divalent aliphatic hydrocarbon group -divalent aromatic hydrocarbon group-.
- the divalent aliphatic hydrocarbon group (alkylene group, alkenylene group) and the divalent aromatic hydrocarbon group may have a substituent. That is, the divalent hydrocarbon group includes an optionally substituted alkylene group, an optionally substituted alkenylene group, and an optionally substituted arylene group.
- the type of the substituent is not particularly limited, and includes the groups exemplified as the substituent that the divalent hydrocarbon group may have.
- the divalent aliphatic hydrocarbon group (alkylene group, alkenylene group) and the divalent aromatic hydrocarbon group (arylene group) have multiple substituents, the substituents combine to form a ring.
- the type of ring to be formed is as described above in the case where the divalent hydrocarbon group has a plurality of substituents.
- the number of carbon atoms contained in the divalent hydrocarbon group is not particularly limited, preferably 1-20, more preferably 1-10.
- the number of carbon atoms in the alkylene group is not particularly limited, and is preferably 1-10, more preferably 1-5, and even more preferably 2-3.
- the alkylene group may be linear, branched, or cyclic.
- the number of carbon atoms in the alkenylene group and the alkynylene group is not particularly limited, and is preferably 2-10, more preferably 2-5, and even more preferably 2-3.
- the arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.
- the arylene group is preferably a phenylene group (1,2-phenylene group, etc.) or a naphthalenediyl group (naphthalene-1,8-diyl group).
- the divalent linking group represented by L 1 is an optionally substituted alkylene group, an optionally substituted alkenylene group, since the effects of the present invention are more excellent. , or an arylene group optionally having a substituent is preferred.
- the --CH 2 -- group in the alkylene group may be substituted with --NH-- group.
- the substituents may combine to form a ring, and when the alkenylene group has multiple substituents, the substituents combine to form a ring. or when the arylene group has a plurality of substituents, the substituents may combine to form a ring.
- L2 represents a tetravalent organic group.
- the tetravalent organic group is not particularly limited, and compounds having chain hydrocarbons such as ethylene and propane as the basic skeleton; compounds having cyclic hydrocarbons such as cyclohexane as the basic skeleton; aromatic hydrocarbons such as benzene and naphthalene.
- tetravalent linking group a tetravalent aromatic ring group optionally having substituent(s), a tetravalent aliphatic group optionally having substituent(s), and A tetravalent group represented by formula (Q1) or a tetravalent group represented by formula (Q2) can be mentioned.
- a tetravalent aromatic ring group represents a group formed by removing any four hydrogen atoms from an aromatic ring.
- the aromatic ring constituting the tetravalent aromatic ring group includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and an aromatic hydrocarbon ring is preferred.
- the aromatic ring may be monocyclic or polycyclic.
- Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, and pyrene rings.
- the tetravalent aromatic ring group may have a substituent. The number of substituents is not particularly limited, and may be one or more.
- the type of the substituent is not particularly limited, and includes the groups exemplified as the substituents that the divalent hydrocarbon group may have. Moreover, when the tetravalent aromatic ring group has a plurality of substituents, the substituents may combine to form a ring.
- the type of ring to be formed is as described above in the case where the divalent hydrocarbon group has a plurality of substituents. Examples of the tetravalent aromatic ring group include the following groups. In the formula, * represents a binding position.
- a tetravalent aliphatic group represents a group formed by removing any four hydrogen atoms from an aliphatic group.
- the number of carbon atoms in the tetravalent aliphatic group is not particularly limited, preferably 2-20, more preferably 3-15.
- Aliphatics can be straight, branched, or cyclic. When the aliphatic is cyclic, any four hydrogen atoms are removed to form a tetravalent aliphatic cyclic group.
- the aliphatic ring constituting the tetravalent aliphatic ring group includes an aliphatic hydrocarbon ring and an aliphatic heterocyclic ring, preferably an aliphatic hydrocarbon group.
- the aliphatic ring may be monocyclic or polycyclic.
- Aliphatic hydrocarbon rings include cyclohexane rings and cycloheptane rings.
- the tetravalent aliphatic group may have a substituent.
- the number of substituents is not particularly limited, and may be one or more.
- the type of the substituent is not particularly limited, and includes the groups exemplified as the substituents that the divalent hydrocarbon group may have.
- the substituents may combine to form a ring.
- the type of ring to be formed is as described above in the case where the divalent hydrocarbon group has a plurality of substituents.
- Examples of the tetravalent aliphatic ring group include the following groups. In the formula, * represents a binding position.
- each X independently represents a trivalent aromatic ring group or a trivalent aliphatic ring group.
- a trivalent aromatic ring group represents a group formed by removing any three hydrogen atoms from an aromatic ring.
- the aromatic ring constituting the trivalent aromatic ring group includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring, with the aromatic hydrocarbon ring being preferred.
- the aromatic ring may be monocyclic or polycyclic.
- Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, and pyrene rings.
- a trivalent aliphatic ring group represents a group formed by removing any three hydrogen atoms from an aliphatic ring.
- the aliphatic ring constituting the trivalent aliphatic ring group includes an aliphatic hydrocarbon ring and an aliphatic heterocyclic ring, preferably an aliphatic hydrocarbon group.
- the aliphatic ring may be monocyclic or polycyclic.
- Aliphatic hydrocarbon rings include cyclohexane rings and cycloheptane rings.
- L q1 represents a single bond or a divalent linking group.
- the divalent linking group is not particularly limited, for example, a divalent hydrocarbon group optionally having a substituent (e.g., an alkylene group, an alkenylene group, and a divalent aliphatic hydrocarbon such as an alkynylene group and a divalent aromatic hydrocarbon group such as an arylene group), a divalent heterocyclic group, -O-, -S-, -NR a -, -CO-, or a group combining these ( For example, -CO-O-, -O-bivalent hydrocarbon group-, -bivalent hydrocarbon group -NR a -bivalent hydrocarbon group-, -bivalent hydrocarbon group -O-CO- , and —CO—O—bivalent hydrocarbon group —O—CO—, etc.).
- Ra represents a hydrogen atom or an optionally substituted alkyl group.
- substituent that the alkyl group represented by R a may have include the groups exemplified as the substituent that the divalent hydrocarbon group may have.
- substituent that the divalent hydrocarbon group may have include the groups exemplified as the substituent that the divalent hydrocarbon group may have.
- the number of carbon atoms in the alkylene group is not particularly limited, and is preferably 1-10, more preferably 1-5, and even more preferably 2-3.
- the above alkylene group may be linear, branched, or cyclic.
- the number of carbon atoms in the alkenylene group and the alkynylene group is not particularly limited, and is preferably 2-10, more preferably 2-5, and even more preferably 2-3.
- the arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.
- the arylene group is preferably a phenylene group.
- Examples of the tetravalent group represented by formula (Q1) include the following groups. In the formula, * represents a binding position.
- L q2 represents a divalent linking group.
- Examples of the divalent linking group represented by L q2 include the groups exemplified for the divalent linking group represented by L q1 .
- L q3 to L q6 each independently represent an alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, and is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
- the alkylene group may be linear, branched, or cyclic.
- carboxylic anhydrides include acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, 2-methylbutyric anhydride, pivalic anhydride, isovaleric anhydride, valeric anhydride, 2-methylvaleric anhydride, 3-methylvaleric anhydride, 4-methylvaleric anhydride, hexanoic anhydride, 2-methylhexanoic anhydride, 3-methylhexanoic anhydride, 4-methylhexanoic anhydride, 5-methylhexanoic anhydride, heptanoic anhydride, 2-methylheptanoic anhydride, 3-methylheptanoic anhydride, 4-methylheptanoic anhydride, 5-methylheptanoic anhydride, 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride , acrylic anhydride, trichloro
- carboxylic anhydrides include, for example, Rikacid MH, Rikacid HNA-100, Rikacid OSA and Rikacid DDSA (manufactured by Shin Nippon Rika Co., Ltd.).
- the content of carboxylic acid anhydride is 0.30 to 10.0% by mass, preferably 0.50 to 8.0% by mass, based on the total solid content of the composition.
- 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 composition may contain only one type of carboxylic acid anhydride, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- the composition of the invention contains a black pigment.
- a black pigment means a pigment that absorbs over the entire wavelength range of 400-700 nm. More specifically, for example, black pigments that meet the evaluation criteria Z described below are preferred.
- a composition containing a black pigment, a transparent resin matrix (acrylic resin or the like), and a solvent, and having a black pigment 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.
- a black pigment may be obtained by combining a plurality of pigments that cannot be used as a black pigment alone and adjusting them to be black as a whole.
- a plurality of pigments having a color other than black alone may be used in combination as a black pigment.
- the black pigment contained in the composition of the present invention has an average particle size of 250 nm or less, preferably 200 nm or less, more preferably 150 nm or less.
- the average particle diameter is preferably 1 nm or more, more preferably 5 nm or more, and still more preferably 20 nm or more, from the viewpoint of better handling.
- the average particle size is calculated by the following method.
- the composition of the present invention is diluted with propylene glycol monomethyl ether acetate (PGMEA) to prepare a measurement solution having a solid concentration of 0.2% by mass.
- PGMEA propylene glycol monomethyl ether acetate
- LB-500 trade name
- JIS8826:2005 a 2 ml quartz cell for measurement is used at a temperature of 25 ° C.
- the data of the above-mentioned measurement solution is taken in 50 times, and the obtained number-based particle diameters are arithmetically averaged to obtain the average particle diameter.
- the measurement solution was prepared using the composition of the present invention, but the above measurement may be performed using a coloring material dispersion in which a black pigment is dispersed.
- a coloring material dispersion in which a black pigment is dispersed.
- the black pigment used in the preparation of the composition of the present invention is dispersed using a colorant dispersion, and the average particle size of the black pigment is Diameter may be measured.
- the average particle size of the black pigment may be measured after separating the black pigment from the other particles by any method.
- the black pigment a pigment that expresses black color by itself is preferable. Also, a black pigment that alone expresses black color and absorbs infrared rays may be used. Here, the black pigment that absorbs infrared rays has absorption in 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 black pigment various known black pigments can be used as long as the particle size is within a predetermined range.
- the black pigment may be an inorganic pigment or an organic pigment.
- the black pigment is preferably an inorganic pigment from the viewpoint that the light resistance of the light shielding film is more excellent.
- the black pigment is preferably one or more selected from the group consisting of titanium black, carbon black and bisbenzofuranone compounds.
- the inorganic pigment used as the black pigment is not particularly limited as long as it is a particle containing an inorganic compound and has a light-shielding property, and 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 oxide, metal nitride and metal oxynitride 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 substances include metal atoms contained in the inorganic pigments.
- 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 determined 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 constant in any color area. It is a color space defined to have a difference.
- the lightness index 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 the adsorption equilibrium state at a constant temperature is By applying the equation showing the relationship between the equilibrium pressure and the amount of adsorption at this pressure, the amount of gas molecules in only one layer can be measured, and the specific surface area can be measured accurately.
- 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.
- zirconium nitrides or oxynitrides or titanium nitrides or oxynitrides are more 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. processing is also possible.
- Titanium black can be produced by heating a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-05432), and ultrafine 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-60-065069, JP-A-61-201610
- a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia JP-A-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
- a composition layer using the substance to be dispersed is patterned by photolithography or the like, residues are less likely to remain in the removed portion, and Si 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 material 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.
- As the carbon black carbon 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. 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 10 nm or more, the particle surface is less likely to be oxidized, and a decrease in light shielding properties is suppressed.
- the crystallite size is 60 nm or less, the shift of the transmission peak to a longer wavelength when made into a colored film is suppressed, the decrease in light transmittance in the ultraviolet region is suppressed, and the light shielding property in the visible light region is reduced. is suppressed.
- 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 zirconium disclosed in JP 2017-222559 A, WO 2019/130772, WO 2019/059359 and JP 2009-091205. , the contents of which are incorporated herein.
- Organic pigment used as the black pigment is not particularly limited as long as it is a particle containing an organic compound and has a light-shielding property, and 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 Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233 and Japanese Patent Publication No. 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.
- the content of the black pigment is preferably 10 to 90% by mass, more preferably 25 to 80% by mass, even more preferably 45 to 70% by mass, based on the total solid content of the composition.
- the composition may contain only 1 type of black pigments, and may contain 2 or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- compositions of the invention may contain inorganic particles or modified inorganic particles.
- the inorganic particles are particles different from the black pigment described above.
- the modified inorganic particles have inorganic particles different from the black pigment and a coating layer covering at least part of the inorganic particles. That is, modified inorganic particles are inorganic particles having a coating layer on their surfaces.
- 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 form of the inorganic particles may be monodisperse particles or aggregated particles.
- the inorganic particles may be hollow particles or solid particles.
- 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 porosity of the hollow particles is preferably 3% or more. Although the upper limit is not particularly limited, it is preferably less than 100%, more preferably 90% or less.
- hollow particles examples 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 porosity of the solid particles is preferably less than 3%. Examples of solid particles include IPA-ST-L (trade name, manufactured by Nissan Chemical Industries, Ltd.).
- the form of the inorganic particles may be a particle aggregate in which a plurality of inorganic particles are linked in a chain (hereinafter also referred to as beaded inorganic particles).
- 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.
- Examples of 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.
- Materials constituting the inorganic particles include, for example, inorganic oxides, inorganic nitrides, inorganic carbides, carbonates, sulfates, silicates, phosphates, and composites of two or more of these. , inorganic oxides, inorganic nitrides, or carbonates, and more preferably inorganic oxides.
- the inorganic particles preferably contain at least silicon.
- Materials constituting inorganic particles include, for example, silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), mica compounds, zinc oxide, zirconium oxide, tin oxide, potassium titanate, strontium titanate, boric acid.
- Inorganic particles containing at least one selected from are preferred, and inorganic particles containing at least one selected from the group consisting of silica, titania, alumina, and calcium carbonate are more preferred, and silica, titania, and Inorganic particles containing at least one selected from the group consisting of alumina are more preferred, and inorganic particles containing silica are particularly preferred.
- 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 modified inorganic particles have a coating layer covering at least part of the inorganic particles.
- the coating layer is a layer that partially or entirely covers the inorganic particles. That is, the coating of the inorganic particles with the coating layer may cover the entire surface of the inorganic particles, or may cover only a part of the inorganic particles.
- 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 coating layer may have a substituent, and examples of the substituent include hydrophobic groups and substituents other than hydrophobic groups.
- the hydrophobic group is not particularly limited as long as it is a group exhibiting hydrophobicity.
- the hydrophobic group includes, for example, a silicon atom-containing group, a fluorine atom-containing group, an optionally substituted alkyl group, and an optionally substituted aryl group. .
- 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.
- the fluorine atom-containing group is preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
- a fluorine atom-containing group may be chain, branched, or cyclic.
- the silicon atoms mentioned above do not include silicon atoms derived from hydrolyzable silyl groups directly bonded to the inorganic particles when a silane coupling agent is used to prepare 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, more preferably 70 to 100% by mass, and even 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, if possible, 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 groups exemplified as the divalent linking group 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, more preferably 60 to 100% by mass, more preferably 90 to 90% by mass, based on the total repeating units. 100% by mass is more preferred.
- the coating layer may have substituents other than the hydrophobic group.
- Substituents other than hydrophobic groups include carboxylic acid groups, carboxylic anhydride groups, (meth)acryloyl groups, styryl groups, vinyl groups, epoxy groups, mercapto groups, ureido groups, and amino groups.
- a (meth)acryloyl group, an epoxy group, or a thiol group is preferred from the viewpoint of imparting curability
- a carboxylic acid group or a carboxylic anhydride group is preferred from the viewpoint of imparting alkali developability.
- the content of the coating layer is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass, with respect to 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 method for producing the modified inorganic particles is not particularly limited, and includes, for example, the following production methods. reacting the inorganic particles with a silane coupling agent containing a hydrophobic group and a silane coupling agent containing a substituent other than the hydrophobic group to form a coating layer on the surface of the inorganic particles; Examples thereof include a method for producing modified inorganic particles, which includes a step of coating the inorganic particles (coating layer forming step).
- the modified inorganic particles obtained by the above production method are silane coupling agents containing at least a silane coupling agent containing a hydrophobic group and a silane coupling agent containing a substituent other than the hydrophobic group. It corresponds to surface-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. Specifically, compounds of the following structural formulas can be mentioned.
- silane coupling agents include KR-515 and KP-983 (each manufactured by Shin-Etsu Silicone Co., Ltd.).
- Silane coupling agents containing substituents other than hydrophobic groups include carboxylic acid groups, carboxylic anhydride groups, (meth)acryloyl groups, styryl groups, vinyl groups, epoxy groups, mercapto groups, ureido groups, or Examples include silane coupling agents containing amino groups.
- silane coupling agents include 3-trimethoxysilylpropylsuccinic anhydride (carboxylic anhydride group), 3-methacryloxypropyltrimethoxysilane, 3-acryloxyprosyltrimethoxysilane, KBM-5803, KR-513 (manufactured by Shin-Etsu Silicone Co., Ltd.) ((meth)acryloyl group), p-styryltrimethoxysilane (styryl group), vinyltrimethoxysilane (vinyl group), 3-glycidoxypropyltrimethoxy silane (epoxy group), 3-mercaptopropyltrimethoxysilane (mercapto group), 3-ureidopropyltrialkoxysilane (ureido group), and 3-aminopropyltrimethoxysilane (amino group).
- carboxylic anhydride group 3-methacryloxypropyltrimethoxysilane
- the uncoated material refers to raw materials remaining unreacted (silane coupling agent or hydrolyzate of its silanol site in the coating layer forming step B) or generated polymerization products (silane cups in the coating layer forming step B condensate between ring agents).
- the purification treatment is not particularly limited, but includes, for example, filtration and washing of filtered material, centrifugation treatment, reprecipitation treatment, liquid separation treatment, ultrafiltration treatment, and adsorption treatment.
- Filtration and washing treatment of the filtered material include filtering (preferably microfiltration) the solution obtained by carrying out the coating layer forming step, obtaining the modified inorganic particles as the filtered material, and removing the uncoated material in the filtrate.
- centrifugal treatment As the centrifugal treatment, the solution obtained by carrying out the coating layer forming step was centrifuged to separate the supernatant containing the uncoated material and the sediment containing the modified inorganic particles, and the supernatant was removed. After that, there is a treatment of adding a solvent to the deposit containing the modified inorganic particles and redispersing it. Re-dispersion includes stirring treatment, bead mill treatment, paint shaker treatment, heat treatment, and the like.
- Examples of the reprecipitation treatment include a method in which a poor solvent for the modified inorganic particles is added to a solution containing the modified inorganic particles to precipitate the modified inorganic particles, and the supernatant containing the uncoated material is removed.
- a method of subjecting the modified inorganic particles precipitated by the method to the above-mentioned filtration and washing treatment of the filter cake can be mentioned.
- liquid separation treatment examples include a treatment in which the solution obtained by carrying out the coating layer forming step is subjected to liquid separation treatment to separate the solution into a solution in which the modified inorganic particles are dispersed and a solution in which the non-coated matter is dissolved.
- ultrafiltration treatment examples include a treatment of ultrafiltrating the solution obtained by carrying out the coating layer forming step to separate the non-coated matter.
- the preferred molecular weight cut off of the ultrafiltration membrane used is preferably 50,000 or more, more preferably 100,000 or more, although it varies depending on the particle size of the particles.
- adsorption treatment As the adsorption treatment, an adsorbent having a particle size sufficiently larger than that of the modified inorganic particles is added to the solution obtained by carrying out the coating layer forming step, the non-coated matter is adsorbed, and the adsorbent is removed by filtration or the like. Treatments to separate uncoated matter are included.
- the solution obtained by carrying out the coating layer forming step is subjected to a treatment for efficiently performing the purification treatment (for example, addition of a suitable solvent and / or removal of the solvent partial distillation, etc.) may be carried out.
- a treatment for efficiently performing the purification treatment for example, addition of a suitable solvent and / or removal of the solvent partial distillation, etc.
- the solvent of the solution obtained by carrying out the coating layer forming step without carrying out the purification treatment may be evaporated to obtain the modified inorganic particles with the polymerization product attached on the surface.
- the content of the uncoated material is such that the effect of the present invention is more excellent. , preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and most preferably 2% by mass or less, relative to the mass of the modified inorganic particles.
- the lower limit is not particularly limited, it may be 0% by mass.
- 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 is a low-molecular-weight polymerizable compound, and is a separate component from the resin described below.
- the content of the polymerizable compound in the composition is preferably 5 to 60% by mass, more preferably 7 to 30% by mass, still more preferably 10 to 20% by mass, based on the total solid content of the composition.
- the content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 50% 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.
- 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 (such as an ethylenically unsaturated group), a polymerization initiator, a surface active agents and polymerization inhibitors.
- the composition may contain only one type of polymerizable compound, or may contain two or more types.
- the molecular weight of the polymerizable compound (the weight average molecular weight when it has a molecular weight distribution) is not particularly limited, but is preferably 2500 or less.
- the lower limit is preferably 100 or more.
- the polymerizable compound is preferably a compound containing an ethylenically unsaturated group (group containing an ethylenically unsaturated bond). That is, the composition of the present invention preferably contains a low-molecular-weight compound containing an ethylenically unsaturated group as a polymerizable compound.
- a compound containing one or more ethylenically unsaturated bonds is preferable, a compound containing two or more is more preferable, a compound containing three or more is more preferable, and a compound containing four or more is particularly 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.
- the polymerizable compound for example, the compounds described in paragraph [0050] of JP-A-2008-260927 and paragraph [0040] of JP-A-2015-068893 can be used, the contents of which are described herein. incorporated into.
- the polymerizable compound may be in any chemical form such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof.
- the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
- the polymerizable 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.
- the compounds described in paragraph [0227] of JP-A-2013-029760 and paragraphs [0254] to [0257] of JP-A-2008-292970 can be used, and the contents thereof are incorporated herein.
- Polymerizable 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; Japan 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; A-DPH-12E manufactured by Nippon Kayaku Co., Ltd.; SR454, SR499 available from Sartomer, Inc.) are preferred.
- 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 trade names, manufactured by Nippon Kayaku Co., Ltd.
- the polymerizable compound may be a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond in the compound. Yaku Co., Ltd.) may be used. Preferred embodiments of the polymerizable compound are shown below.
- the polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups and phosphoric acid groups.
- the polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. is more preferred, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is more preferred.
- Commercially available products include, for example, Aronix TO-2349, M-305, M-510 and M-520 manufactured by Toagosei.
- the acid value of the polymerizable compound containing an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g.
- the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- a preferred embodiment of the polymerizable compound is a compound containing a caprolactone structure.
- 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. Among them, 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 compounds containing a caprolactone structure include, for example, M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.
- a compound represented by the following formula (Z-4) or formula (Z-5) can also be used as the polymerizable 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 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 compound may contain a cardo skeleton.
- a polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
- Examples of polymerizable 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 compound is also preferably a compound containing an isocyanuric acid skeleton as a central nucleus.
- Examples of such a polymerizable compound include NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the content of ethylenically unsaturated groups in the polymerizable compound (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 5.0 mmol/ g or more is preferable.
- the upper limit is preferably 20.0 mmol/g or less.
- the composition of the invention contains 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 dispersant contains neither fluorine atoms nor 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 more than 2,500 and 2,000,000 or less.
- 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, Examples include polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins and polyalkyleneimine resins (polyethyleneimine resins, etc.). One of these resins may be used alone, or two or more may be mixed and used.
- norbornene resin is preferable from the viewpoint of improving heat resistance.
- Commercially available 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 esters.
- epoxy resins Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (Japanese Epoxy group-containing polymer manufactured by Oil Co., Ltd.) and the like can also be used. Also, resins described in Examples of International Publication No. 2016/088645 can be used as the resin.
- 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 bonded via a divalent linking group containing an alicyclic structure. It is also preferred that The resin may be a cardo resin having a cardo skeleton.
- the resin may have a polymerizable group such as an ethylenically unsaturated group, and part or all of the resin may have polymerizability. Not included in polymerizable compounds.
- the resin in this case preferably has an ethylenically unsaturated group, and examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group and a (meth)acryloyl group.
- the content of the polymerizable resin in the composition of the present invention is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 85 to 100% by mass, relative to the total mass of the resin. .
- the composition of the present invention preferably contains an alkali-soluble resin.
- an alkali-soluble resin By containing an alkali-soluble resin in the composition of the present invention, the developability of the composition is improved, and when the composition of the present invention is patterned by photolithography, generation of development residues is effectively prevented. can be effectively suppressed.
- Alkali-soluble resins include resins having acid groups. 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 repeating units having an acid group on its side chain, and more preferably contains repeating units having an acid group on its side chain in an amount of 5 to 70 mol% of 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 repeating unit derived from 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 an "ether dimer"). It is also preferred to contain
- 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 repeating units 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 from 1 to 15;
- the alkali-soluble resin may be a cardo resin having a cardo skeleton.
- Cardo resins include, for example, V-259ME (manufactured by Nippon Steel & Sumikin Co., Ltd.).
- V-259ME manufactured by Nippon Steel & Sumikin Co., Ltd.
- paragraphs [0558] to [0571] of JP-A-2012-208494 corresponding paragraphs [0685] to [0700] of US Patent Application Publication No. 2012/0235099
- the descriptions in paragraphs [0076] to [0099] of JP-A-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.
- 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 or more, more preferably 1.2 mmol/g or more.
- the upper limit is preferably 2.3 mmol/g or less, more preferably 2.0 mmol/g or less.
- the 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 composition of the 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.
- the resin having a basic group further has an acid group, such a resin is also an alkali-soluble resin.
- the amine value of the resin having a basic group is preferably 10-250 mgKOH/g, more preferably 50-200 mgKOH/g.
- 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.
- the resin having a tertiary amino group and a quaternary ammonium group contains an ethylenically unsaturated monomer having a tertiary amino group, an ethylenically unsaturated monomer having a quaternary ammonium group, and optionally other ethylenically unsaturated monomers. It can be produced by copolymerizing saturated monomers. Ethylenically unsaturated monomers having a tertiary amino group, ethylenically unsaturated monomers having a quaternary ammonium base, described in paragraphs [0150] to [0170] of WO 2018/230486 , the contents of which are incorporated herein. Also, a resin having an acidic group described in paragraphs [0079] to [0160] of JP-A-2018-087939 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 (poly(ethyleneimine)-based repeating units, etc.), polyallylamine-based repeating units, polydiallylamine-based It preferably contains at least one repeating unit having a nitrogen atom selected from repeating units, metaxylenediamine-epichlorohydrin polycondensate-based 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 an atom number of 40 to 10000.
- 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 composition of the present invention can also contain a resin as a dispersant, and preferably contains a resin as a dispersant.
- a resin as a dispersant may correspond to an alkali-soluble resin.
- Resins as 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 (basic resin) 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 as the dispersant examples include the above-described resin having a tertiary amino group and a quaternary ammonium base, and oligoimine resins.
- 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.
- a graft chain containing at least one type is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.
- the resin 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). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs [0196] to [0209] of JP-A-2013-043962.
- the alkali-soluble resin mentioned above can also be used as a dispersing agent.
- Resins as dispersants are also available as commercial products, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 20000, Solsperse 76500 (manufactured by Nippon Lubrizol), and the like. Dispersants described in paragraphs [0041] to [0130] of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
- compositions of the invention may contain polyalkyleneimines.
- Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
- Polyalkyleneimine is a polymer having a branched structure each containing a primary amino group, a secondary amino group, and a tertiary amino group.
- the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
- Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine.
- the molecular weight of the polyalkyleneimine is preferably 100 or more, more preferably 200 or more, even more preferably 250 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
- the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
- the value of the number average molecular weight measured by the boiling point elevation method is used.
- the value of the number average molecular weight measured by the viscosity method is used.
- the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
- the amine value of the polyalkyleneimine is preferably 2.7 mmol/g or more, more preferably 5 mmol/g or more, still more preferably 10 mmol/g or more, and particularly preferably 15 mmol/g or more.
- Polyethyleneimine is preferable as the polyalkyleneimine.
- the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
- Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
- the resin content is preferably 1 to 50% by mass based on the total solid content of the 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 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 composition is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total mass of the resin. .
- the content of the resin as a dispersant in the resin contained in the composition (for example, a resin that corresponds to both an alkali-soluble resin and a resin as a dispersant, and a resin that does not correspond to an alkali-soluble resin and serves as a dispersant
- the total content of resins corresponding to (1) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 90 to 100% by mass.
- the composition may contain only one type of resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- the composition may also contain a dispersing aid.
- the dispersing aid is a component other than the above-described resin, and is a component capable of suppressing aggregation and/or sedimentation of components present in a solid state in the composition, such as black pigments.
- Dispersing aids include, for example, pigment derivatives.
- the content of the dispersing aid is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, still more preferably 0.3 to 4% by mass, based on the total solid content of the composition.
- the composition of the present 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.
- the composition may contain only one polymerization initiator, or may contain two or more polymerization initiators. When two or more kinds are contained, it is preferable that the total amount thereof is 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, a compound having photosensitivity to light in the ultraviolet region to the visible light region is preferred. As the photopolymerization initiator, a photoradical polymerization initiator is preferred.
- 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, triaryl imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound or 3-aryl-substituted coumarin compound, oxime compound, ⁇ -hydroxyketone compound, ⁇ -Compounds selected from aminoketone compounds and acylphosphine compounds are more preferred, and oxime compounds are even more preferred.
- Examples of 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
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.) and the like (former BASF, Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 2959, Irgacure in that order). .
- ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E and Omnirad 379EG (manufactured by IGM Resins B.V.) (Irgacure 907, Irgacure 369, Irgacure 369E, Ir73EG, former BASF).
- 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-ethoxycarbonyloxyimino -1-phenylpropan-1-one.
- IRGACURE-OXE01 IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tenryu Electric 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 being resistant 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, preferably 1000 to 300000, more preferably 2000 to 300000, more preferably 5000 to 200000. is more preferred.
- 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, even more preferably 1 to 20% by mass, based on the total solid content of the composition.
- the composition may contain only 1 type of photoinitiators, and may contain 2 or more types. When two or more kinds are contained, 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 agents (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
- the content of the polymerization inhibitor is preferably 0.0001 to 0.5 mass%, more preferably 0.001 to 0.2 mass%, and 0.002 to 0.05, based on the total solid content of the composition. % by mass is more preferred.
- the composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is 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 may contain a surfactant.
- a surfactant contributes to improving the coatability of the composition.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, preferably 0.003 to 0.5%, based on the total solid content of the composition. % by mass is more preferred, and 0.005 to 0.1% by mass is even more preferred.
- the composition may contain only one type of surfactant, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants.
- fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781F (manufactured by DIC Corporation); Florado FC430, FC431 and FC171 (manufactured by Sumitomo 3M); Surflon S-382, SC-101 and SC -103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, Examples include PF6520 and PF7002 (manufactured by OMNOVA).
- a block polymer can also be used as the fluorosurfactant, and specific examples thereof include the compounds described in JP-A-2011-089090.
- the composition of the invention preferably contains a solvent.
- An organic solvent is preferable as the solvent.
- Organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon 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, 3-methoxybutyl acetate, 3- Methyl 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.
- organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm ( parts per million), 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 solvent content is preferably 10 to 97% by mass based on 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 65% by mass or more.
- the upper limit is more preferably 95% by mass or less, and even more preferably 80% 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 contained, it is preferable that the total amount thereof is within the above range.
- the composition may further contain other optional ingredients than those mentioned above.
- coloring materials other than black pigments (pigments or dyes), ultraviolet absorbers, silane coupling agents, surfactants, sensitizers, co-sensitizers, cross-linking agents, curing accelerators, thermosetting accelerators, plasticizers, diluents and oil sensitizers, etc., as well as adhesion promoters to the substrate surface and other aids (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, Known additives such as release accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be added as necessary.
- the composition is preferably prepared by preparing a black pigment dispersion and mixing the resulting composition with other components.
- Each component referred to in the description of the method for producing the composition is as described above. More specifically, it is preferable to produce the composition by a production method comprising steps 1 and 2 below. According to this method, it is possible to obtain a composition that exhibits more excellent effects of the present invention.
- Step 1 A step of mixing a pre-mixture containing a black pigment, a resin, and a carboxylic anhydride in a bead mill to obtain a mixture (colorant dispersion, etc.)
- Step 2 Mixing the mixture and a polymerizable compound Step of obtaining a composition (black photosensitive composition)
- the pre-mixture may contain components other than a black pigment, a resin (preferably a resin as a dispersant), and a carboxylic anhydride.
- Such components include, for example, a dispersing aid, a polymerization inhibitor, and a solvent. mentioned.
- the components contained in the pre-mixture may be blended together, or may be blended sequentially after dissolving or dispersing each component in a solvent. good.
- the premix is mixed in a bead mill to form a mixture. If the premixture contains solvent and the mixture contains solvent, such a mixture is in particular also referred to as colorant dispersion. It is also preferable that the pre-mixture is coarsely mixed before mixing with a bead mill.
- the rough mixing method is not particularly limited, and known means can be used.
- Inorganic beads such as glass beads and zirconia beads, resin beads, or the like can be used as the beads in the bead mill.
- the bead diameter is preferably 0.01 to 1.0 mm, more preferably 0.03 to 0.65 mm.
- the bead filling rate is preferably 50-90%, more preferably 60-80%.
- the rotational speed (peripheral speed) is preferably 1 to 20 m/s, more preferably 5 to 14 m/s.
- the temperature of the object to be treated is preferably 5 to 80°C, more preferably 30 to 60°C.
- the bead mill may be, for example, any of a batch type device, a circulation type device and a continuous type device, and may be used in combination with a plurality of devices.
- the processing time is preferably 0.5 to 6 hours, more preferably 2 to 4 hours.
- the number of passes is preferably 10-1000, more preferably 60-200.
- the content of the solvent in the premixture and/or mixture is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and 50 to 80% by mass, based on the total mass of the premixture and/or mixture. More preferred.
- the content of the resin preferably resin as a dispersant
- the content of the carboxylic anhydride is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content of the premixture and / or mixture. More preferred.
- the content of the black pigment is preferably 20 to 95% by mass, more preferably 40 to 90% by mass, still more preferably 60 to 80% by mass, based on the total solid content of the premixture and/or mixture.
- the content of the dispersing aid is preferably 0.05 to 30% by mass, more preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total solid content of the premixture and / or mixture. preferable.
- the mass ratio of the total content of resin and acid anhydride to the content of black pigment was 0. 10 to 2.00 is preferred, 0.15 to 1.00 is more preferred, and 0.25 to 0.45 is even more preferred.
- Step 2 the mixture obtained in step 1 and a polymerizable compound are mixed to obtain a composition (black photosensitive composition).
- a polymerizable compound may be mixed with the above mixture, and other components (polymerization initiator, polymerization inhibitor, surfactant, further added resin and / or further added solvent, etc.) are further added. May be mixed.
- Each component mixed to obtain the composition in step 2 may be blended together, or each component may be dissolved or dispersed in a solvent and then They may be blended sequentially.
- a 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, wet disperser, or the like).
- a mixing method for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, wet disperser, or the like.
- a mixing method for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, wet disperser, or the like.
- a mixing method for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, wet disperser, or the like.
- a black pigment, a resin and/or a carboxylic acid anhydride, etc. may be further mixed in the step 2, in addition to the components previously used.
- the content of the solvent derived from the mixture obtained in step 1 is preferably 10 to 100% by mass, more preferably 50 to 95% by mass, and 70 to 90% by mass. % by mass is more preferred.
- the content of the resin derived from the mixture obtained in step 1 is preferably 10 to 100% by mass, more preferably 70 to 100% by mass, and 80 to 100% by mass. % by mass is more preferred.
- the content of the carboxylic anhydrides contained in the composition obtained in step 2 is preferably 10 to 100% by mass, and 70 to 100% by mass. More preferably, 95 to 100% by mass is even more preferable.
- the content of the black pigment derived from the mixture obtained in step 1 is preferably 10 to 100% by mass, more preferably 70 to 100% by mass, 95 ⁇ 100% by mass is more preferred.
- the content of the dispersing aids contained in the composition obtained in step 2 is preferably 10 to 100% by mass, more preferably 70 to 100% by mass. , 95 to 100% by mass is more preferable.
- the content of the polymerizable compound derived from the mixture obtained in step 1 is preferably 0 to 30% by mass, more preferably 0 to 5% by mass. , 0 to 1% by mass is more preferable.
- 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 Nippon Pall Co., Ltd., Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
- 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 in which an imaging device (light receiving device) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a 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 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.
- the radiation that can be used for exposure is preferably ultraviolet rays such as g-line, h-line and 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 a heating means such as a hot plate, a convection oven (hot air circulation dryer), or 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.
- the cured film formed using the composition of the present invention has an excellent light-shielding property, and has an optical density (OD) per 1.5 ⁇ m film thickness in a wavelength region of 400 to 1100 nm. 5 or more is preferable, and 3.0 or more is more preferable. 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.
- 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 Measurement is performed using a unit, the film thickness at the measurement location is also measured, 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-mentioned cured film can be used in portable devices such as personal computers, tablets, mobile phones, smartphones and digital cameras; OA (Office Automation) devices such as multi-function printers and scanners; (ATM: automated teller machine), industrial equipment such as equipment with personal authentication functions using high-speed cameras and facial image authentication or biometric authentication; vehicle-mounted camera equipment; endoscopes, capsule endoscopes, catheters, etc. medical camera equipment; and space equipment such as biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resource exploration cameras and exploration cameras for space astronomy and deep space targets. ; and the like, as well as light-shielding members and light-shielding films of modules and 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 instruments 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 .
- 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). ing.
- 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 image display devices such as color filters, solid-state imaging devices, and liquid crystal display devices.
- 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; black portions; dot-shaped and/or linear black patterns for TFT (thin film transistor) light shielding;
- TFT thin film transistor
- 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 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; From this point of view, 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.
- a series of operations can be performed using, for example, a composition for each color containing red, green and blue pigments to produce a color filter having red, green and blue pixels.
- 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 visible light shielding properties 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 bisbenzofuranone compound etc.) and an infrared absorbent (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, etc.).
- 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 and irradiation range of the light L.
- 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.
- 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.
- [Production of colorant dispersion] 100 g of titanium oxide MT-150A (trade name: manufactured by Tayca Corporation) having an average particle diameter of 15 nm, 25 g of silica particles AEROGIL (registered trademark) 300/30 (manufactured by Evonik Corporation) having a BET surface area of 300 m 2 /g, and a dispersant Disperbyk 190 ( Product name: BYK Chemie) is weighed, 71 g of ion-exchanged water is added, and using KURABO's MAZERSTAR KK-400W, the revolution speed is 1360 rpm and the rotation speed is 1047 rpm for 20 minutes.
- aqueous mixture solution was obtained.
- This aqueous solution is filled in a quartz container, heated to 920° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is flowed at 100 mL/min for 5 hours at the same temperature.
- Nitriding reduction treatment was carried out.
- the recovered powder was pulverized in a mortar to obtain a powdery titanium black (a-1) containing Si atoms and having a specific surface area of 73 m 2 /g [titanium black particles and a substance to be dispersed containing Si atoms]. Obtained.
- Resin X-1 (7.5 parts by mass) and S-1 (0.13 parts by mass) as an evaluation compound were added to titanium black (a-1) (25 parts by mass) prepared above, and further, Propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone were added at a ratio (mass ratio) of 74.6 to 25.4 so that the total liquid amount was 100 parts by mass, to obtain a dispersion.
- the resulting dispersion was thoroughly stirred with a stirrer for premixing.
- the obtained dispersion was subjected to dispersion treatment using NPM Pilot (bead mill) manufactured by Shinmaru Enterprises under the following conditions to obtain a colorant dispersion AA1.
- X-1 (resin) and S-1 (evaluation compound) used in the production of colorant dispersion AA1 are as follows.
- X-1 and S-1 are the same compounds in the following color material adjusting liquids.
- ⁇ S-1 a compound having the structure shown below
- Resin X-1 A resin having the structure shown below (weight average molecular weight 18,000, acid value 67 mgKOH/g, ethylenically unsaturated bond equivalent 0.4 mmol/g, corresponding to a resin having a graft chain)
- Tables 1 to 5 show various requirements such as the average particle size of titanium black, the presence or absence of the evaluation compound, the type of the evaluation compound, the amount of the evaluation compound, and the amount of the resin, with reference to the method for producing the colorant dispersion AA1.
- Other coloring material dispersions containing titanium black (TiBk) were produced in the same manner, except that they were changed as follows.
- Average particle size (nm) represents the average particle size of titanium black in the colorant dispersion.
- Carbon black was produced by a conventional oil furnace method. However, ethylene bottom oil with low Na content, Ca content and S content was used as raw material oil, and gas fuel was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the water for stopping the reaction. Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry.
- This slurry was transferred to a container equipped with a screw type stirrer, and toluene (600 g) in which epoxy resin "Epikote 828" (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, all of the carbon black dispersed in water migrated to the toluene side and became particles of about 1 mm. Next, after draining with a 60-mesh wire mesh, the separated grains were placed in a vacuum dryer and dried at 70° C. for 7 hours to remove toluene and water to obtain coated carbon black. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of carbon black and resin.
- the obtained carbon black (coated carbon black) was pulverized and then used for the preparation of the colorant dispersion.
- the average particle size of the carbon black after pulverization (coated carbon black) was 120 nm.
- resin X-1 7.5 parts by mass
- S-1 (0.13 parts by mass) as an evaluation compound
- S12000 manufactured by Lubrizol
- PPGMEA propylene glycol monomethyl ether acetate
- cyclopentanone were added at a ratio (mass ratio) of 74.6 to 25.4 so that the total liquid amount was 100 parts by mass, and dispersed.
- Tables 6 to 10 show various requirements such as the average particle size of carbon black, the presence or absence of the evaluation compound, the type of the evaluation compound, the amount of the evaluation compound, and the amount of the resin, with reference to the method for producing the colorant dispersion BA1.
- Other colorant dispersions containing carbon black coated carbon black described above were prepared in the same manner, except that they were changed as follows.
- Average particle size (nm) in Tables 6 to 10 represents the average particle size of carbon black in the colorant dispersion.
- the obtained preliminary dispersion is supplied to an Ultra Apex mill (bead mill manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 75% of 0.30 mm ⁇ zirconia beads (YTZ balls; manufactured by Neturen), and rotated at a speed of 8 m / s for 3 hours to obtain a colorant dispersion CA1 having a solid concentration of 32.6% by mass.
- the resin SOLSPERSE 20000 has an amine value of 29 mgKOH/g, has no acid value, and has a tertiary amine as a pigment adsorption group. Also, the SP value of MBA is 8.7.
- Tables 11 to 15 show various requirements such as the average particle size of the organic black, the presence or absence of the evaluation compound, the type of the evaluation compound, the amount of the evaluation compound, and the amount of the resin, with reference to the method for producing the colorant dispersion CA1.
- Each of the other colorant dispersions containing organic black (Irgaphor Black S0100CF) was prepared in the same manner, except with the following modifications.
- "Average particle size (nm)" in Tables 11 to 15 represents the average particle size of organic black in the colorant dispersion.
- Tables 16 to 20 show various requirements such as the average particle size of zirconium oxynitride, the presence or absence of the evaluation compound, the type of the evaluation compound, the amount of the evaluation compound, and the amount of the resin, with reference to the method for producing the colorant dispersion DA1.
- Other colorant dispersions containing zirconium oxynitride were prepared in the same manner, except for the changes shown.
- Average particle size (nm) represents the average particle size of zirconium oxynitride in the colorant dispersion.
- Resin X-2 (hereinafter, structural formula)
- Tables 21 to 25 show various requirements such as the average particle size of titanium black, the presence or absence of the evaluation compound, the type of the evaluation compound, the amount of the evaluation compound, and the amount of the resin, with reference to the method for producing the colorant dispersion EA1.
- Other coloring material dispersions containing titanium black (TiBk) were produced in the same manner, except that they were changed as follows.
- Average particle size (nm) represents the average particle size of titanium black in the colorant dispersion.
- the following table shows the formulation of each colorant dispersion.
- the formulation of the composition in the table indicates the amount (parts by mass) of each component added.
- TiBK means titanium black.
- the average particle size of the black pigment contained in each colorant dispersion is as shown in the "Average particle size (nm)" column in the table.
- the “evaluation compound (specific compound or comparative compound)” column shows the type and blending amount (parts by mass) of the evaluation compound used.
- evaluation compound Specific structures of the evaluation compounds described in the above table are shown below.
- the evaluation compounds are acid anhydrides and compounds other than acid anhydrides to be compared.
- the evaluation compound S-18 is a mixture of the following two compounds (S-18-1, S-18-2).
- the evaluation compound S-20 is a mixture of the following four compounds (S-20-1 to S-20-4).
- the molecular weight, ClogP value, and pKa of the evaluation compounds are shown below.
- the "Mw” column indicates the molecular weight of the evaluation compound.
- the "ClogP” column shows the ClogP value of the evaluation compound.
- A indicates the ClogP value in a state where the evaluation compound (cyclic acid anhydride) is not ring-opened
- “B” indicates the evaluation. It represents the ClogP value of a compound obtained by ring-opening a compound (cyclic acid anhydride).
- “-” indicates that no evaluation was made.
- S-14 represents the ClogP of the compound itself.
- the "pKa” column indicates the pKa of the compound to be evaluated.
- C indicates the pKa in the state where the evaluation compound (cyclic acid anhydride) is not ring-opened
- “D” indicates the evaluation compound.
- Cyclic acid anhydride represents the pKa of a compound formed by ring-opening.
- "-" indicates that no evaluation was made.
- S-14 represents the pKa of the compound itself.
- compositions (black photosensitive compositions) of Examples and Comparative Examples were prepared by using the following raw materials and mixing them according to the formulations (parts by mass) shown in Tables 26 to 57 shown below.
- the above resins B-1 and B-2 correspond to alkali-soluble resins.
- ⁇ M-1 KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
- ⁇ M-2 Aronix TO-2349 (acid-modified polyfunctional acrylate, manufactured by Toagosei Co., Ltd.)
- ⁇ M-4 M-305 (pentaerythritol tetraacrylate, manufactured by Toagosei Co., Ltd.)
- Ini-1 IRGACURE OXE02 (manufactured by BASF)
- Ini-2 See the structural formula below
- Ini-4 NCI-831 (manufactured by ADEKA)
- Ini-5 N-1919 (manufactured by ADEKA)
- Ini-6 NCI-930 (manufactured by ADEKA)
- Ini-7 an initiator with the following structural formula
- ⁇ 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.)
- the above-mentioned coating film after exposure is paddle-developed for 15 seconds with developer "CD-1040" (manufactured by Fuji Film Electronic Materials Co., Ltd.) using AD-1200 (manufactured by Mikasa), and using a shower nozzle. was washed with pure water for 30 seconds. The uncured portion of the coating film was removed by development. Thereafter, the substrate was post-baked at 220° C. for 300 seconds to obtain a patterned light-shielding film substrate (light-shielding patterned substrate).
- a patterned light-shielding film was prepared using each composition in the same manner as described above except that the opening line width of the mask used in the exposure was changed to 10 ⁇ m and the exposure was performed while changing the exposure amount.
- a substrate was produced. With respect to the obtained patterned light-shielding film substrate, a line pattern with a width of 10 ⁇ m was observed using an optical microscope, and the presence or absence of pattern peeling was evaluated from the following viewpoints. It is preferable that the amount of exposure is as small as possible to form a pattern (image portion) that adheres to the substrate and does not peel off. (Adhesion: evaluation criteria) A: A pattern free from peeling can be formed at an exposure amount of 1000 mJ or less.
- a pattern free from peeling can be formed at an exposure amount of more than 1000 mJ and 1400 mJ or less.
- C A pattern free from peeling can be formed at an exposure amount of more than 1400 mJ and 1700 mJ or less.
- D A pattern free from peeling can be formed at an exposure amount of more than 1700 mJ.
- the line width at the portion where the line width is the widest in the pattern cross section is 300 ⁇ m.
- the table below shows the formulation of the composition, the characteristics of the evaluation compounds used, and the evaluation results.
- the formulation of the composition in the table indicates the amount (parts by mass) of each component added.
- the "colorant dispersion” column indicates the type of colorant dispersion used and the blending amount (parts by mass).
- the “amount (%)" column in the “evaluation compound” column in the table indicates the content amount of the evaluation compound relative to the total solid content in the composition of each example or comparative example.
- composition of the present invention can form a pattern with excellent adhesion and is excellent in suppressing residue. It was also confirmed that the composition of the present invention can form patterns in which undercuts are suppressed.
- trimellitic anhydride (S-1) of Example 137 was replaced with succinic anhydride, pyromellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, and glutaric anhydride. , or when 4,4′-biphthalic anhydride was used, the same effect as in Example 137 was obtained. Further, the trimellitic anhydride (S-1) of Example 138 was replaced with succinic anhydride, pyromellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, and glutaric anhydride.
- Example 139 the trimellitic anhydride (S-1) of Example 139 was replaced with succinic anhydride, pyromellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, and glutaric anhydride. , or when 4,4'-biphthalic anhydride was used, the same effect as in Example 139 was obtained.
- trimellitic anhydride (S-1) of Example 140 was replaced with succinic anhydride, pyromellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, and glutaric anhydride. , or when 4,4′-biphthalic anhydride was used, the same effect as in Example 140 was obtained.
- KP983 manufactured by Shin-Etsu Silicone Co., Ltd.
- KBM-5803 manufactured by Shin-Etsu Silicone Co., Ltd.
- An inorganic particle dispersion liquid T-3 was prepared in the same manner as in Synthesis Example 1 except that KP983 was changed to a fluorine-containing silane coupling agent of the following formula and KBM-5803 was changed to 3-glycidoxypropyltrimethoxysilane.
- the content of the coating layer in the obtained modified inorganic particles was 7 parts by mass with respect to 100 parts by mass of the modified inorganic particles.
- the content of the uncoated material was 0.1 parts by mass with respect to 100 parts by mass of the entire modified inorganic particles.
- the resulting dispersion was thoroughly stirred with a stirrer for premixing.
- the resulting dispersion was subjected to dispersion treatment using NPM Pilot (bead mill) manufactured by Shinmaru Enterprises under the following conditions to obtain a colorant dispersion FA1.
- the average particle size of zirconium nitride in the resulting dispersion was 49 nm.
- a composition (black photosensitive composition) of an example was prepared by using the raw materials described above and mixing them according to the formulation (parts by mass) shown in Table 58 shown below. The evaluation described above was carried out using the resulting composition. The results are shown in Table 58.
- Example 58 As shown in Table 58, it was confirmed that the composition of the present invention can form a pattern with excellent adhesion and is excellent in suppressing residue. It was confirmed that even when the colorant dispersion liquid AA24 of Example 603 was replaced with the colorant dispersion liquid BA1 or CA1 described above, the same effect as in Example 143 was obtained. Similar effects can be obtained by replacing the colorant dispersions AA5, AA14, AA24 and AA25 in Examples 601 to 603 and 606 with the colorant dispersion FA1.
Abstract
Description
また、現在、携帯電話及びPDA(Personal Digital Assistant)等の電子機器の携帯端末には、小型で薄型な撮像ユニットが搭載されている。CCD(Charge Coupled Device)イメージセンサ及びCMOS(Complementary Metal-Oxide Semiconductor)イメージセンサ等の固体撮像素子には、ノイズ発生防止及び画質の向上等を目的として遮光膜が設けられている。
また、本発明は、黒色感光性組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、光学素子、固体撮像素子及びヘッドライトユニットの提供も課題とする。
カルボン酸無水物の分子量が50~550であり、
カルボン酸無水物の含有量が、黒色感光性組成物の全固形分に対して、0.30~10.0質量%であり、
黒色顔料の平均粒径が250nm以下である、黒色感光性組成物。
(2) カルボン酸無水物が、環状カルボン酸無水物であり、
環状カルボン酸無水物が開環してなる化合物のpKaが、-1.20~4.50である、(1)に記載の黒色感光性組成物。
(3) カルボン酸無水物のClogP値が6.00以下である、(1)又は(2)に記載の黒色感光性組成物。
(4) カルボン酸無水物の炭素数が1~40である、(1)~(3)のいずれかに記載の黒色感光性組成物。
(5) カルボン酸無水物が、後述する式(P1)で表されるカルボン酸無水物、及び、後述する式(P2)で表されるカルボン酸無水物からなる群から選択されるカルボン酸無水物である、(1)~(4)のいずれかに記載の黒色感光性組成物。
(6) 2価の有機基は、置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、又は、置換基を有していてもよいアリーレン基を表し、
アルキレン基中の-CH2-基は-NH-基に置換されていてもよく、
アルキレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、アルケニレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、アリーレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、
4価の有機基は、置換基を有していてもよい4価の芳香環基、置換基を有していてもよい4価の脂肪族基、後述する式(Q1)で表される4価の基、又は、後述する式(Q2)で表される4価の基を表す、(5)に記載の黒色感光性組成物。
(7) 黒色顔料が、チタンブラック、カーボンブラック及びビスベンゾフラノン化合物からなる群から選択される1種以上である、(1)~(6)のいずれかに記載の黒色感光性組成物。
(8) 黒色顔料とは異なる無機粒子を含有するか、または、
黒色顔料とは異なる無機粒子および無機粒子の少なくとも一部を被覆する被覆層を有する修飾無機粒子を含有する、(1)~(7)のいずれかに記載の黒色感光性組成物。
(9) (1)~(8)のいずれかに記載の黒色感光性組成物の製造方法であって、
黒色顔料と、樹脂と、カルボン酸無水物とを含有するプレ混合物をビーズミルで混合して混合物を得る工程1及び
混合物と重合性化合物とを混合して黒色感光性組成物を得る工程2を有する、黒色感光性組成物の製造方法。
(10) (1)~(8)のいずれかに記載の黒色感光性組成物を用いて形成された、硬化膜。
(11) (10)に記載の硬化膜を含有する、カラーフィルタ。
(12) (10)に記載の硬化膜を含有する、遮光膜。
(13) (10)に記載の硬化膜を含有する、光学素子。
(14) (10)に記載の硬化膜を含有する、固体撮像素子。
(15) 車両用灯具のヘッドライトユニットであって、
光源と、
光源から出射された光の少なくとも一部を遮光する遮光部とを有し、
遮光部が、(10)に記載の硬化膜を含有する、ヘッドライトユニット。
また、本発明によれば、黒色感光性組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、光学素子、固体撮像素子及びヘッドライトユニットも提供できる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含有する範囲を意味する。
また、本明細書において有機基とは、少なくとも1つの炭素原子を含む基である。
本明細書における「GPC法」は、測定機器としてHLC-8020GPC(東ソー製)を、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法を意味する。
本発明の黒色感光性組成物(以下、単に「組成物」ともいう。)は、黒色顔料と、樹脂と、カルボン酸無水物と、重合性化合物とを含有する組成物であって、上記カルボン酸無水物の分子量が50~550であり、上記カルボン酸無水物の含有量が、組成物の全固形分に対して、0.3~10質量%であり、上記黒色顔料の平均粒径が250nm以下である。
上記構成の組成物を用いた場合、本発明の課題が解決されるメカニズムは必ずしも定かではないが、本発明者らは、以下のように推測している。
すなわち、組成物が所定のカルボン酸無水物を所定量以上含有することで、組成物を用いて形成される塗膜の酸性度が増大するとともに、組成物中で適当量のカルボン酸無水物が黒色顔料表面に相互作用している。そのため、本発明の組成物における非露光部は現像液との親和性が良好であり、現像してパターンを形成する際の残渣が抑制される。また、組成物中に含まれるカルボン酸無水物の量が所定量以下であるため、パターンの基材に対する密着性も良好に保たれる。また、現像前にはカルボン酸無水物は開環せずに親水度が大きくならないため、現像液が浸透しづらく、パターンの基材に対する密着性が向上しているとも推測される。更に、黒色感光性組成物は平均粒径が所定値以下の黒色顔料を含有し、上記黒色顔料は平均粒径が大きすぎないことから、パターン形成の際の現像時にパターン間等に残渣として残留することが抑制されている、と推測している。
また、本発明の組成物は、形成されるパターンのアンダーカットも抑制できる。
以下、組成物を用いてパターンを形成した際の残渣抑制性がより優れること、より少ない露光量でより優れた密着性を示すパターンを形成できること、及び、組成物を用いて形成されるパターンのアンダーカット抑制性がより優れること、の少なくとも1つ以上の効果が得られることを、本発明の効果がより優れるともいう。
以下、本発明の組成物が含有する成分について説明する。
本発明の組成物は、カルボン酸無水物を含有する。
上記カルボン酸無水物の分子量は50~550の範囲内であり、上記分子量の要件を満たす酸無水物を特定酸無水物ともいう。
カルボン酸無水物は、カルボン酸無水物基(-CO-O-CO-で表される基)を有する化合物である。
特定酸無水物は、環状カルボン酸無水物であることも好ましい。環状カルボン酸無水物とは、環状構造を形成する構成要素としてカルボン酸無水物基を含有する環(酸無水環)を有する化合物である。
環状カルボン酸無水物がカルボン酸無水物基を複数有する場合、一部のカルボン酸無水物基のみが酸無水環に含まれていてもよいし、全てのカルボン酸無水物基が酸無水環に含まれていてもよい。
環状カルボン酸無水物は、通常、アルカリ(後述するアルカリ現像液等)と接触して酸無水環を開環(加水分解)する。
特定酸無水物が有し得る酸無水環の環員原子数は、4~20が好ましく、5~6がより好ましい。なお、ここでいう酸無水環の好ましい環員原子数は、酸無水環が他の環と縮環している場合であっても、酸無水物基を含有する環のみの環員原子数を意図する。例えば-CO-O-CO-で表される基がその両末端で、ベンゼン環基における隣り合う炭素原子同士にそれぞれ結合している場合、形成される酸無水環の環員原子数は5である。
特定酸無水物の炭素数は、1~40が好ましく、2~30がより好ましく、4~20が更に好ましい。
また、特定酸無水物が環状カルボン酸無水物である場合、上記特定酸無水物がアルカリと接触する等して開環してなる化合物のClogP値は、8.00以下が好ましく、6.00以下がより好ましく、5.00以下が更に好ましく、3.00以下が特に好ましい。上記開環してなる化合物のClogP値は、-6.00以上が好ましく、-3.00以上がより好ましい。
A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.
logP=log(Coil/Cwater)
式中、Coilは油相中の化合物のモル濃度を、Cwaterは水相中の化合物のモル濃度を表す。
logPの値が0をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。
また、特定酸無水物が環状酸無水物である場合、上記特定酸無水物がアルカリと接触する等して開環してなる化合物のpKaは、-3.00~8.00が好ましく、-2.00~6.00がより好ましく、-1.20~4.50が更に好ましい。
2価の有機基としては、置換基を有していてもよい2価の炭化水素基、及び、置換基を有していてもよい2価の炭化水素基と-O-、-S-、-NRa-、-CO-、又は、2価の複素環基とを組み合わせた基が挙げられる。
Raは、水素原子又はアルキル基を表す。
上記組み合わせた基としては、-NRa-2価の炭化水素基--、及び、-2価の炭化水素基-CO-2価の炭化水素基-等が挙げられる。
2価の炭化水素基は、1つの置換基を有してもよいし、複数(2以上)の置換基を有していてもよい。
置換基は、1価の置換基であってもよいし、2価の置換基であってもよい。
1価の置換基は特に制限されず、例えば、アルキル基、カルボキシル基、アミノ基、アルコキシ基、アリールオキシ基、芳香族ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルチオ基、アリールチオ基、芳香族ヘテロ環チオ基、ウレイド基、ハロゲン原子、シアノ基、ヒドラジノ基、ヘテロ環基(例えば、ヘテロアリール基)、シリル基、及び、これらを組み合わせた基(例えば、*-NH-CO-O-アルキレン基-アリール基。*は結合位置を表す。)などが挙げられる。なお、上記置換基は、更に置換基で置換されていてもよい。
2価の置換基は特に制限されず、例えば、*=P(Ph)3が挙げられる。*は、結合位置を表す。
2価の炭化水素基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい。形成される環は、芳香族環でもよいし、脂肪族環でもよい。
形成される環は、単環でもよいし、多環でもよい。
芳香族環としては、芳香族炭化水素環及び芳香族複素環が挙げられる。
芳香族炭化水素環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、及び、ピレン環が挙げられる。芳香族複素環としては、フラン環、ピロール環、ピラゾール環、イミダゾール環、チオフェン環、オキサゾール環、及び、チアゾール環が挙げられる。
芳香環を構成する芳香環が多環である場合、芳香族炭化水素環と芳香族複素環とを組み合わせた多環であってもよい。
上記2価の脂肪族炭化水素基(アルキレン基、アルケニレン基)及び上記2価の芳香族炭化水素基は、置換基を有してもよい。つまり、2価の炭化水素基としては、置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、及び、置換基を有していてもよいアリーレン基であってもよい。
上記置換基の種類は特に制限されず、上述した2価の炭化水素基が有していてもよい置換基で例示した基が挙げられる。
また、2価の脂肪族炭化水素基(アルキレン基、アルケニレン基)及び2価の芳香族炭化水素基(アリーレン基)が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい。形成される環の種類は、上述した、2価の炭化水素基が複数の置換基を有する場合で説明した通りである。
アルキレン基の炭素数は特に制限されず、1~10が好ましく、1~5がより好ましく、2~3が更に好ましい。
上記アルキレン基は、直鎖状でも、分岐鎖状でも、環状でもよい。
アルケニレン基及びアルキニレン基の炭素数は特に制限されず、2~10が好ましく、2~5がより好ましく、2~3が更に好ましい。
上記アリーレン基は、単環でも多環でもよく、炭素数は6~15が好ましい。上記アリーレン基は、フェニレン基(1,2-フェニレン基等)又はナフタレンジイル基(ナフタレン-1,8-ジイル基)が好ましい。
なお、アルキレン基中の-CH2-基は-NH-基に置換されていてもよい。
また、アルキレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、アルケニレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、アリーレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい。
4価の有機基は特に制限されず、エチレン及びプロパン等の鎖式炭化水素を基本骨格に有する化合物;シクロヘキサン等の環式炭化水素を基本骨格に有する化合物;ベンゼン及びナフタレン等の芳香族炭化水素を基本骨格に有する化合物;ベンゾフェノン等のベンゾフェノン骨格を有する化合物;ジフェニルエーテル等のジフェニルエーテル骨格を有する化合物;ジフェニルスルホン等のジフェニルスルホン骨格を有する化合物;ビフェニル等のビフェニル骨格を有する化合物;などの種々の化合物から任意の4個の水素原子を除いて形成される基が挙げられる。
4価の連結基としては、本発明の効果がより優れる点で、置換基を有していてもよい4価の芳香環基、置換基を有していてもよい4価の脂肪族基、式(Q1)で表される4価の基、又は、式(Q2)で表される4価の基が挙げられる。
芳香環は、単環でもよいし、多環でもよい。
芳香族炭化水素環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、及び、ピレン環が挙げられる。
4価の芳香環基は、置換基を有していてもよい。置換基の数は特に制限されず、1つでも、複数でもよい。置換基の種類は特に制限されず、上述した2価の炭化水素基が有していてもよい置換基で例示した基が挙げられる。
また、4価の芳香環基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい。形成される環の種類は、上述した、2価の炭化水素基が複数の置換基を有する場合で説明した通りである。
4価の芳香環基としては、例えば、以下の基が挙げられる。式中、*は結合位置を表す。
4価の脂肪族基の炭素数は特に制限されず、2~20が好ましく、3~15がより好ましい。
脂肪族は、直鎖状でも、分岐鎖状でも、環状でもよい。脂肪族が環状である場合、任意の4個の水素原子が除かれることにより、4価の脂肪族環基が形成される。
4価の脂肪族環基を構成する脂肪族環としては、脂肪族炭化水素環及び脂肪族複素環が挙げられ、脂肪族炭化水素基が好ましい。
脂肪族環は、単環でもよいし、多環でもよい。
脂肪族炭化水素環としては、シクロヘキサン環、及び、シクロヘプタン環が挙げられる。
4価の脂肪族基は、置換基を有していてもよい。置換基の数は特に制限されず、1つでも、複数でもよい。置換基の種類は特に制限されず、上述した2価の炭化水素基が有していてもよい置換基で例示した基が挙げられる。
また、4価の脂肪族基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい。形成される環の種類は、上述した、2価の炭化水素基が複数の置換基を有する場合で説明した通りである。
4価の脂肪族環基としては、以下の基が挙げられる。式中、*は結合位置を表す。
3価の芳香環基は、芳香環から任意の3個の水素原子を除いて形成される基を表す。3価の芳香環基を構成する芳香環としては、芳香族炭化水素環及び芳香族複素環が挙げられ、芳香族炭化水素環が好ましい。
芳香環は、単環でもよいし、多環でもよい。
芳香族炭化水素環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、及び、ピレン環が挙げられる。
3価の脂肪族環基は、脂肪族環から任意の3個の水素原子を除いて形成される基を表す。3価の脂肪族環基を構成する脂肪族環としては、脂肪族炭化水素環及び脂肪族複素環が挙げられ、脂肪族炭化水素基が好ましい。
脂肪族環は、単環でもよいし、多環でもよい。
脂肪族炭化水素環としては、シクロヘキサン環、及び、シクロヘプタン環が挙げられる。
2価の連結基は特に制限されず、例えば、置換基を有していてもよい2価の炭化水素基(例えば、アルキレン基、アルケニレン基、及び、アルキニレン基などの2価の脂肪族炭化水素基、並びに、アリーレン基などの2価の芳香族炭化水素基)、2価の複素環基、-O-、-S-、-NRa-、-CO-、又は、これらを組み合わせた基(例えば、-CO-O-、-O-2価の炭化水素基-、-2価の炭化水素基-NRa-2価の炭化水素基-、-2価の炭化水素基-O-CO-、及び、-CO-O-2価の炭化水素基-O-CO-など)が挙げられる。Raは、水素原子又は置換基を有していてもよいアルキル基を表す。Raで表されるアルキル基が有していてもよい置換基としては、上述した2価の炭化水素基が有していてもよい置換基で例示した基が挙げられる。
2価の炭化水素基が有していてもよい置換基としては、上述した2価の炭化水素基が有していてもよい置換基で例示した基が挙げられる。
アルキレン基の炭素数は特に制限されず、1~10が好ましく、1~5がより好ましく、2~3が更に好ましい。
上記アルキレン基は、直鎖状でも、分岐鎖状でも、環状でもよい。
アルケニレン基及びアルキニレン基の炭素数は特に制限されず、2~10が好ましく、2~5がより好ましく、2~3が更に好ましい。
上記アリーレン基は、単環でも多環でもよく、炭素数は6~15が好ましい。上記アリーレン基は、フェニレン基が好ましい。
式(Q1)で表される4価の基としては、以下の基が挙げられる。式中、*は結合位置を表す。
Lq2で表される2価の連結基としては、Lq1で表される2価の連結基で例示した基が挙げられる。
Lq3~Lq6は、それぞれ独立に、アルキレン基を表す。
アルキレン基の炭素数は特に制限されず、1~10が好ましく、1~5がより好ましく、1~3が更に好ましい。
上記アルキレン基は、直鎖状でも、分岐鎖状でも、環状でもよい。
無水安息香酸、無水フタル酸、4-メチル無水フタル酸、トリメリット酸無水物、ピロメリット酸無水物、無水ナフタル酸、4,4’-ビフタル酸無水物等の芳香族カルボン酸無水物;が挙げられる。
本明細書における組成物の「固形分」とは、硬化膜を形成する成分を意味し、組成物が溶剤(有機溶剤、水等)を含有する場合、溶剤を除いた全ての成分を意味する。また、硬化膜を形成する成分であれば、液体状の成分も固形分とみなす。
組成物はカルボン酸無水物を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
本発明の組成物は、黒色顔料を含有する。
本明細書において、黒色顔料は、波長400~700nmの全ての範囲にわたって吸収を有する顔料を意味する。
より具体的には、例えば、以下に説明する評価基準Zに適合する黒色顔料が好ましい。
まず、黒色顔料と、透明な樹脂マトリックス(アクリル樹脂等)と、溶剤とを含有し、全固形分に対する黒色顔料の含有量が60質量%である組成物を調製する。得られた組成物を、ガラス基板上に、乾燥後の硬化膜の膜厚が1μmになるように塗布し、硬化膜を形成する。乾燥後の硬化膜の遮光性を、分光光度計(日立株式会社製UV-3600等)を用いて評価する。乾燥後の硬化膜の波長400~700nmにおける透過率の最大値が10%未満であれば、上記色材は評価基準Zに適合する黒色着色剤であると判断できる。黒色着色剤は、評価基準Zにおいて、乾燥後の硬化膜の波長400~700nmにおける透過率の最大値が8%未満であることがより好ましく、5%未満であることが更に好ましい。
例えば、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。
本発明の組成物をプロピレングリコールモノメチルエーテルアセテート(PGMEA)で希釈して、固形分濃度が0.2質量%である測定溶液を用意する。次に、JIS8826:2005に準じた動的光散乱式粒径分布測定装置(堀場製作所社製LB-500(商品名))を用いて、温度25℃で2mlの測定用石英セルを使用して、上記測定溶液のデータ取り込みを50回行い、得られた個数基準の粒径を算術平均して平均粒径とする。
なお、上記では本発明の組成物を用いて測定溶液を用意したが、黒色顔料を分散させた色材分散液を用いて、上記測定を実施してもよい。例えば、本発明の組成物に黒色顔料以外の他の粒子が含まれる場合、本発明の組成物の調製に使用される黒色顔料を分散させた色材分散液を用いて、黒色顔料の平均粒径を測定してもよい。また、本発明の組成物に黒色顔料以外の他の粒子が含まれる場合、何れかの方法により黒色顔料と他の粒子を分離した上で、黒色顔料の平均粒径を測定してもよい。
ここで、赤外線を吸収する黒色顔料は、赤外領域(好ましくは、波長650~1300nm)の波長領域に吸収を有する。波長675~900nmの波長領域に極大吸収波長を有する黒色顔料も好ましい。
黒色顔料は、遮光膜の耐光性がより優れる点から、無機顔料が好ましい。
中でも、黒色顔料は、チタンブラック、カーボンブラック及びビスベンゾフラノン化合物からなる群から選択される1種以上が好ましい。
黒色顔料として使用される無機顔料としては、遮光性を有し、無機化合物を含有する粒子であれば、特に制限されないが、公知の無機顔料が使用できる。
遮光膜の低反射性及び遮光性がより優れる点から、黒色着色剤としては、無機顔料が好ましい。
なかでも、チタン(Ti)、ジルコニウム(Zr)、バナジウム(V)、イットリウム(Y)、アルミニウム(Al)及び鉄(Fe)からなる群から選択される1種又は2種以上の金属元素を含有する、金属酸化物、金属窒化物又は金属酸窒化物が好ましい。つまり、無機顔料は、2種以上の金属原子を含有してもよい。
上記金属酸化物、金属窒化物及び金属酸窒化物としては、更に他の金属原子が混在した粒子を使用してもよい。上記としては、例えば、更に周期表13~17族元素から選択される原子(好ましくは酸素原子及び/又は硫黄原子)を含有する金属窒化物含有粒子が使用できる。
また、上記金属酸化物、金属窒化物及び金属酸窒化物は、無機物及び/又は有機物で被覆していてもよい。
上記無機物としては、上記無機顔料に含まれる金属原子が挙げられる。
上記有機物としては、上記疎水性基を有する有機物が挙げられ、シラン化合物が好ましい。
上記の金属窒化物、金属酸化物又は金属酸窒化物には、表面修飾処理が施されていてもよい。例えば、シリコーン基とアルキル基とを併せ持つ表面処理剤で表面修飾処理が施されていてもよい。そのような無機粒子としては、「KTP-09」シリーズ(信越化学工業社製)が挙げられる。
組成物がイットリウムを含有する窒化ジルコニウムを含有する場合、i線透過率を保ちつつ、可視遮光性を向上できる。
イットリウムを含有する窒化ジルコニウムの粒子径(平均一次粒子径)は、波長550nm(可視光)における遮光性の低下を抑制できる点から、10~100nmが好ましい。イットリウム含有の窒化ジルコニウム粉末の平均一次粒子径は、比表面積の測定値からの球形換算により測定できる。
なお、イットリウムは、窒化ジルコニウム粉末に対して、固溶した状態で含有される。
イットリウムを含有する窒化ジルコニウム粉末の濃度を50ppmの分散液としたときの分光透過スペクトルにおいて、波長550nmの光透過率をX1とし、波長365nmの光透過率をX2とするとき、X1は、7.5%以下が好ましく、6.5%以下がより好ましい。X2は、25%以上が好ましく、26%以上がより好ましい。
X1に対するX2の比(X2/X1)は、3.5以上が好ましく、4.0以上がより好ましい。
アルミニウムを含有するジルコニウムとしては、アルミナで被覆された窒化ジルコニウムが好ましい。窒化ジルコニウムがアルミナで被覆されることで、耐湿性が向上する。
アルミナで被覆された窒化ジルコニウムの体積抵抗率は、1×106Ω・cm以上が好ましく、1×107Ω・cm以上がより好ましい。
アルミナで被覆された窒化ジルコニウムの体積抵抗率は、次のようにして求められる。
アルミナで被覆された窒化ジルコニウムを圧力容器に入れて5~10MPaで圧縮して圧粉体とし、この圧粉体の抵抗値をデジタルマルチメーターで測定する。そして、得られた抵抗値に対し、圧粉体の厚み及び装置形状と圧粉体の厚みを元に参照される抵抗率補正係数(RCF)とを乗ずることで、粉体の体積抵抗率(Ω・cm)が得られる。
アルミナの被覆量は、窒化ジルコニウム100質量%に対して、1.5~9質量%が好ましく、3~7質量%がより好ましい。
アルミナで被覆された窒化ジルコニウムの等電点は、5.7以上が好ましく、5.8以上がより好ましい。
「アルミナで被覆された窒化ジルコニウムの等電点」とは、アルミナで被覆された窒化ジルコニウムが分散した分散液のpHを変化させたとき、1個あたりの電荷が全体としてゼロになり、分散液に電圧を印加しても粉末が移動しないpHを意味する。
換言すれば、窒化ジルコニウム粉末のような無機窒化物粉末は、pHが変わるとゼータ電位が大きく変化し、ある特定のpHで表面電位(ゼータ電位)がゼロとなり、電気泳動を全く示さない等電点を有する。なお、「ゼータ電位」とは、分散液中で、ある極性の電荷を持つ粉末の周りに、反対極性の電荷を持つイオンが引き寄せられて形成された電気的二重構造である電気二重層に、液体流動が起こり始めるスベリ面の電位を意味する。このゼータ電位は、例えば、DispersionTechnorogy社製のゼータ電位計(型式:DT1202)を用いて次のように測定される。本装置は、コロイド振動電流法を用いて測定される。上記分散液を容器に入れて一対の電極で挟み、これらの電極に所定の電圧を印加して分散液中の粉末が移動する。その結果、荷電粒子とその周囲のカウンターイオンの分極を生じコロイド振動電位と呼ばれる電場が発生し電流として検出できる。この電流がコロイド振動電流となる。測定されたコロイド振動電流からSmoluchowskiの式と連結総理論とを用いてゼータ電位が求められる。そして、ゼータ電位がゼロになったときのpHが上記粉末の等電点である。
「アルミナで被覆された窒化ジルコニウムのL*値」とは、CIE1976L*a*b*色空間(測定用光源C:色温度6774K)における明度指数である。上記CIE1976L*a*b*色空間は、国際照明委員会(CIE)が1976年にCIEXYZ表色系を変換し、表色系内の一定距離がどの色の領域でもほぼ知覚的に等歩度の差をもつように定めた色空間である。また、明度指数L*値、a*値及びb*値は、CIE1976L*a*b*色空間内の直交座標系で定められる量であり、式(1)~(3)で表される。
L*=116(Y/Y0)1/3-16 (1)
a*=500[(X/X0)1/3-(Y/Y0)1/3] (2)
b*=200[(Y/Y0)1/3-(Z/Z0)1/3] (3)
ただし、X/X0、Y/Y0、Z/Z0>0.008856であり、X、Y、Zは、物体色の三刺激値である。また、X0、Y0、Z0は物体色を照明する光源の三刺激値であり、Y0=100に基準化されている。また、アルミナで被覆された窒化ジルコニウムの明度指数L*値は、例えば、日本電色工業社製の分光色差計(型式:SE7700)を用いて求める。L*値が13以下である場合、黒色度が充足して黒色顔料として所定の色調が得られる。
BET比表面積は、例えば、柴田科学社製の比表面積測定装置(型式:SA1100)を用いて、上記粉末(黒色顔料)の表面に、吸着占有面積の分かったガス分子(例えば、窒素ガス等)を吸着させ、その吸着量から求められる。ただし、アルミナで被覆された窒化ジルコニウムの表面に吸着したガス分子が1層目の吸着から多層吸着に移行する過程の情報に対して、BETの式(一定温度で吸着平衡状態であるとき、吸着平衡圧とこの圧力での吸着量との関係を示す式)を適用することにより、1層だけのガス分子の量が測定され、正確な比表面積を測定できるようになっている。BET比表面積が20m2/g以上である場合、着色力(発色力)の低下を抑制できる。
チタンブラックは、分散性向上、凝集性抑制等の目的で必要に応じ、表面を修飾することが可能である。チタンブラックは、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム又は酸化ジルコニウムで被覆することが可能であり、また、特開2007-302836号公報に表されるような撥水性物質での処理も可能である。
また、被分散体のSi/Tiが所定値以上であれば、被分散体を使用した組成物層を光リソグラフィー等によりパターニングした際に、除去部に残渣が残りにくくなり、被分散体のSi/Tiは所定値以下であれば遮光能が良好になりやすい。
なお、被分散体中のSi原子とTi原子との含有比(Si/Ti)は、例えば、国際公開第2011/049090号公報の段落[0054]~[0056]に記載の方法(2-1)又は方法(2-3)を用いて測定できる。
カーボンブラックとしては、例えば、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック及びランプブラックが挙げられる。
カーボンブラックとしては、オイルファーネス法等の公知の方法で製造されたカーボンブラックを使用してもよく、市販品を使用してもよい。
カーボンブラックの市販品の具体例としては、C.I.ピグメントブラック7等の無機顔料が挙げられる。
被覆樹脂としては、エポキシ樹脂、ポリアミド、ポリアミドイミド、ノボラック樹脂、フェノール樹脂、ウレア樹脂、メラミン樹脂、ポリウレタン、ジアリルフタレート樹脂、アルキルベンゼン樹脂、ポリスチレン、ポリカーボネート、ポリブチレンテレフタレート及び変性ポリフェニレンオキサイドが挙げられる。
被覆樹脂の含有量は、遮光膜の遮光性及び絶縁性がより優れる点から、カーボンブラック及び被覆樹脂の合計に対して、0.1~40質量%が好ましく、0.5~30質量%がより好ましい。
無機顔料の結晶子サイズを上記範囲とすることにより、着色膜の透過光はそのピーク波長が400nm以下であるような青紫色を呈し、紫外領域における光透過性を向上させることができる。従来の遮光材よりも紫外領域(特にi線(365nm))における透過性に優れるため、膜底部まで光硬化又は光溶解が十分進み、感度を向上させることができる。
結晶子サイズが10nm以上である場合、粒子表面が酸化されにくくなり、遮光性の低下が抑制される。結晶子サイズが60nm以下である場合、着色膜とした際の透過ピークが長波長へシフトが抑制され紫外領域における光透過性が低下するのが抑制されるともに、可視光領域における遮光性の低下が抑制される。
CuKα線をX線源としたときのX線回折スペクトルにおける(111)面に由来するX線回折ピークの半値幅から計算できる。
例えば、窒化ジルコニウム、酸化ジルコニウム及び/又は酸窒化ジルコニウムを含有するジルコニア化合物粒子の、CuKα線をX線源としたときのX線回折スペクトルは、窒化ジルコニウムの場合、(111)面に由来するピークが回折角2θ=33.5~34.0°近傍に観測される。酸化ジルコニウムの場合、(011)面に由来するピークが回折角2θ=30.3°近傍に、(-111)面に由来するピークが回折角2θ=28.2°近傍に観測される。酸窒化ジルコニウムの場合、(211)面に由来するピークが2θ=33.4°近傍に観測される。そして、これらのX線回折ピークの半値幅から、下記式(4)に示すシェラーの式により、結晶子サイズを算出することができる。
結晶子サイズ(nm) = Kλ/βcosθ (4)
β = √(βe 2-βO 2) (5)
式(4)中、Kは定数0.9を表す。λは0.15406(nm)を表す。βは上記式(5)で表される値である。θは上記のとおりである。式(5)中、βeは、回折ピークの半値幅を表す。βOは半値幅の補正値(0.12°)を表す。ただし、β、βe及びβOはラジアンで計算される。
X線回折スペクトルは、X線源をCuKα線として、広角X線回折法により測定する。
X線回折装置としては、例えば、理学社製RU-200Rを用いることができる。測定条件は、出力は50kV/200mA、スリット系は1°-1°-0.15mm-0.45mm、測定ステップ(2θ)は0.02°、スキャン速度は2°/分とする。
また、上記X回析ピークの値としては、例えば、特開2009-091205号公報の段落[0027]~[0028]が挙げられ、これらの内容は本明細書に組み込まれる。
黒色顔料として使用される有機顔料としては、遮光性を有し、有機化合物を含有する粒子であれば、特に制限されないが、公知の有機顔料が使用できる。
本発明において、有機顔料としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物及びアゾ系化合物が挙げられ、ビスベンゾフラノン化合物又はペリレン化合物が好ましい。
ペリレン化合物としては、特開昭62-001753号公報及び特公昭63-026784号公報に記載された化合物が挙げられる。ペリレン化合物は、C.I.Pigment Black 21、30、31、32、33及び34として入手可能である。
組成物は黒色顔料を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
本発明の組成物は、無機粒子、または、修飾無機粒子を含有していてもよい。
無機粒子とは、上述した黒色顔料とは異なる粒子である。
修飾無機粒子は、黒色顔料とは異なる無機粒子と、その無機粒子の少なくとも一部を被覆する被覆層とを有する。つまり、修飾無機粒子とは、その表面に被覆層を有する無機粒子である。
なお、「粒子径」は、以下の方法により測定した粒子の平均一次粒子径を意味する。平均一次粒子径は、透過型電子顕微鏡(Transmission Electron Microscope、TEM)を用いて測定できる。透過型電子顕微鏡としては、例えば、日立ハイテクノロジーズ社製の透過型顕微鏡HT7700を使用できる。
透過型電子顕微鏡を用いて得た粒子像の最大長(Dmax:粒子画像の輪郭上の2点における最大長さ)、及び最大長垂直長(DV-max:最大長に平行な2本の直線で画像を挟んだ時、2直線間を垂直に結ぶ最短の長さ)を測長し、その相乗平均値(Dmax×DV-max)1/2を粒子径とした。この方法で100個の粒子の粒子径を測定し、その算術平均値を粒子の平均一次粒子径とした。
無機粒子の形態は、単分散粒子であってもよく、凝集粒子であってもよい。
中空粒子は、粒子の内部に空洞が存在する粒子をいう。中空粒子は、粒子が、内部の空洞と、空洞を包囲する外殻とからなる構造であってもよい。また、中空粒子は、粒子の内部に空洞が複数存在する構造であってもよい。
中空粒子の空隙率は、3%以上が好ましい。上限は特に制限されないが、100%未満が好ましく、90%以下がより好ましい。
具体的には、中実粒子の空隙率は、3%未満が好ましい。
中実粒子としては、例えば、IPA-ST-L(商品名、日産化学社製)が挙げられる。
数珠状無機粒子としては、例えば、特許第4328935号公報、及び、特開2013-253145号公報に記載されているシリカゾルが挙げられ、数珠状コロイダル無機粒子が好ましい。
中でも、シリカ、チタニア、アルミナ、雲母化合物、硝子、チタン酸カリウム、チタン酸ストロンチウム、硼酸アルミニウム、酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、リン酸カルシウム、及び、硫酸カルシウムからなる群から選択される少なくとも1種を含有する無機粒子が好ましく、シリカ、チタニア、アルミナ、及び、炭酸カルシウムからなる群から選択される少なくとも1種を含有する無機粒子がより好ましく、シリカ、チタニア、及び、アルミナからなる群から選択される少なくとも1種を含有する無機粒子が更に好ましく、シリカを含有する無機粒子が特に好ましい。
無機粒子がシリカ(二酸化ケイ素)を含有する場合、シリカ(二酸化ケイ素)の含有量は、無機粒子の全質量に対して、75~100質量%が好ましく、90~100質量%がより好ましく、99~100質量%が更に好ましい。
言い換えれば、被覆層は、無機粒子の一部又は全部を被覆する層である。つまり、被覆層による無機粒子の被覆は、無機粒子の全面を被覆してもよく、無機粒子の一部のみを被覆してもよい。上記被覆層による無機粒子の被覆率は、無機粒子の全表面積に対して、10%以上が好ましく、30%以上がより好ましく、50%以上が更に好ましい。上限は、無機粒子の全表面積に対して、100%以下が好ましく、80%以下がより好ましい。
被覆層は無機粒子の表面に直接配置されていてもよく、無機粒子との間に他の層を介して配置されていてもよい。
疎水性基としては、例えば、ケイ素原子を含有する基、フッ素原子を含有する基、置換基を含有していてもよいアルキル基、及び、置換基を含有していてもよいアリール基が挙げられる。
中でも、疎水性基は、フッ素原子及びケイ素原子からなる群から選択される少なくとも1種を含有することが好ましく、ケイ素原子を含有することがより好ましい。
ケイ素原子を含有する基としては、シロキサン基、又は、シリル基が好ましく、シロキサン基がより好ましく、ジアルキルシロキサン基が更に好ましい。ケイ素原子を含む基は、鎖状、分岐鎖状、及び、環状のいずれであってもよい。
フッ素原子を含有する基としては、フルオロアルキル基が好ましく、パーフルオロアルキル基がより好ましい。フッ素原子を含む基は、鎖状、分岐鎖状、及び、環状のいずれであってもよい。
例えば、シリカに対して、3-メタクリロキシプロピルトリメトキシシランのトリメトキシシリル基を反応させて、メタクリロイル基を有する修飾シリカを作製した場合であっても、シリカと反応した上記トリメトキシシリル基に由来するケイ素原子は、被覆層が有するケイ素原子には該当しない。
被覆層は、上記重合体を一部に含んでいてもよいし、被覆層が上記重合体そのものであってもよい。上記重合体の含有量は、被覆層の全質量に対して、10~100質量%が好ましく、70~100質量%がより好ましく、95~100質量%が更に好ましい。
上記アルキル基は、直鎖状及び分岐鎖状のいずれであってもよい。また、上記アルキル基は、全体が環状構造であってもよく、部分的に環状構造を含有してもよい。
上記アルキル基の炭素数は、1~10が好ましく、1~3がより好ましい。ここでいう好ましい炭素数は、上記アルキル基が置換基を含有する場合において、置換基中に存在し得る炭素原子の数をも計上した炭素数を意図する。
中でも、RS1は、水素原子又はメチル基が好ましい。
上記2価の連結基としては、例えば、エーテル基(-O-)、カルボニル基(-CO-)、エステル基(-COO-)、チオエーテル基(-S-)、-SO2-、-NRN-(RNは、水素原子、又は、アルキル基を表す)、2価の炭化水素基(アルキレン基、アルケニレン基(例:-CH=CH-)、又は、アルキニレン基(例:-C≡C-等)、及びアリーレン基)、-SiRSX 2-(RSXは、水素原子、又は、置換基を表す)、並びに、これらを組み合わせた基が挙げられる。
上記2価の連結基は、可能な場合、置換基を有してもよく、上記2価の連結基の置換基が、後述するSS1で表される基であってもよく、後述するSS1で表される基を一部に含有する基であってもよい。
中でも、上記2価の連結基は、エステル基、及び、アルキレン基(好ましくは炭素数1~10のアルキレン基)からなる群から選択される基を組み合わせた基であるのが好ましい。
*Bは、式(A1)中のSS1との結合位置を表し、*Aは、*Bとは反対側の結合位置を表す。
上記アルキレン基は、直鎖状及び分岐鎖状のいずれであってもよい。また、上記アルキレン基は、全体が環状構造であってもよく、部分的に環状構造を含有してもよい。上記アルキレン基は、直鎖状であるのが好ましい。
上記アルキレン基の炭素数は、1~10が好ましく、1~3がより好ましい。ここでいう好ましい炭素数は、上記アルキレン基が置換基を含有する場合において、置換基中に存在し得る炭素原子の数をも計上した炭素数を意図する。上記アルキレン基は無置換であるのが好ましい。
上記疎水性基は、ケイ素原子又はフッ素原子を含有するのが好ましい。
上記疎水性基としては、無置換のアルキル基、フルオロアルキル基、又は、後述する式(SS1)で表される基が好ましく、フルオロアルキル基、又は、後述する式(SS1)で表される基がより好ましく、ジアルキルシロキサン基、又は、フルオロアルキル基が更に好ましい。
上記無置換のアルキル基の炭素数は、1~10が好ましく、1~5がより好ましい。
上記アルキル基部分の炭素数は、1~15が好ましく、1~10がより好ましい。
上記アルキル基部分は、フッ素原子以外の置換基を含有しないのも好ましい。
上記フルオロアルキル基が有するフッ素原子の数は、1~30個が好ましく、5~20個がより好ましい。
上記フルオロアルキル基は、その全体又は一部が、パーフルオロアルキル基になっているのも好ましい。
*-LS2-O-SiRS2 3 (SS1)
式(SS1)中、RS2は、置換基を含有してもよい炭素数1~20の炭化水素基を表す。*は結合位置を表す。
上記炭化水素基の炭素数は、1~20が好ましく、1~10がより好ましく、1~5が更に好ましい。ここでいう炭素数は、上記炭化水素基が置換基を含有する場合において、置換基中に存在し得る炭素原子の数をも計上した炭素数を意図する。
上記炭化水素基は、アルキル基であるのが好ましい。
上記アルキル基は、直鎖状及び分岐鎖状のいずれであってもよい。また、上記アルキル基は、全体が環状構造であってもよく、部分的に環状構造を含有してもよい。
複数存在するRS2は、それぞれ同一でも異なっていてもよい。
LS2における2価の連結基としては、例えば、式(A1)中のLS1における2価の連結基の例として挙げた基が同様に挙げられる。
また、LS2における2価の連結基が、1個以上(例えば1~1000個)の-SiRS2 2-O-を含有してもよい。なお、上記-SiRS2 2-O-におけるRS2は、上述したRS2と同様である。
式(A2)中、複数存在するRS3は、それぞれ同一でも、異なっていてもよい。
RS3で表され得る上記炭化水素基としては、例えば、上述したRS2で表され得る置換基を有してもよい炭化水素基が挙げられる。
中でも、式(A2)中の、右端のSiと結合するRS3は、それぞれ独立に、上記炭化水素基であるのが好ましい。
式(A2)中のsaが1の場合、「-(-SiRS3 2-O-)sa-」中のRS3は、それぞれ独立に、後述する式(A3)で表される基であるのが好ましい。
「-(-SiRS3 2-O-)sa-」中の「2×sa」個存在するRS3中、式(A3)で表される基であるRS3の数は、0~1000が好ましく、0~10がより好ましく、0~2が更に好ましい。
式(A3)で表される基を以下に示す。
式(A3)中、複数存在するRS4は、それぞれ同一でも、異なっていてもよい。
RS4で表され得る上記炭化水素基としては、例えば、上述したRS2で表され得る置換基を有してもよい炭化水素基が挙げられる。
上記その他の繰り返し単位としては、(メタ)アクリルに由来する繰り返し単位、又は、ケイ素原子を含有しない繰り返し単位が好ましい。
上記その他の繰り返し単位の分子量は、86~1000が好ましく、100~500がより好ましい。
中でも、硬化性を付与する点から、(メタ)アクリロイル基、エポキシ基、又は、チオール基が好ましく、アルカリ現像性を付与する点から、カルボン酸基、又は、カルボン酸無水物基が好ましい。
中でも、修飾無機粒子は、1種を単独で用いること、又は、2種の混合で用いることが好ましい。
2種以上の修飾無機粒子を使用する場合には、合計含有量が下記範囲内であることが好ましい。
修飾無機粒子の含有量は、組成物の全固形分に対して、0.1~30.0質量%が好ましく、0.5~20.0質量%がより好ましく、本発明の効果がより優れる点から、1.0~20.0質量%が更に好ましく、2.5~16.0質量%が特に好ましい。
無機粒子に対して、疎水性基を含有するシランカップリング剤と、疎水性基以外の置換基を含有するシランカップリング剤とを反応させて、被覆層を無機粒子の表面上に形成し、無機粒子を被覆する工程(被覆層形成工程)を有する、修飾無機粒子の製造方法が挙げられる。
なお、上記製造方法にて得られた修飾無機粒子は、疎水性基を含有するシランカップリング剤と、疎水性基以外の置換基を含有するシランカップリング剤とを少なくとも含むシランカップリング剤で表面修飾された無機粒子に該当する。
シランカップリング剤の化合物例および商品例としては、3-トリメトキシシリルプロピルコハク酸無水物(カルボン酸無水物基)、3-メタクリロキシプロピルトリメトキシシラン、3-アクリロキシプロシルトリメトキシシラン、KBM-5803、KR-513(それぞれ信越シリコーン社製)((メタ)アクリロイル基)、p-スチリルトリメトキシシラン(スチリル基)、ビニルトリメトキシシラン(ビニル基)、3-グリシドキシプロピルトリメトキシシラン(エポキシ基)、3-メルカプトプロピルトリメトキシシラン(メルカプト基)、3-ウレイドプロピルトトリアルコキシシラン(ウレイド基)、及び、3-アミノプロピルトリメトキシシラン(アミノ基)が挙げられる。
精製処理としては、特に制限はないが、例えば、ろ過およびろ物の洗浄、遠心処理、再沈殿処理、分液処理、限外ろ過処理、並びに、吸着材処理等が挙げられる。
ろ過およびろ物の洗浄処理としては、被覆層形成工程を実施して得られた溶液をろ過(好ましくは精密ろ過)し、修飾無機粒子をろ物として得て、上記非被覆物をろ液中に分離する処理が挙げられる。さらに、ろ物を非被覆物が溶解しやすい溶媒で洗浄する工程を追加で実施する方法も挙げられる。
遠心処理としては、被覆層形成工程を実施して得られた溶液を遠心して、上記非被覆物を含有する上澄み液と、修飾無機粒子を含有する堆積物とに分離し、上澄み液を除去した後、修飾無機物粒子を含有する堆積物に溶媒を加え再分散する処理が挙げられる。再分散は、撹拌処理、ビーズミル処理、ペイントシェーカー処理、及び、加熱処理等が挙げられる。
再沈殿処理としては、修飾無機粒子を含む溶液に、修飾無機粒子の貧溶媒を加えることで修飾無機粒子を沈殿させ、上記非被覆物を含有する上澄みを除去する方法が挙げられる。また、該方法で沈殿させた修飾無機粒子を上記のろ過およびろ物の洗浄処理をする方法が挙げられる。
分液処理としては、被覆層形成工程を実施して得られた溶液を分液処理し、修飾無機粒子が分散した溶液と、非被覆物が溶解した溶液とに分離する処理が挙げられる。
限外ろ過処理としては、被覆層形成工程を実施して得られた溶液を限外ろ過し、非被覆物を分離する処理が挙げられる。使用する限外ろ過膜の好ましい分画分子量は、粒子の粒径によっても異なるが50000以上が好ましく、100000以上がより好ましい。
吸着処理としては、被覆層形成工程を実施して得られた溶液に修飾無機粒子より十分粒径の大きい吸着材を添加し非被覆物を吸着処理し、吸着材をろ過等で取り除くことで、非被覆物を分離する処理が挙げられる。
本発明の組成物は、重合性化合物を含有する。
本明細書において、「重合性化合物」とは、後述する重合開始剤等の作用を受けて重合可能な有機化合物(例えば、エチレン性不飽和基を含有する有機化合物)を意味する。
本発明の組成物が溶媒を含有する場合、重合性化合物は溶媒に溶解して存在するのが好ましい。
組成物中における重合性化合物の含有量は、組成物の全固形分に対して、5~60質量%が好ましく、7~30質量%がより好ましく、10~20質量%が更に好ましい。
また、重合性化合物の含有量は、組成物の全非着色有機固形分に対して、10~70質量%が好ましく、20~60質量%がより好ましく、25~50質量%が更に好ましい。
非着色有機固形分とは、固形分であって、非着色性の有機成分をいう。例えば、上述の、無機粒子は、有機成分には該当せず、非着色有機固形分に含まれない。
また、有機成分であっても色材又は着色剤として使用される成分(有機顔料等)は着色性の成分であるため、非着色有機固形分に含まれない。
非着色有機固形分としては、例えば、重合性化合物、後述する樹脂であって重合開始剤の作用を受けて重合する基(エチレン性不飽和基等)を含有しない樹脂、重合開始剤、界面活性剤及び重合禁止剤が挙げられる。
組成物は重合性化合物を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
重合性化合物の分子量(分子量分布を有する場合は重量平均分子量)は、特に制限されないが、2500以下が好ましい。下限は、100以上が好ましい。
つまり、本発明の組成物は、エチレン性不飽和基を含有する低分子化合物を、重合性化合物として含有することが好ましい。
重合性化合物としては、エチレン性不飽和結合を1個以上含有する化合物が好ましく、2個以上含有する化合物がより好ましく、3個以上含有する化合物が更に好ましく、4個以上含有する化合物が特に好ましい。上限は、例えば、15個以下である。エチレン性不飽和基としては、例えば、ビニル基、(メタ)アリル基及び(メタ)アクリロイル基が挙げられる。
重合性化合物は、3~15官能の(メタ)アクリレート化合物が好ましく、3~6官能の(メタ)アクリレート化合物がより好ましい。
以下に好ましい重合性化合物の態様を示す。
カプロラクトン構造を含有する化合物としては、例えば、分子内にカプロラクトン構造を含有する限り特に制限されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール及びトリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンとをエステル化して得られる、ε-カプロラクトン変性多官能(メタ)アクリレートが挙げられる。中でも、下記式(Z-1)で表されるカプロラクトン構造を含有する化合物が好ましい。
式(Z-4)中、(メタ)アクリロイル基の合計は3個又は4個であり、mは0~10の整数を表し、各mの合計は0~40の整数である。
式(Z-5)中、(メタ)アクリロイル基の合計は5個又は6個であり、nは0~10の整数を表し、各nの合計は0~60の整数である。
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数が更に好ましい。
式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が更に好ましい。
また、式(Z-4)又は式(Z-5)中の-((CH2)yCH2O)-又は-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。
式(Z-4)又は式(Z-5)で表される化合物の中でも、ペンタエリスリトール誘導体及び/又はジペンタエリスリトール誘導体がより好ましい。
カルド骨格を含有する重合性化合物は、9,9-ビスアリールフルオレン骨格を含有する重合性化合物が好ましい。
カルド骨格を含有する重合性化合物としては、例えば、オンコートEXシリーズ(長瀬産業社製)及びオグソール(大阪ガスケミカル社製)が挙げられる。
重合性化合物は、イソシアヌル酸骨格を中心核として含有する化合物も好ましい。このような重合性化合物としては、例えば、NKエステルA-9300(新中村化学株式会社製)が挙げられる。
重合性化合物のエチレン性不飽和基の含有量(重合性化合物中のエチレン性不飽和基の数を、重合性化合物の分子量(g/mol)で除した値を意味する)は5.0mmol/g以上が好ましい。上限は、20.0mmol/g以下が好ましい。
本発明の組成物は、樹脂を含有する。
樹脂は、例えば、顔料等の粒子を組成物中で分散させる用途及びバインダーの用途で配合される。なお、主に顔料等の粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、上記分散剤には、フッ素原子及びケイ素原子のいずれも含まれないのも好ましい。
樹脂用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。
樹脂は、カルド骨格を有する、カルド樹脂であってもよい。
この場合の樹脂は、エチレン性不飽和基を有することが好ましく、エチレン性不飽和基としては、例えば、ビニル基、(メタ)アリル基及び(メタ)アクリロイル基が挙げられる。
本発明の組成物中、重合性を有する樹脂の含有量は、樹脂の全質量に対して、10~100質量%が好ましく、60~100質量%がより好ましく、85~100質量%が更に好ましい。
本発明の組成物は、アルカリ可溶性樹脂を含有することが好ましい。本発明の組成物がアルカリ可溶性樹脂を含有することにより、組成物の現像性が向上し、本発明の組成物を用いてフォトリソグラフィ法でパターン形成した際においては、現像残渣の発生等を効果的に抑制できる。アルカリ可溶性樹脂としては、酸基を有する樹脂が挙げられる。酸基としては、カルボキシル基、リン酸基、スルホ基及びフェノール性ヒドロキシ基等が挙げられ、カルボキシル基が好ましい。アルカリ可溶性樹脂が有する酸基は、1種のみであってもよいし、2種以上であってもよい。なお、アルカリ可溶性樹脂は、分散剤として用いることもできる。
アルカリ可溶性樹脂については、特開2012-208494号公報の段落[0558]~[0571](対応する米国特許出願公開第2012/0235099号明細書の段落[0685]~[0700])の記載、特開2012-198408号公報の段落[0076]~[0099]の記載を参酌でき、これらの内容は本明細書に組み込まれる。
樹脂(特に、アルカリ可溶性樹脂)のエチレン性不飽和結合当量(重合性化合物中のエチレン性不飽和基の数を、重合性化合物の分子量(g/mol)で除した値を意味する)は、0.4~2.5mmol/gが好ましい。下限は、1.0mmol/g以上が好ましく、1.2mmol/g以上がより好ましい。上限は、2.3mmol/g以下が好ましく、2.0mmol/g以下がより好ましい。
特に、本発明の組成物が、酸価が10~100mgKOH/gであり、かつ、エチレン性不飽和結合当量が1.0~2.0mmol/gである樹脂を含有する場合、耐湿試験後の剥がれの発生をより抑制できる。
塩基性基を有する樹脂のアミン価は、10~250mgKOH/gが好ましく、50~200mgKOH/gがより好ましい。
本発明の組成物は、分散剤としての樹脂を含有することもでき、分散剤としての樹脂を含有することが好ましい。分散剤としての樹脂がアルカリ可溶性樹脂に該当していてもよい。
分散剤としての樹脂は、酸性分散剤(酸性樹脂)、及び、塩基性分散剤(塩基性樹脂)が挙げられる。ここで、酸性分散剤(酸性樹脂)とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤(酸性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、酸基の量が70モル%以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤(酸性樹脂)が有する酸基は、カルボキシル基が好ましい。また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。分散剤としては、塩基性基を有する樹脂であることが好ましく、塩基性分散剤であることがより好ましい。
グラフト鎖と溶剤との相互作用性を向上させ、それにより色材等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造及びポリ(メタ)アクリレート構造からなる群から選ばれた少なくとも1種を含有するグラフト鎖であることが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含有するグラフト鎖であることがより好ましい。
本発明の組成物は、ポリアルキレンイミンを含有していてもよい。
ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーのことである、ポリアルキレンイミンは、1級アミノ基と、2級アミノ基と、3級アミノ基とをそれぞれ含む分岐構造を有するポリマーであることが好ましい。アルキレンイミンの炭素数は、2~6が好ましく、2~4がより好ましく、2又は3が更に好ましく、2が特に好ましい。
アルキレンイミンの具体例としては、エチレンイミン、プロピレンイミン、1,2-ブチレンイミン、及び、2,3-ブチレンイミンが挙げられ、エチレンイミン又はプロピレンイミンが好ましく、エチレンイミンがより好ましい。
なお、ポリアルキレンイミンの分子量の値について、構造式から分子量が計算できる場合は、ポリアルキレンイミンの分子量は構造式から計算した値である。一方、ポリアルキレンイミンの分子量が構造式から計算できない、又は、計算が困難な場合には、沸点上昇法で測定した数平均分子量の値を用いる。また、沸点上昇法でも測定できない、又は、測定が困難な場合は、粘度法で測定した数平均分子量の値を用いる。また、粘度法でも測定できない、あるいは、粘度法での測定が困難な場合は、GPC(ゲルパーミエーションクロマトグラフィ)法により測定したポリスチレン換算値での数平均分子量の値を用いる。
また、組成物に含まれる樹脂中における分散剤としての樹脂の含有量(例えば、アルカリ可溶性樹脂にも分散剤としての樹脂にも該当する樹脂及びアルカリ可溶性樹脂には該当せず分散剤としての樹脂に該当する樹脂の合計含有量)は、50~100質量%が好ましく、75~100質量%がより好ましく、90~100質量%が更に好ましい。
組成物は、分散助剤を含んでもよい。
分散助剤は、上述した樹脂以外の成分であって、黒色顔料のように組成物中に固体状態で存在する成分の凝集及び/又は沈降を抑制し得る成分である。
分散助剤としては、例えば、顔料誘導体が挙げられる。
分散助剤の含有量は、組成物の全固形分に対して、0.01~10質量%が好ましく、0.1~8質量%がより好ましく、0.3~4質量%が更に好ましい。
本発明の組成物は、重合開始剤を含んでもよい。
重合開始剤としては、例えば、公知の重合開始剤を使用できる。重合開始剤としては、例えば、光重合開始剤及び熱重合開始剤等が挙げられ、光重合開始剤が好ましい。
重合開始剤の含有量は、組成物の全固形分に対して、0.5~20質量%が好ましく、1.0~10質量%がより好ましく、1.5~8質量%が更に好ましい。
組成物は重合開始剤を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
熱重合開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル(AIBN)、3-カルボキシプロピオニトリル、アゾビスマレノニトリル及びジメチル-(2,2’)-アゾビス(2-メチルプロピオネート)[V-601]等のアゾ化合物、並びに、過酸化ベンゾイル、過酸化ラウロイル及び過硫酸カリウム等の有機過酸化物が挙げられる。
熱重合開始剤の具体例としては、加藤清視著「紫外線硬化システム」(株式会社総合技術センター発行:平成元年)の第65~148頁に記載されている重合開始剤が挙げられる。
光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択できる。例えば、紫外線領域から可視光領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤としては、光ラジカル重合開始剤が好ましい。
光重合開始剤としては、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン-ベンゼン-鉄錯体、ハロメチルオキサジアゾール化合物又は3-アリール置換クマリン化合物が好ましく、オキシム化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物及びアシルホスフィン化合物から選ばれる化合物がより好ましく、オキシム化合物が更に好ましい。
光重合開始剤としては、特開2014-130173号公報の段落[0065]~[0111]、特許第6301489号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。
組成物は光重合開始剤を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
組成物は、重合禁止剤を含有してもよい。
重合禁止剤としては、例えば、公知の重合禁止剤を使用できる。重合禁止剤としては、例えば、フェノール系重合禁止剤(例えば、p-メトキシフェノール、2,5-ジ-tert-ブチル-4-メチルフェノール、2,6-ジtert-ブチル-4-メチルフェノール、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、4-メトキシナフトール等);ハイドロキノン系重合禁止剤(例えば、ハイドロキノン、2,6-ジ-tert-ブチルハイロドロキノン等);キノン系重合禁止剤(例えば、ベンゾキノン等);フリーラジカル系重合禁止剤(例えば、2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル等);ニトロベンゼン系重合禁止剤(例えば、ニトロベンゼン、4-ニトロトルエン等);及びフェノチアジン系重合禁止剤(例えば、フェノチアジン、2-メトキシフェノチアジン等);が挙げられる。
中でも、本発明の効果がより優れる点から、フェノール系重合禁止剤又はフリーラジカル系重合禁止剤が好ましい。
組成物は重合禁止剤を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
また、組成物中の重合性化合物の含有量に対する、重合禁止剤の含有量の比(重合禁止剤の含有量/重合性化合物の含有量(質量比))は、0.00005~0.02が好ましく、0.0001~0.005がより好ましい。
組成物は、界面活性剤を含有してもよい。界面活性剤は、組成物の塗布性向上に寄与する。
上記組成物が、界面活性剤を含有する場合、界面活性剤の含有量は、組成物の全固形分に対して、0.001~2.0質量%が好ましく、0.003~0.5質量%がより好ましく、0.005~0.1質量%が更に好ましい。
組成物は界面活性剤を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
フッ素系界面活性剤としてブロックポリマーも使用でき、具体例としては、例えば、特開第2011-089090号公報に記載されたが化合物が挙げられる。
本発明の組成物は、溶剤を含有することが好ましい。溶剤としては有機溶剤が好ましい。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤及び炭化水素系溶剤が挙げられる。これらの詳細については、国際公開第2015/166779号の段落[0223]を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシブチルアセテート、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル及びプロピレングリコールモノメチルエーテルアセテートが挙げられる。ただし、有機溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン及びエチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
組成物は溶媒を1種のみ含有してもよく、2種以上含有していてもよい。2種以上含有する場合は、それらの合計量が上記範囲となることが好ましい。
組成物は、上述した成分以外のその他の任意成分を更に含有してもよい。
例えば、黒色顔料以外の色材(顔料でも染料でもよい)、紫外線吸収剤、シランカップリング剤、界面活性剤、増感剤、共増感剤、架橋剤、硬化促進剤、熱硬化促進剤、可塑剤、希釈剤及び感脂化剤等が挙げられ、更に、基板表面への密着促進剤及びその他の助剤類(例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤及び連鎖移動剤等)等の公知の添加剤を必要に応じて加えてもよい。
これらの成分は、例えば、特開2012-003225号公報の段落[0183]~[0228](対応する米国特許出願公開第2013/0034812号明細書の段落[0237]~[0309])、特開2008-250074号公報の段落[0101]~[0102]、段落[0103]~[0104]、段落[0107]~[0109]及び特開2013-195480号公報の段落[0159]~[0184]等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
組成物は、黒色顔料の分散液を製造し、得られた組成物を更にその他の成分と混合して組成物とすることが好ましい。
なお、組成物の製造方法の説明中で言及される各成分については上述の通りである。
より具体的には、下記工程1及び工程2を有する製造方法で、組成物を製造することが好ましい。この方法によれば、本発明の効果がより優れる組成物を得ることができる。
工程1:黒色顔料と、樹脂と、カルボン酸無水物とを含有するプレ混合物をビーズミルで混合して混合物(色材分散液等)を得る工程
工程2:混合物と重合性化合物とを混合して組成物(黒色感光性組成物)を得る工程
上記プレ混合物は、黒色顔料と樹脂(好ましくは分散剤としての樹脂)とカルボン酸無水物以外の成分を含んでもよく、そのような成分としては、例えば、分散助剤、重合禁止剤及び溶剤が挙げられる。
工程1で混合の対象となるプレ混合物を得る際、プレ混合物に含まれる成分は、各成分を一括配合してもよいし、各成分をそれぞれ、溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。
プレ混合物は、ビーズミルによる混合を行う前に、粗混合しておくことも好ましい。粗混合の方法は特に制限されず、公知の手段を使用できる。
ビーズ径は、0.01~1.0mmが好ましく、0.03~0.65mmがより好ましい。
ビーズ充填率は、50~90%が好ましく、60~80%がより好ましい。
回転速度(周速)は、1~20m/sが好ましく、5~14m/sがより好ましい。
被処理物の温度は、5~80℃が好ましく、30~60℃がより好ましい。
ビーズミルは、例えば、バッチ式装置、循環式装置及び連続式装置のいずれでもよく、複数の装置を組み合わせて用いてもよい。
ビーズミルがバッチ式の場合、処理時間は、0.5~6時間が好ましく、2~4時間がより好ましい。
ビーズミルが循環式の場合、パス回数は、10~1000が好ましく、60~200がより好ましい。
樹脂(好ましくは分散剤としての樹脂)の含有量は、プレ混合物及び/又は混合物の全固形分に対して、1~50質量%が好ましく、5~40質量%がより好ましく、15~35質量%が更に好ましい。
カルボン酸無水物の含有量は、プレ混合物及び/又は混合物の全固形分に対して、0.05~30質量%が好ましく、0.1~20質量%がより好ましく、1~10質量%が更に好ましい。
黒色顔料の含有量は、プレ混合物及び/又は混合物の全固形分に対して、20~95質量%が好ましく、40~90質量%がより好ましく、60~80質量%が更に好ましい。
分散助剤の含有量は、プレ混合物及び/又は混合物の全固形分に対して、0.05~30質量%が好ましく、0.5~10質量%がより好ましく、1~5質量%が更に好ましい。
プレ混合物及び/又は混合物中、黒色顔料の含有量に対する、樹脂と酸無水物との合計含有量の質量比(樹脂と酸無水物との合計含有量/黒色顔料の含有量)は、0.10~2.00が好ましく、0.15~1.00がより好ましく、0.25~0.45が更に好ましい。
工程2では、工程1で得られた混合物と重合性化合物とを混合して組成物(黒色感光性組成物)を得る。
工程2では、上記混合物に対して少なくとも重合性化合物を混合すればよく、その他の成分(重合開始剤、重合禁止剤、界面活性剤、更に添加する樹脂及び/又は更に添加する溶剤等)を更に混合してもよい。
工程2で組成物を得るために混合される各成分(工程1で得られた混合物を含む)は、各成分を一括配合してもよいし、各成分をそれぞれ、溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。
上記の各成分を公知の混合方法(例えば、撹拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機又は湿式分散機等を用いた混合方法)により混合して組成物を調製できる。
工程2では得られる組成物では、組成物に含まれる黒色顔料、樹脂及びカルボン酸無水物中の少なくとも一部が、工程1で得られた混合物に由来していればよく、上記混合物に含まれていた成分とは別の、黒色顔料、樹脂及び/又はカルボン酸無水物等を工程2において更に混合してもよい。
工程2で得られる組成物が含有する溶剤のうち、工程1で得られた混合物に由来する溶剤の含有量は、10~100質量%が好ましく、50~95質量%がより好ましく、70~90質量%が更に好ましい。
工程2で得られる組成物が含有する樹脂のうち、工程1で得られた混合物に由来する樹脂の含有量は、10~100質量%が好ましく、70~100質量%がより好ましく、80~100質量%が更に好ましい。
工程2で得られる組成物が含有するカルボン酸無水物のうち、工程1で得られた混合物に由来するカルボン酸無水物の含有量は、10~100質量%が好ましく、70~100質量%がより好ましく、95~100質量%が更に好ましい。
工程2で得られる組成物が含有する黒色顔料のうち、工程1で得られた混合物に由来する黒色顔料の含有量は、10~100質量%が好ましく、70~100質量%がより好ましく、95~100質量%が更に好ましい。
工程2で得られる組成物が含有する分散助剤のうち、工程1で得られた混合物に由来する分散助剤の含有量は、10~100質量%が好ましく、70~100質量%がより好ましく、95~100質量%が更に好ましい。
工程2で得られる組成物が含有する重合性化合物のうち、工程1で得られた混合物に由来する重合性化合物の含有量は、0~30質量%が好ましく、0~5質量%がより好ましく、0~1質量%が更に好ましい。
フィルタの孔径は、0.1~7.0μmが好ましく、0.2~2.5μmがより好ましく、0.2~1.5μmが更に好ましく、0.3~0.7μmが特に好ましい。この範囲とすれば、顔料(黒色顔料を含む)のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物等、微細な異物を確実に除去できるようになる。
フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が同じ又は大きい方が好ましい。また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照できる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)及び株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択できる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたフィルタを使用できる。第2のフィルタの孔径は、0.2~10.0μmが好ましく、0.2~7.0μmがより好ましく、0.3~6.0μmが更に好ましい。
組成物は、金属、ハロゲンを含有する金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量は、1質量ppm以下が好ましく、1質量ppb以下がより好ましく、100質量ppt以下が更に好ましく、10質量ppt以下が特に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が最も好ましい。
なお、上記不純物は、誘導結合プラズマ質量分析装置(横河アナリティカルシステムズ製、Agilent 7500cs型)により測定できる。
本発明の組成物を用いて形成された組成物層を硬化して、硬化膜(パターン状の硬化膜を含む)を得られる。
硬化膜の製造方法は、特に制限されないが、以下の工程を含有するが好ましい。
・組成物層形成工程
・露光工程
・現像工程
以下、各工程について説明する。
組成物層形成工程においては、露光に先立ち、支持体等の上に、組成物を付与して組成物の層(組成物層)を形成する。支持体としては、例えば、基板(例えば、シリコン基板)上にCCD(Charge Coupled Device)又はCMOS(Complementary Metal-Oxide Semiconductor)等の撮像素子(受光素子)が設けられた固体撮像素子用基板を使用できる。また、支持体上には、必要により、上部の層との密着改良、物質の拡散防止及び基板表面の平坦化等のために下塗り層を設けてもよい。
露光工程では、組成物層形成工程において形成された組成物層に活性光線又は放射線を照射して露光し、光照射された組成物層を硬化させる。
光照射の方法は、パターン状の開口部を有するフォトマスクを介して光照射することが好ましい。
露光は放射線の照射により行うことが好ましい。露光に際して使用できる放射線は、g線、h線及びi線等の紫外線が好ましく、光源は高圧水銀灯が好ましい。照射強度は5~1500mJ/cm2が好ましく、10~1000mJ/cm2がより好ましい。
なお、組成物が熱重合開始剤を含有する場合、上記露光工程において、組成物層を加熱してもよい。加熱の温度として特に制限されないが、80~250℃が好ましい。また、加熱の時間は、30~300秒間が好ましい。
なお、露光工程において、組成物層を加熱する場合、後述する後加熱工程を兼ねてもよい。言い換えれば、露光工程において、組成物層を加熱する場合、硬化膜の製造方法は後加熱工程を含有しなくてもよい。
現像工程は、露光後の上記組成物層を現像して硬化膜を形成する工程である。本工程により、露光工程における光未照射部分の組成物層が溶出し、光硬化した部分だけが残り、パターン状の硬化膜が得られる。
現像工程で使用される現像液の種類は特に制限されないが、下地の撮像素子及び回路等にダメージを起こさない、アルカリ現像液が望ましい。
現像温度としては、例えば、20~30℃である。
現像時間としては、例えば、20~90秒間である。残渣をよりよく除去するため、近年では120~180秒間実施する場合もある。更には、残渣除去性をより向上するため、現像液を60秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返す場合もある。
アルカリ性化合物は、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム,硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシ、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン及び1,8-ジアザビシクロ[5.4.0]-7-ウンデセンが挙げられる(このうち、有機アルカリが好ましい。)。
なお、アルカリ現像液として用いた場合は、一般に現像後に水で洗浄処理が施される。
露光工程の後、加熱処理(ポストベーク)を行うことが好ましい。ポストベークは、硬化を完全にするための現像後の加熱処理である。その加熱温度は、240℃以下が好ましく、220℃以下がより好ましい。下限は特にないが、効率的かつ効果的な処理を考慮すると、50℃以上が好ましく、100℃以上がより好ましい。
ポストベークは、ホットプレート、コンベクションオーブン(熱風循環式乾燥機)及び高周波加熱機等の加熱手段を用いて、連続式又はバッチ式で行える。
この場合、上述した組成物は、更にUV硬化剤を含有することが好ましい。UV硬化剤は、通常のi線露光によるリソグラフィー工程のために添加する重合開始剤の露光波長である365nmより短波の波長で硬化できるUV硬化剤が好ましい。UV硬化剤としては、例えば、チバ イルガキュア 2959(商品名)が挙げられる。UV照射を行う場合においては、組成物層が波長340nm以下で硬化する材料であることが好ましい。波長の下限値は特に制限されないが、220nm以上が好ましい。また、UV照射の露光量は、100~5000mJが好ましく、300~4000mJがより好ましく、800~3500mJが更に好ましい。このUV硬化工程は、露光工程の後に行うことが、低温硬化をより効果的に行うために、好ましい。露光光源はオゾンレス水銀ランプを使用することが好ましい。
〔硬化膜の物性〕
本発明の組成物を用いて形成される硬化膜は、優れた遮光性を有する点で、400~1100nmの波長領域における膜厚1.5μmあたりの光学濃度(OD:Optical Density)が、2.5以上が好ましく、3.0以上がより好ましい。なお、上限値は特に制限されないが、一般に10以下が好ましい。上記硬化膜は、遮光膜として好ましく使用できる。
なお、本明細書において、400~1100nmの波長領域における膜厚1.5μmあたりの光学濃度が2.5以上であるとは、波長400~1100nmの全域において、膜厚1.5μmあたりの光学濃度が2.5以上であることを意味する。
なお、本明細書において、硬化膜の光学濃度の測定方法としては、まず、ガラス基板上硬化膜を形成して、分光光度計U-4100(商品名、日立ハイテクノロジーズ社製)積分球型受光ユニットを用いて測定し、測定箇所の膜厚も測定し、所定の膜厚あたりの光学濃度を算出する。
硬化膜の膜厚は、例えば、0.1~4.0μmが好ましく、1.0~2.5μmがより好ましい。また、硬化膜は、用途にあわせてこの範囲よりも薄膜としてもよいし、厚膜としてもよい。
また、硬化膜を光減衰膜として使用する場合、上記範囲よりも薄膜(例えば、0.1~0.5μm)として遮光性を調整してもよい。この場合、400~1200nmの波長領域における膜厚1.0μmあたりの光学濃度は、0.1~1.5が好ましく、0.2~1.0がより好ましい。
反射率とは、日本分光株式会社製分光器V7200(商品名)VARユニットを用いて角度5°の入射角で波長400~1100nmの光を入射し、得られた反射率スペクトルより求められる。具体的には、波長400~1100nmの範囲で最大反射率を示した波長の光の反射率を、硬化膜の反射率とする。
マイクロLED及びマイクロOLEDとしては、例えば、特表2015-500562号公報及び特表2014-533890号公報に記載された例が挙げられる。
本発明の硬化膜は、いわゆる遮光膜として使用することも好ましい。このような遮光膜は、固体撮像素子に使用することも好ましい。
本発明の遮光性組成物を用いて形成された硬化膜は、上述のとおり、遮光性及び低反射性に優れる。
なお、遮光膜は、本発明の硬化膜における好ましい用途の1つであって、本発明の遮光膜の製造は、上述の硬化膜の製造方法として説明した方法で同様に行える。具体的には、基板に組成物を塗布して、組成物層を形成し、露光及び現像して遮光膜を製造できる。
中でも、上記光学素子としては、例えば、カメラ等に搭載される固体撮像素子が好ましい。
本発明の固体撮像素子が硬化膜(遮光膜)を含有する形態としては、例えば、基板上に、固体撮像素子(CCDイメージセンサ、CMOSイメージセンサ等)の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側(例えば、受光部以外の部分及び/又は色調整用画素等)又は形成面の反対側に硬化膜を有する形態が挙げられる。
また、硬化膜を光減衰膜として使用する場合、例えば、一部の光が光減衰膜を通過した上で受光素子に入射するように、光減衰膜を配置すれば、固体撮像素子のダイナミックレンジを改善できる。
固体撮像装置は、上記固体撮像素子を具備する。
図1は、本発明の固体撮像素子を含有する固体撮像装置の構成例を示す概略断面図である。
図1に示すように、固体撮像装置100は、矩形状の固体撮像素子101と、固体撮像素子101の上方に保持され、この固体撮像素子101を封止する透明なカバーガラス103とを備えている。更に、このカバーガラス103上には、スペーサー104を介してレンズ層111が重ねて設けられている。レンズ層111は、支持体113とレンズ材112とで構成されている。レンズ層111は、支持体113とレンズ材112とが一体成形された構成でもよい。レンズ層111の周縁領域に迷光が入射すると光の拡散によりレンズ材112での集光の効果が弱くなり、撮像部102に届く光が低減する。また、迷光によるノイズの発生も生じる。そのため、このレンズ層111の周縁領域は、遮光膜114が設けられて遮光されている。本発明の硬化膜は上記遮光膜114としても使用できる。
遮光膜212上には、BPSG(borophospho silicate glass)からなる絶縁膜213、P-SiNからなる絶縁膜(パシベーション膜)214、透明樹脂等からなる平坦化膜215からなる透明な中間層が設けられている。カラーフィルタ202は、中間層上に形成されている。
本発明の画像表示装置は、本発明の硬化膜を具備する。
画像表示装置が硬化膜を有する形態としては、例えば、硬化膜がブラックマトリクスに含有され、このようなブラックマトリクスを含有するカラーフィルタが、画像表示装置に使用される形態が挙げられる。
次に、ブラックマトリクス及びブラックマトリクスを含有するカラーフィルタについて説明し、更に、画像表示装置の具体例として、このようなカラーフィルタを含有する液晶表示装置について説明する。
本発明の硬化膜は、ブラックマトリクスに含有されることも好ましい。ブラックマトリクスは、カラーフィルタ、固体撮像素子及び液晶表示装置等の画像表示装置に含有される場合がある。
ブラックマトリクスとしては、例えば、上記で既に説明したもの;液晶表示装置等の画像表示装置の周縁部に設けられた黒色の縁;赤、青及び緑の画素間の格子状及び/又はストライプ状の黒色の部分;TFT(thin film transistor)遮光のためのドット状及び/又は線状の黒色パターン;が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第2版、日刊工業新聞社、1996年、p.64に記載がある。
ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ(TFT)を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性(光学濃度ODで3以上)を有することが好ましい。
本発明の硬化膜は、カラーフィルタに含有されることも好ましい。
カラーフィルタが硬化膜を含有する形態としては、例えば、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板上に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色及び青色の着色画素と、を備えるカラーフィルタが例示できる。
まず、基板上に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する顔料を含有した組成物の組成物層を形成する。なお、各色用組成物としては、例えば、公知の組成物を使用できるが、本明細書で説明した組成物において、黒色色材を、各画素に対応した着色剤に置き換えた組成物を使用することが好ましい。
次に、組成物層に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークしてブラックマトリクスの開口部に着色画素を形成できる。一連の操作を、例えば、赤色、緑色及び青色顔料を含有した各色用組成物を用いて行えば、赤色、緑色及び青色画素を有するカラーフィルタを製造できる。
本発明の硬化膜は、液晶表示装置に含有されることも好ましい。液晶表示装置が硬化膜を含有する形態としては、例えば、すでに説明したブラックマトリクス(硬化膜)を含有するカラーフィルタを含有する形態が挙げられる。
本発明の硬化膜は、赤外線センサに含有されることも好ましい。
上記実施態様に係る赤外線センサについて、図3を用いて説明する。図3は、本発明の硬化膜を備える赤外線センサの構成例を示す概略断面図である。図3に示す赤外線センサ300は、固体撮像素子310を備える。
固体撮像素子310上に設けられている撮像領域は、赤外線吸収フィルタ311と本発明の実施形態に係るカラーフィルタ312とを組み合せて構成されている。
赤外線吸収フィルタ311は、可視光領域の光(例えば、波長400~700nmの光)を透過し、赤外領域の光(例えば、波長800~1300nmの光、好ましくは波長900~1200nmの光、より好ましくは波長900~1000nmの光)を遮蔽する膜であり、着色剤として赤外線吸収剤(赤外線吸収剤の形態は既に説明したとおりである。)を含有する硬化膜を使用できる。
カラーフィルタ312は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色(R)、緑色(G)、青色(B)の画素が形成されたカラーフィルタ等が用いられ、その形態は既に説明したとおりである。
赤外線透過フィルタ313と固体撮像素子310との間には、赤外線透過フィルタ313を透過した波長の光を透過可能な樹脂膜314(例えば、透明樹脂膜等)が配置されている。
赤外線透過フィルタ313は、可視光遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、可視光領域の光を吸収する着色剤(例えば、ペリレン化合物及び/又はビスベンゾフラノン化合物等)と、赤外線吸収剤(例えば、ピロロピロール化合物、フタロシアニン化合物、ナフタロシアニン化合物及びポリメチン化合物等)と、を含有する、本発明の硬化膜を使用できる。赤外線透過フィルタ313は、例えば、波長400~830nmの光を遮光し、波長900~1300nmの光を透過させることが好ましい。
カラーフィルタ312及び赤外線透過フィルタ313の入射光hν側には、マイクロレンズ315が配置されている。マイクロレンズ315を覆うように平坦化膜316が形成されている。
図3に示す形態では、樹脂膜314が配置されているが、樹脂膜314に代えて赤外線透過フィルタ313を形成してもよい。すなわち、固体撮像素子310上に、赤外線透過フィルタ313を形成してもよい。
また、図3に示す形態では、カラーフィルタ312の膜厚と、赤外線透過フィルタ313の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
また、図3に示す形態では、カラーフィルタ312が、赤外線吸収フィルタ311よりも入射光hν側に設けられているが、赤外線吸収フィルタ311と、カラーフィルタ312との順序を入れ替えて、赤外線吸収フィルタ311を、カラーフィルタ312よりも入射光hν側に設けてもよい。
また、図3に示す形態では、赤外線吸収フィルタ311とカラーフィルタ312は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていてもよい。本発明の硬化膜は、赤外線吸収フィルタ311の表面の端部及び/又は側面等の遮光膜として使用できるほか、赤外線センサの装置内壁に用いれば、内部反射及び/又は受光部への意味しない光の入射を防ぎ、感度を向上させられる。
この赤外線センサによれば、画像情報を同時に取り込めるため、動きを検知する対象を認識したモーションセンシング等が可能である。また、この赤外線センサによれば、距離情報を取得できるため、3D情報を含んだ画像の撮影等も可能である。更に、この赤外線センサは、生体認証センサとしても使用できる。
上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含有する。なお、固体撮像装置の各構成については、特開2011-233983号公報の段落0032~0036を参酌でき、この内容は本願明細書に組み込まれる。
本発明の硬化膜は、遮光膜として、自動車等の車両用灯具のヘッドライトユニットに含有されることも好ましい。遮光膜としてヘッドライトユニットに含有される本発明の硬化膜は、光源から出射される光の少なくとも一部を遮光するように、パターン状に形成されることが好ましい。
上記実施態様に係るヘッドライトユニットについて、図4及び図5を用いて説明する。図4は、ヘッドライトユニットの構成例を示す模式図であり、図5はヘッドライトユニットの遮光部の構成例を示す模式的斜視図である。
図4に示すように、ヘッドライトユニット10は、光源12と、遮光部14と、レンズ16とを有し、光源12、遮光部14及びレンズ16の順で配置されている。
遮光部14は、図5に示すように基体20と、遮光膜22とを有する。
遮光膜22は、光源12から出射される光を特定の形状に照射するためのパターン状の開口部23が形成されている。遮光膜22の開口部23の形状により、レンズ16から照射される配光パターンが決定される。レンズ16は、遮光部14を通過した光源12からの光Lを投影するものである。光源12から、特定の配光パターンを照射することができれば、レンズ16は、必ずしも必要ではない。レンズ16は、光Lの照射距離及び照射範囲に応じて適宜決定されるものである。
また、基体20は、遮光膜22を保持することができれば、その構成は、特に限定されるものではないが、光源12の熱等により変形しないものであることが好ましく、例えば、ガラスで構成される。
図5では、配光パターンの一例を示したが、これに限定されるものではない。
また、光源12も1つに限定されるものではなく、例えば、列状に配置してもよく、マトリクス状に配置してもよい。光源を複数設ける場合、例えば、1つの光源12に対して、1つの遮光部14を設ける構成でもよい。この場合、複数の遮光部14の各遮光膜22は、全て同じパターンでもよく、それぞれ異なるパターンでもよい。
図6はヘッドライトユニットによる配光パターンの一例を示す模式図であり、図7はヘッドライトユニットによる配光パターンの他の例を示す模式図である。なお、図6に示す配光パターン30と図7に示す配光パターン32はいずれも光が照射される領域を示している。また、図6に示す領域31及び図7に示す領域31は、いずれも遮光膜22を設けていない場合に光源12(図4参照)で照射される照射領域を示す。
遮光膜22のパターンにより、例えば、図6に示す配光パターン30のように、エッジ30aで光の強度が急激に低下している。図6に示す配光パターン30は、例えば、左側通行において、対向車に光を照らさないパターンとなる。
また、図7に示す配光パターン32のように、図6に示す配光パターン30の一部を切り欠いたパターンとすることもできる。この場合も、図6に示す配光パターン30と同じく、エッジ32aで光の強度が急激に低下しており、例えば、左側通行において、対向車に光を照らさないパターンとなる。更に、切欠部33でも光の強度が急激に低下している。このため、切欠部33に対応する領域に、例えば、道路がカーブしている、上り傾斜、下り傾斜等の状態を示すマークを表示することができる。これにより、夜間走行時の安全性を向上させることができる。
また、遮光部14で、光源12からの光を遮光可能なシェード部材を構成してもよい。この場合、図示しない駆動機構により、光源12とレンズ16との間に、必要に応じて進入させて、特定の配光パターンを得る構成とすることもできる。
〔色材分散液AA1の製造〕
平均粒径15nmの酸化チタンMT-150A(商品名:テイカ社製)を100g、BET表面積300m2/gのシリカ粒子AEROGIL(登録商標)300/30(エボニック社製)を25g及び分散剤Disperbyk190(商品名:ビックケミー社製)を100g秤量し、イオン電気交換水71gを加えてKURABO社製MAZERSTAR KK-400Wを使用して、公転回転数1360rpm、自転回転数1047rpmにて20分間処理することにより均一な混合物水溶液を得た。この水溶液を石英容器に充填し、小型ロータリーキルン(モトヤマ社製)を用いて酸素雰囲気中で920℃に加熱した後、窒素で雰囲気を置換し、同温度でアンモニアガスを100mL/minで5時間流すことにより窒化還元処理を実施した。終了後、回収した粉末を乳鉢で粉砕し、Si原子を含有し、粉末状の比表面積73m2/gのチタンブラック(a-1)〔チタンブラック粒子及びSi原子を含有する被分散体〕を得た。
上記で調製したチタンブラック(a-1)(25質量部)に対し、樹脂X-1(7.5質量部)及び評価化合物としてのS-1(0.13質量部)を加え、更に、液総量が100質量部となるようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)とシクロペンタノンを74.6対25.4の割合(質量比)で加えて、分散物を得た。
得られた分散物を撹拌機により十分に撹拌し、プレミキシングを行った。得られた分散物に対し、シンマルエンタープライゼス製のNPM Pilot(ビーズミル)を使用して下記条件にて分散処理を行い、色材分散液AA1を得た。
・ビーズ径:φ0.05mm
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレーター周速:11m/s
・分散処理する混合液量:15.0kg
・循環流量(ポンプ供給量):60kg/hour
・処理液温度:20~25℃
・冷却水:水道水 5℃
・ビーズミル環状通路内容積:2.2L
・パス回数:84パス
なお、以降の色材調整液においてもX-1とS-1とは同様の化合物である。
なお、表1~5中の「平均粒径(nm)」は、色材分散液中のチタンブラックの平均粒径を表す。
通常のオイルファーネス法で、カーボンブラックを製造した。但し、原料油としては、Na分量、Ca分量及びS分量の少ないエチレンボトム油を用い、ガス燃料を用いて燃焼を行った。更に、反応停止水としては、イオン交換樹脂で処理した純水を用いた。
ホモミキサーを用いて、得られたカーボンブラック(540g)を純水(14500g)と共に5,000~6,000rpmで30分撹拌し、スラリーを得た。このスラリーをスクリュー型撹拌機付容器に移して、約1,000rpmで混合しながらエポキシ樹脂「エピコート828」(ジャパンエポキシレジン製)(60g)を溶解したトルエン(600g)を少量ずつ添加した。約15分で、水に分散していたカーボンブラックは全量トルエン側に移行し、約1mmの粒となった。
次に、60メッシュ金網で水切りを行った後、分離された粒を真空乾燥機に入れ、70℃で7時間乾燥し、トルエン及び水を除去して、被覆カーボンブラックを得た。得られた被覆カーボンブラックの樹脂被覆量は、カーボンブラックと樹脂の合計量に対して10質量%であった。
なお、得られたカーボンブラック(被覆カーボンブラック)は粉砕してから、色材分散液の調製に使用した。粉砕後のカーボンブラック(被覆カーボンブラック)の平均粒径は120nmであった。
被覆カーボンブラック(25質量部)に対し、樹脂X-1(7.5質量部)、評価化合物としてのS-1(0.13質量部)及び顔料誘導体としてのS12000(ルーブリゾール社製)(1質量部)を加え、更に、液総量が100質量部となるようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)とシクロペンタノンを74.6対25.4の割合(質量比)で加えて、分散物を得た。
得られた分散物を撹拌機により十分に撹拌し、プレミキシングを行った。更に、分散物に対し、寿工業社製のウルトラアペックスミルUAM015(ビーズミル)を使用して下記条件にて分散処理を行い、分散組成物を得た。分散終了後、フィルターによりビーズと分散液を分離して、色材分散液BA1を調製した。
・ビーズ径:φ0.05mm
・ビーズ充填率:75体積%
・ミル周速:8m/sec
・分散処理する混合液量:500g
・循環流量(ポンプ供給量):13kg/hour
・処理液温度:25~30℃
・冷却水:水道水
・ビーズミル環状通路内容積:0.15L
・パス回数:90パス
なお、表6~10中の「平均粒径(nm)」は、色材分散液中のカーボンブラックの平均粒径を表す。
有機ブラックIrgaphor BlackS0100CF(BASF社製、平均粒径90nm)(25質量部)に、評価化合物としてのS-1(0.12質量部)及び樹脂としてのSOLSPERSE 20000(ルーブリゾール社製)(7.5質量部)及び液総量が100質量部となるように3-メトキシブチルアセテート(以下「MBA」)を加え、混合し、ホモミキサー(プライミクス製)で20分間撹拌して、予備分散液を得た。得られた予備分散液を、0.30mmφジルコニアビーズ(YTZボール;ネツレン製)を75%充填した遠心分離セパレーターを具備したウルトラアペックスミル(寿工業社製、ビーズミル)に供給し、回転速度8m/sで3時間分散させて、固形分濃度32.6質量%の色材分散液CA1を得た。なお、樹脂SOLSPERSE 20000のアミン価は29mgKOH/gで酸価はなく、顔料吸着基として3級アミンを有する。また、MBAのSP値は8.7である。
なお、表11~15中の「平均粒径(nm)」は、色材分散液中の有機ブラックの平均粒径を表す。
酸窒化ジルコニウム(三菱マテリアル社製、粉末状の比表面積65m2/g)(25質量部)に対し、樹脂DISPERBYK-2159(ビックケミー・ジャパン社製、7.5質量部)及び評価化合物としてのS-1(0.13質量部)を加え、更に、液総量が100質量部となるようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)とシクロペンタノンを74.6対25.4の割合(質量比)で加えて、分散物を得た。得られた分散物を撹拌機により十分に撹拌し、プレミキシングを行った。得られた分散物に対し、シンマルエンタープライゼス製のNPM Pilot(ビーズミル)を使用して下記条件にて分散処理を行い、色材分散液DA1を得た。
(分散条件)
・ビーズ径:φ0.05mm
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレーター周速:11m/s
・分散処理する混合液量:15.0kg
・循環流量(ポンプ供給量):60kg/hour
・処理液温度:20~25℃
・冷却水:水道水 5℃
・ビーズミル環状通路内容積:2.2L
・パス回数:84パス
なお、表16~20中の「平均粒径(nm)」は、色材分散液中の酸窒化ジルコニウムの平均粒径を表す。
チタンブラック(a-1)(25質量部)に対し、樹脂X-2(7.5質量部)及び評価化合物としてのS-1(0.13質量部)を加え、更に、液総量が100質量部となるようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)とシクロペンタノンを74.6対25.4の割合(質量比)で加えて、分散物を得た。得られた分散物を撹拌機により十分に撹拌し、プレミキシングを行った。得られた分散物に対し、シンマルエンタープライゼス製のNPM Pilot(ビーズミル)を使用して下記条件にて分散処理を行い、色材分散液EA1を得た。
(分散条件)
・ビーズ径:φ0.05mm
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレーター周速:11m/s
・分散処理する混合液量:15.0kg
・循環流量(ポンプ供給量):60kg/hour
・処理液温度:20~25℃
・冷却水:水道水 5℃
・ビーズミル環状通路内容積:2.2L
・パス回数:84パス
なお、表21~25中の「平均粒径(nm)」は、色材分散液中のチタンブラックの平均粒径を表す。
次の表に、各色材分散液の配合を示す。
表中の組成物の配合は、各成分の添加量(質量部)を示している。
なお、下記表中、TiBKはチタンブラックを意味する。各色材分散液に含まれる黒色顔料の平均粒径は、表中の「平均粒径(nm)」欄に示す通りである。
また、「評価化合物(特定化合物又は比較化合物)」欄は使用した評価化合物の種類及び配合量(質量部)を表す。
上記表中に記載した評価化合物の具体的な構造を以下に示す。
なお、評価化合物は、酸無水物、及び、その比較対象となる酸無水物以外の化合物である。
表中、「Mw」欄は、評価化合物の分子量を示す。
表中、「ClogP」欄は、評価化合物のClogP値を示す。なお、「ClogP」欄に記載の「A/B」の表記において、「A」はその評価化合物(環状酸無水物)が開環していない状態におけるClogP値を示し、「B」はその評価化合物(環状酸無水物)が開環してなる化合物のClogP値を表す。なお、「-」は評価をしていないことを表す。なお、S-14においては、その化合物自体のClogPを表す。
表中、「pKa」欄は、評価化合物のpKaを示す。なお、「pKa」欄に記載の「C/D」の表記において、「C」はその評価化合物(環状酸無水物)が開環していない状態におけるpKaを示し、「D」はその評価化合物(環状酸無水物)が開環してなる化合物のpKaを表す。なお、「-」は評価をしていないことを表す。なお、S-14においては、その化合物自体のpKaを表す。
下記原料を使用し、後段に示す表26~57に記載の配合(質量部)で混合して、実施例及び比較例の組成物(黒色感光性組成物)を調製した。
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
・B-1:下記に示す構造の樹脂(重量平均分子量1.1万、酸価32mgKOH/g、各繰り返し単位に付した数値は、各繰り返し単位のモル比を意味する)
・M-1:KAYARAD DPHA (ジペンタエリストールヘキサアクリレート、日本化薬社製)
・M-2:アロニックスTO-2349(酸変性多官能アクリレート、東亞合成社製)
・M-3:下記構造式参照(式中、a+b=4、n=4)
・Ini-1:IRGACURE OXE02(BASF社製)
・Ini-2:下記構造式参照
・Ini-5:N-1919(ADEKA社製)
・Ini-6:NCI-930(ADEKA社製)
・Ini-7:以下構造式の開始剤
・A-1:p-メトキシフェノール
・A-2:下記の化合物(式中、t-Buは、tert-ブチル基を表す。)
・W-1:下記の界面活性剤(各繰り返し単位に付した数字又は文字は各繰り返し単位のモル比を示す。重量平均分子量1.5万)
・W-4:FZ-2122(東レダウケミカル社製)
・T-1:PMA-ST-L(表面修飾中実シリカ、日産化学)
・上述の通り製造した各色材分散液を組成物の調製に用いた。
〔組成物を用いたパターン付き遮光膜基板の作製〕
上記で得られた組成物をガラス基板上にスピンコート法により塗布し、乾燥後の膜厚が厚さ1.5μmとなる塗膜を作製した。上記基板に対して100℃で120秒間のプリベイクを行った後、開口線幅50μmのL/Sパターン(ライン幅:スペース幅=1:1)のマスクを介して、UX-1000SM-EH04(ウシオ電機社製)を用いて高圧水銀ランプ(ランプパワー50mW/cm2)にて500mJ/cm2の露光量でプロキシミティ方式による露光を行った。次に、露光後の上記塗膜を、AD-1200(ミカサ社製)を使用して現像液「CD-1040」(富士フイルムエレクトロニクスマテリアルズ社製)で15秒間パドル現像し、シャワーノズルを用いて純水で30秒洗浄した。現像により塗膜の未硬化部を除去した。その後、上記基板を、220℃で300秒間のポストベイクし、パターン付き遮光膜基板(遮光性パターン付きの基板)を得た。
各組成物を用いて上述の方法で作製したパターン付き遮光膜基板について、透過型顕微鏡を用いて基板上のパターンが形成されていないスペース部(非露光部)を観察し、以下の観点により、評価した。
A:スペース部に残渣が存在していない。
B:スペース部の33.3%未満の領域に残渣が確認される。
C:スペース部の33.3%以上66.7%未満の領域に残渣が確認される。
D:スペース部の66.7%以上の領域に残渣が確認される。
露光の際に使用したマスクの開口線幅を10μmに変更したことと、露光量をそれぞれ変化させながら露光したことと以外は上述の方法と同様にして、各組成物を用いてパターン付き遮光膜基板を作製した。
得られたパターン付き遮光膜基板について、光学顕微鏡を用いて10μm幅のラインパターンを観察し、パターン剥がれの有無に関して以下の観点により、評価した。基板に密着していて剥がれがないパターン(画像部)を形成できるようになる露光量が小さいほど、好ましい。
(密着:評価基準)
A:1000mJ以下の露光量にて、剥がれがないパターンを形成できる。
B:1000mJ超1400mJ以下の露光量にて、剥がれがないパターンを形成できる。
C:1400mJ超1700mJ以下の露光量にて、剥がれがないパターンを形成できる。
D:1700mJ超の露光量にて、剥がれがないパターンを形成できる。
露光の際に使用したマスクの開口線幅を300μmに変更したこと以外は上述した手順と同様にして、各組成物を用いてパターン付き遮光膜基板を作製した。
得られたパターン付き遮光膜基板について、走査型電子顕微鏡S-4800(日立ハイテクノロジーズ社製)を用いて300μm幅のパターンの断面SEM像を観察し、アンダーカット幅を実測し、以下の観点により、評価した。
なお、アンダーカット幅は、「〔(パターン断面においてライン幅が最も広い箇所の上記ライン幅)-(パターン断面におけるラインパターンが基板と触れる部分でのライン幅)〕÷2」と定義される。
なお、上記「パターン断面においてライン幅が最も広い箇所の上記ライン幅」とは300μmである。
A:アンダーカット幅が1.0μm未満
B:アンダーカット幅が1.0μm以上1.5μm未満
C:アンダーカット幅が1.5μm以上2.0未満
D:アンダーカット幅が2.0μm以上
表中の組成物の配合は、各成分の添加量(質量部)を示している。
表中、「色材分散液」欄は、使用した色材分散液の種類、および、配合量(質量部)を表す。
表中「評価化合物」欄の「量(%)」欄は、各実施例又は比較例の組成物における、全固形分に対する評価化合物の含有質量を示す。
また、本発明の組成物は、アンダーカットが抑制されたパターンを形成できることも確認された。
また、実施例117と他の実施例より、カルボン酸無水物のClogPが5.00以下の場合、本発明の効果がより優れることが確認された。
また、実施例138のトリメリット酸無水物(S-1)を、コハク酸無水物、ピロメリット酸無水物、無水フタル酸、テトラヒドロフタル酸無水物、4-メチルフタル酸無水物、グルタル酸無水物、または、4,4’-ビフタル酸無水物に変更した場合も、実施例138と同様の効果が得られた。
また、実施例139のトリメリット酸無水物(S-1)を、コハク酸無水物、ピロメリット酸無水物、無水フタル酸、テトラヒドロフタル酸無水物、4-メチルフタル酸無水物、グルタル酸無水物、または、4,4’-ビフタル酸無水物に変更した場合も、実施例139と同様の効果が得られた。
また、実施例140のトリメリット酸無水物(S-1)を、コハク酸無水物、ピロメリット酸無水物、無水フタル酸、テトラヒドロフタル酸無水物、4-メチルフタル酸無水物、グルタル酸無水物、または、4,4’-ビフタル酸無水物に変更した場合も、実施例140と同様の効果が得られた。
(合成例1:無機粒子分散液T-2の製造)
(被覆層形成工程)
スルーリア4110(日揮触媒化成社製、固形分濃度20質量%、イソプロピルアルコール溶剤、中空シリカゾル、平均一次粒子径60nm)150質量部、エタノール100質量部、疎水性基を含有するシランカップリング剤であるKP983(信越シリコーン社製)3質量部、及び、メタクリレート基を含有するシランカップリング剤であるKBM-5803(信越シリコーン社製)0.5質量部を混合した溶液に、1質量%アンモニア水1質量%を添加し、25℃で72時間撹拌した。
得られた溶液を遠心分離(毎分100000回転)し、上澄み液を廃棄した。1-メトキシ-2-プロパノール100質量部を沈殿物に添加して、撹拌羽で撹拌し再分散させた後、再度遠心分離を実施し、上澄み液を除去した。再度、1-メトキシ-2-プロパノールを沈殿物に固形分が30質量%になるように添加して、撹拌羽で撹拌し再分散させることで、無機粒子分散液T-2を作製した。得られた修飾無機粒子において被覆層の含有量は、修飾無機粒子100質量部に対して、5質量部であった。また、無機粒子分散液T-2中において、非被覆物の含有量は、修飾無機粒子全体100質量部に対して、0.5質量部であった。
KP983を下式のフッ素含有シランカップリング剤、KBM-5803を3-グリシドキシプロピルトリメトキシシランに変更した以外は合成例1と同様にして、無機粒子分散液T-3を作製した。得られた修飾無機粒子において被覆層の含有量は、修飾無機粒子100質量部に対して、7質量部であった。また、無機粒子分散液T-3中において、非被覆物の含有量は、修飾無機粒子全体100質量部に対して、0.1質量部であった。
スルーリア4110(150質量部)をIPA-ST-L(日産化学社製、中実シリカ粒子のイソプロパノール分散液、固形分濃度30質量%、平均一次粒子径45nm)100質量部、KBM-5803を3-アクリロキシプロシルトリメトキシシランに変更した以外は合成例1と同様にして、無機粒子分散液T-4を作製した。得られた修飾無機粒子において被覆層の含有量は、修飾無機粒子100質量部に対して、3質量部であった。また、無機粒子分散液T-4中において、非被覆物の含有量は、修飾無機粒子100質量部に対して、0.3質量部であった。
スルーリア4110(150質量部)をIPA-ST-L(日産化学社製、中実シリカ粒子のイソプロパノール分散液、固形分濃度30質量%、平均一次粒子径45nm)100質量部、KBM-5803を3-ウレイドプロピルトトリアルコキシシランに変更した以外は合成例1と同様にして、無機粒子分散液T-5を作製した。得られた修飾無機粒子において被覆層の含有量は、修飾無機粒子100質量部に対して、2.5質量部であった。また、無機粒子分散液T-4中において、非被覆物の含有量は、修飾無機粒子100質量部に対して、2質量部であった。
窒化ジルコニウム(日清エンジニアリング製)(25質量部)に対し、3級アミノ基と4級アンモニウム塩をもつ樹脂DISPERBYK-21116(ビックケミー・ジャパン社製、6.7質量部)及び評価化合物としてのS-1(0.79質量部)を加え、更に、液総量が100質量部となるようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)とシクロペンタノンを74.6対25.4の割合(質量比)で加えて、分散物を得た。得られた分散物を撹拌機により十分に撹拌し、プレミキシングを行った。得られた分散物に対し、シンマルエンタープライゼス製のNPM Pilot(ビーズミル)を使用して下記条件にて分散処理を行い、色材分散液FA1を得た。得られた分散液中の窒化ジルコニウムの平均粒径は49nmであった。
(分散条件)
・ビーズ径:φ0.05mm
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレーター周速:11m/s
・分散処理する混合液量:15.0kg
・循環流量(ポンプ供給量):60kg/hour
・処理液温度:20~25℃
・冷却水:水道水 5℃
・ビーズミル環状通路内容積:2.2L
・パス回数:84パス
得られた組成物を用いて上述した評価を実施した。結果を表58に示す。
なお、実施例603の色材分散液AA24を、上述した色材分散液BA1またはCA1に置き換えた場合においても、実施例143と同様の効果が得られることが確認された。
実施例601~603、606における、色材分散液AA5、AA14、AA24、AA25をそれぞれ色材分散液FA1に置き換えても、同様の効果が得られる。
12・・・光源
14・・・遮光部
16・・・レンズ
20・・・基体
22・・・遮光膜
23・・・開口部
30・・・配光パターン
30a・・・エッジ
31・・・領域
32・・・配光パターン
32a・・・エッジ
33・・・切欠部
100・・・固体撮像装置
101・・・固体撮像素子
102・・・撮像部
103・・・カバーガラス
104・・・スペーサー
105・・・積層基板
106・・・チップ基板
107・・・回路基板
108・・・電極パッド
109・・・外部接続端子
110・・・貫通電極
111・・・レンズ層
112・・・レンズ材
113・・・支持体
114、115・・・遮光膜
201・・・受光素子
202・・・カラーフィルタ
203・・・マイクロレンズ
204・・・基板
205b・・・青色画素
205r・・・赤色画素
205g・・・緑色画素
205bm・・・ブラックマトリクス
206・・・pウェル層
207・・・読み出しゲート部
208・・・垂直転送路
209・・・素子分離領域
210・・・ゲート絶縁膜
211・・・垂直転送電極
212・・・遮光膜
213、214・・・絶縁膜
215・・・平坦化膜
300・・・赤外線センサ
310・・・固体撮像素子
311・・・赤外線吸収フィルタ
312・・・カラーフィルタ
313・・・赤外線透過フィルタ
314・・・樹脂膜
315・・・マイクロレンズ
316・・・平坦化膜
Claims (15)
- 黒色顔料と、樹脂と、カルボン酸無水物と、重合性化合物とを含有する黒色感光性組成物であって、
前記カルボン酸無水物の分子量が50~550であり、
前記カルボン酸無水物の含有量が、前記黒色感光性組成物の全固形分に対して、0.30~10.0質量%であり、
前記黒色顔料の平均粒径が250nm以下である、黒色感光性組成物。 - 前記カルボン酸無水物が、環状カルボン酸無水物であり、
前記環状カルボン酸無水物が開環してなる化合物のpKaが、-1.20~4.50である、請求項1に記載の黒色感光性組成物。 - 前記カルボン酸無水物のClogP値が6.00以下である、請求項1又は2に記載の黒色感光性組成物。
- 前記カルボン酸無水物の炭素数が1~40である、請求項1~3のいずれか1項に記載の黒色感光性組成物。
- 前記2価の有機基は、置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、又は、置換基を有していてもよいアリーレン基を表し、
前記アルキレン基中の-CH2-基は-NH-基に置換されていてもよく、
前記アルキレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、前記アルケニレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、前記アリーレン基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、
前記4価の有機基は、置換基を有していてもよい4価の芳香環基、置換基を有していてもよい4価の脂肪族基、式(Q1)で表される4価の基、又は、式(Q2)で表される4価の基を表し、
前記4価の芳香環基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよく、前記4価の脂肪族基が複数の置換基を有する場合、置換基同士が結合して環を形成してもよい、請求項5に記載の黒色感光性組成物。
Xは、それぞれ独立に、3価の芳香環基又は3価の脂肪族環基を表す。Lq1は、単結合又は2価の連結基を表す。
Lq2は、2価の連結基を表す。Lq3~Lq6は、それぞれ独立に、アルキレン基を表す。
式(Q1)及び(Q2)中、*は結合位置を表す。 - 前記黒色顔料が、チタンブラック、カーボンブラック及びビスベンゾフラノン化合物からなる群から選択される1種以上である、請求項1~6のいずれか1項に記載の黒色感光性組成物。
- 前記黒色顔料とは異なる無機粒子を含有するか、または、
前記黒色顔料とは異なる無機粒子および前記無機粒子の少なくとも一部を被覆する被覆層を有する修飾無機粒子を含有する、請求項1~7のいずれか1項に記載の黒色感光性組成物。 - 請求項1~8のいずれか1項に記載の黒色感光性組成物の製造方法であって、
前記黒色顔料と、前記樹脂と、前記カルボン酸無水物とを含有するプレ混合物をビーズミルで混合して混合物を得る工程1、及び、
前記混合物と前記重合性化合物とを混合して前記黒色感光性組成物を得る工程2を有する、黒色感光性組成物の製造方法。 - 請求項1~8のいずれか1項に記載の黒色感光性組成物を用いて形成された、硬化膜。
- 請求項10に記載の硬化膜を含有する、カラーフィルタ。
- 請求項10に記載の硬化膜を含有する、遮光膜。
- 請求項10に記載の硬化膜を含有する、光学素子。
- 請求項10に記載の硬化膜を含有する、固体撮像素子。
- 車両用灯具のヘッドライトユニットであって、
光源と、
前記光源から出射された光の少なくとも一部を遮光する遮光部とを有し、
前記遮光部が、請求項10に記載の硬化膜を含有する、ヘッドライトユニット。
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Citations (79)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS495432A (ja) | 1972-05-04 | 1974-01-18 | ||
JPS57205322A (en) | 1981-06-15 | 1982-12-16 | Mitsubishi Metal Corp | Manufacture of fine powder of black lower titanium oxide |
JPS6065069A (ja) | 1983-09-21 | 1985-04-13 | Mitsubishi Metal Corp | 黒色顔料 |
JPS61201610A (ja) | 1985-02-28 | 1986-09-06 | Mitsubishi Metal Corp | 黒色粉末およびその製造方法 |
JPS621753A (ja) | 1985-06-26 | 1987-01-07 | バスフ アクチェン ゲゼルシャフト | ペリレン−3,4,9,10−テトラカルボン酸ジイミド色素 |
JPS6326784B2 (ja) | 1981-01-22 | 1988-05-31 | Basf Ag | |
JP2000066385A (ja) | 1998-08-18 | 2000-03-03 | Ciba Specialty Chem Holding Inc | 高感度で高レジスト厚さのi線ホトレジスト用スルホニルオキシム類 |
JP2000080068A (ja) | 1998-06-26 | 2000-03-21 | Ciba Specialty Chem Holding Inc | 新規o―アシルオキシム光開始剤 |
JP2001233611A (ja) | 2000-02-24 | 2001-08-28 | Catalysts & Chem Ind Co Ltd | シリカ系微粒子、該微粒子分散液の製造方法、および被膜付基材 |
JP2001233842A (ja) | 1999-12-15 | 2001-08-28 | Ciba Specialty Chem Holding Inc | オキシムエステルの光開始剤 |
JP3272111B2 (ja) | 1993-08-06 | 2002-04-08 | 住友大阪セメント株式会社 | 低屈折率膜形成用塗料、帯電防止・反射防止膜および帯電防止・反射防止膜付き透明積層体並びに陰極線管 |
JP2004534797A (ja) | 2001-06-11 | 2004-11-18 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | 組み合わされた構造を有するオキシムエステルの光開始剤 |
JP2005258254A (ja) | 2004-03-15 | 2005-09-22 | Sumitomo Chemical Co Ltd | 黒色感光性樹脂組成物 |
JP2007302836A (ja) | 2006-05-15 | 2007-11-22 | Mikuni Color Ltd | ブラックマトリックス形成用カーボンブラック分散液 |
JP2008203841A (ja) * | 2007-01-25 | 2008-09-04 | Mitsubishi Chemicals Corp | 感光性組成物、ブラックマトリックス、カラーフィルタ、及び画像表示装置 |
JP2008250074A (ja) | 2007-03-30 | 2008-10-16 | Fujifilm Corp | 感光性樹脂組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 |
WO2008131313A2 (en) | 2007-04-18 | 2008-10-30 | Invisage Technologies, Inc. | Materials systems and methods for optoelectronic devices |
JP2008260927A (ja) | 2007-03-20 | 2008-10-30 | Toray Ind Inc | 黒色樹脂組成物、樹脂ブラックマトリクス、カラーフィルターおよび液晶表示装置 |
JP2008266045A (ja) | 2007-04-17 | 2008-11-06 | Mitsubishi Materials Corp | 高抵抗黒色粉末およびその分散液、塗料、黒色膜 |
JP2008292970A (ja) | 2006-09-27 | 2008-12-04 | Fujifilm Corp | 化合物及びその互変異性体、金属錯体化合物、感光性着色硬化性組成物、カラーフィルタ、及びその製造方法 |
JP4223071B2 (ja) | 2006-12-27 | 2009-02-12 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する光重合開始剤 |
JP2009091205A (ja) | 2007-10-10 | 2009-04-30 | Tayca Corp | 微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体およびその製造方法 |
JP2009145884A (ja) * | 2007-11-21 | 2009-07-02 | Mitsubishi Chemicals Corp | インクジェット法カラーフィルター用ブラックマトリックス形成用組成物、およびこれを用いたブラックマトリックスの形成方法、ブラックマトリックス、カラーフィルターおよび液晶表示装置 |
JP4328935B2 (ja) | 1998-09-10 | 2009-09-09 | 日産化学工業株式会社 | 数珠状のシリカゾル、その製法及びインクジェット記録媒体 |
JP2010168539A (ja) | 2008-12-26 | 2010-08-05 | Nippon Shokubai Co Ltd | α−アリルオキシメチルアクリル酸系重合体及びその製造方法 |
JP2010527339A (ja) | 2007-05-11 | 2010-08-12 | ビーエーエスエフ ソシエタス・ヨーロピア | オキシムエステル光重合開始剤 |
JP2010534726A (ja) | 2007-07-19 | 2010-11-11 | ビーエーエスエフ ソシエタス・ヨーロピア | ビス−オキソジヒドロインドリレン−ベンゾジフラノンを含むnir不活性基体 |
JP2010262028A (ja) | 2009-04-30 | 2010-11-18 | Nippon Steel Chem Co Ltd | ブラックマトリックス用感光性樹脂組成物 |
WO2011049090A1 (ja) | 2009-10-19 | 2011-04-28 | 富士フイルム株式会社 | チタンブラック分散物、感光性樹脂組成物、ウェハレベルレンズ、遮光膜及びその製造方法、並びに固体撮像素子 |
JP2011089090A (ja) | 2009-10-26 | 2011-05-06 | Toray Ind Inc | ポリエステル樹脂組成物、その製造方法、およびフィルム |
JP2011524436A (ja) | 2008-06-06 | 2011-09-01 | ビーエーエスエフ ソシエタス・ヨーロピア | 光開始剤混合物 |
JP2011233983A (ja) | 2010-04-23 | 2011-11-17 | Panasonic Corp | 撮像装置 |
JP2012003225A (ja) | 2010-01-27 | 2012-01-05 | Fujifilm Corp | ソルダーレジスト用重合性組成物及びソルダーレジストパターンの形成方法 |
JP2012014052A (ja) | 2010-07-02 | 2012-01-19 | Fujifilm Corp | 着色感光性樹脂組成物、カラーフィルタ、カラーフィルタの製造方法、及び液晶表示装置 |
JP2012515234A (ja) | 2009-01-19 | 2012-07-05 | ビーエーエスエフ ソシエタス・ヨーロピア | 有機黒色顔料およびその製造 |
JP2012515233A (ja) | 2009-01-19 | 2012-07-05 | ビーエーエスエフ ソシエタス・ヨーロピア | カラーフィルタ用のブラックマトリックス |
US20120235099A1 (en) | 2011-03-17 | 2012-09-20 | Fujifilm Corporation | Radiation-sensitive colored composition, colored cured film, color filter and method of producing the same, solid-state imaging device, liquid crystal display apparatus, and method of producing dye |
JP2012198408A (ja) | 2011-03-22 | 2012-10-18 | Fujifilm Corp | 着色感放射線性組成物、パターンの形成方法、カラーフィルタ及びそのカラーフィルタの製造方法、並びに、固体撮像素子 |
JP2012255128A (ja) | 2011-05-18 | 2012-12-27 | Fujifilm Corp | 組成物、並びに、これを用いた透明膜、マイクロレンズ、固体撮像素子、透明膜の製造方法、マイクロレンズの製造方法、及び、固体撮像素子の製造方法 |
JP2013029760A (ja) | 2011-07-29 | 2013-02-07 | Fujifilm Corp | 着色硬化性組成物、着色硬化膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子及び画像表示装置 |
JP2013043962A (ja) | 2011-08-26 | 2013-03-04 | Fujifilm Corp | 着色剤含有粒子、着色剤含有粒子分散液、及び高分子化合物 |
JP2013114249A (ja) | 2011-12-01 | 2013-06-10 | Toppan Printing Co Ltd | 黒色感光性樹脂組成物およびカラーフィルタ |
WO2013083505A1 (en) | 2011-12-07 | 2013-06-13 | Basf Se | Oxime ester photoinitiators |
JP2013522445A (ja) | 2010-03-22 | 2013-06-13 | ヘンケル コーポレイション | マクロ光開始剤およびそれらの硬化性組成物 |
JP2013164471A (ja) | 2012-02-09 | 2013-08-22 | Jsr Corp | 硬化性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子 |
JP2013195480A (ja) | 2012-03-16 | 2013-09-30 | Fujifilm Corp | 赤外線吸収性組成物および赤外線カットフィルタ |
WO2013167515A1 (en) | 2012-05-09 | 2013-11-14 | Basf Se | Oxime ester photoinitiators |
JP2013253145A (ja) | 2012-06-06 | 2013-12-19 | Mitsubishi Materials Corp | 低屈折率膜形成用組成物及びこれを用いた低屈折率膜の形成方法 |
JP2014500852A (ja) | 2010-10-05 | 2014-01-16 | ビーエーエスエフ ソシエタス・ヨーロピア | ベンゾカルバゾール化合物のオキシムエステル誘導体ならびに前記誘導体の光重合性の組成物における光開始剤としての使用 |
JP2014130338A (ja) | 2012-11-29 | 2014-07-10 | Fujifilm Corp | 組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー |
JP2014130173A (ja) | 2012-12-27 | 2014-07-10 | Fujifilm Corp | カラーフィルタ用組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー |
JP2014137466A (ja) | 2013-01-16 | 2014-07-28 | Jsr Corp | 感放射線性着色組成物、着色硬化膜及び表示素子 |
JP2014533890A (ja) | 2011-11-18 | 2014-12-15 | ルクスビュー テクノロジー コーポレイション | 電気的絶縁層を持つマイクロled構造体及びマイクロled構造体のアレイの形成方法 |
JP2015500562A (ja) | 2011-11-18 | 2015-01-05 | ルクスビュー テクノロジー コーポレイション | マイクロ発光ダイオード |
WO2015004565A1 (en) | 2013-07-08 | 2015-01-15 | Basf Se | Oxime ester photoinitiators |
WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
JP2015068893A (ja) | 2013-09-27 | 2015-04-13 | 東レ株式会社 | 樹脂ブラックマトリクス基板 |
WO2015152153A1 (ja) | 2014-04-04 | 2015-10-08 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する光重合開始剤 |
WO2015166779A1 (ja) | 2014-05-01 | 2015-11-05 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサ |
WO2016034963A1 (en) | 2014-09-04 | 2016-03-10 | Basf Se | Polycyclic photoinitiators |
WO2016088645A1 (ja) | 2014-12-04 | 2016-06-09 | Jsr株式会社 | 固体撮像装置 |
WO2017033680A1 (ja) | 2015-08-26 | 2017-03-02 | パナソニックヘルスケアホールディングス株式会社 | 超低温フリーザ |
WO2017051680A1 (ja) | 2015-09-25 | 2017-03-30 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する重合開始剤 |
JP2017523465A (ja) | 2014-07-15 | 2017-08-17 | 常州強力電子新材料股▲ふん▼有限公司Cahngzhou Tronly New Electronic Materials Co.,Ltd. | オキシムエステル類光開始剤含有感光性組成物及びその使用 |
JP2017151342A (ja) | 2016-02-26 | 2017-08-31 | 東洋インキScホールディングス株式会社 | 感光性着色組成物およびカラーフィルタ |
JP2017167399A (ja) | 2016-03-17 | 2017-09-21 | 株式会社Dnpファインケミカル | カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、表示装置 |
WO2017164127A1 (ja) | 2016-03-25 | 2017-09-28 | 東レ株式会社 | 着色樹脂組成物、カラーフィルタ基板、および液晶表示装置 |
JP2017198865A (ja) | 2016-04-27 | 2017-11-02 | 東京応化工業株式会社 | 感光性組成物 |
JP2017222559A (ja) | 2016-09-29 | 2017-12-21 | 三菱マテリアル電子化成株式会社 | 窒化ジルコニウム粉末及びその製造方法 |
JP6301489B2 (ja) | 2014-03-18 | 2018-03-28 | 常州強力電子新材料股▲ふん▼有限公司Cahngzhou Tronly New Electronic Materials Co.,Ltd. | ニトロ基含有ビスオキシムエステル系光重合開始剤及びその合成製造方法と応用 |
JP2018087939A (ja) | 2016-11-30 | 2018-06-07 | 東洋インキScホールディングス株式会社 | 近赤外線吸収性組成物およびフィルタ |
WO2018230486A1 (ja) | 2017-06-13 | 2018-12-20 | 東洋インキScホールディングス株式会社 | スクアリリウム色素およびそれを含む組成物 |
WO2019059359A1 (ja) | 2017-09-25 | 2019-03-28 | 東レ株式会社 | 着色樹脂組成物、着色膜、カラーフィルターおよび液晶表示装置 |
WO2019088055A1 (ja) | 2017-10-30 | 2019-05-09 | 株式会社Adeka | 化合物、組成物、硬化物及び硬化物の製造方法 |
JP2019078878A (ja) | 2017-10-24 | 2019-05-23 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性組成物、及びカラーフィルタ |
WO2019130772A1 (ja) | 2017-12-26 | 2019-07-04 | 三菱マテリアル電子化成株式会社 | 黒色遮光膜形成用粉末及びその製造方法 |
JP2020158377A (ja) | 2019-03-28 | 2020-10-01 | 三菱マテリアル電子化成株式会社 | アルミナにより被覆された窒化ジルコニウム粉末及びその製造方法 |
WO2020203080A1 (ja) * | 2019-03-29 | 2020-10-08 | 富士フイルム株式会社 | 組成物、遮光膜、カラーフィルタ、光学素子、センサ、固体撮像素子、ヘッドライトユニット |
JP2020180036A (ja) | 2019-04-24 | 2020-11-05 | 三菱マテリアル電子化成株式会社 | 黒色材料及びその製造方法、黒色感光性組成物及びその製造方法、並びに黒色パターニング膜及びその形成方法 |
-
2022
- 2022-03-23 WO PCT/JP2022/013566 patent/WO2022210175A1/ja active Application Filing
- 2022-03-23 EP EP22780390.5A patent/EP4318057A1/en active Pending
- 2022-03-23 JP JP2023511065A patent/JPWO2022210175A1/ja active Pending
- 2022-03-28 TW TW111111735A patent/TW202307141A/zh unknown
-
2023
- 2023-09-25 US US18/473,296 patent/US20240045328A1/en active Pending
Patent Citations (86)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS495432A (ja) | 1972-05-04 | 1974-01-18 | ||
JPS6326784B2 (ja) | 1981-01-22 | 1988-05-31 | Basf Ag | |
JPS57205322A (en) | 1981-06-15 | 1982-12-16 | Mitsubishi Metal Corp | Manufacture of fine powder of black lower titanium oxide |
JPS6065069A (ja) | 1983-09-21 | 1985-04-13 | Mitsubishi Metal Corp | 黒色顔料 |
JPS61201610A (ja) | 1985-02-28 | 1986-09-06 | Mitsubishi Metal Corp | 黒色粉末およびその製造方法 |
JPS621753A (ja) | 1985-06-26 | 1987-01-07 | バスフ アクチェン ゲゼルシャフト | ペリレン−3,4,9,10−テトラカルボン酸ジイミド色素 |
JP3272111B2 (ja) | 1993-08-06 | 2002-04-08 | 住友大阪セメント株式会社 | 低屈折率膜形成用塗料、帯電防止・反射防止膜および帯電防止・反射防止膜付き透明積層体並びに陰極線管 |
JP2000080068A (ja) | 1998-06-26 | 2000-03-21 | Ciba Specialty Chem Holding Inc | 新規o―アシルオキシム光開始剤 |
JP2000066385A (ja) | 1998-08-18 | 2000-03-03 | Ciba Specialty Chem Holding Inc | 高感度で高レジスト厚さのi線ホトレジスト用スルホニルオキシム類 |
JP4328935B2 (ja) | 1998-09-10 | 2009-09-09 | 日産化学工業株式会社 | 数珠状のシリカゾル、その製法及びインクジェット記録媒体 |
JP2001233842A (ja) | 1999-12-15 | 2001-08-28 | Ciba Specialty Chem Holding Inc | オキシムエステルの光開始剤 |
JP2001233611A (ja) | 2000-02-24 | 2001-08-28 | Catalysts & Chem Ind Co Ltd | シリカ系微粒子、該微粒子分散液の製造方法、および被膜付基材 |
JP2004534797A (ja) | 2001-06-11 | 2004-11-18 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | 組み合わされた構造を有するオキシムエステルの光開始剤 |
JP2006342166A (ja) | 2001-06-11 | 2006-12-21 | Ciba Specialty Chem Holding Inc | 組み合わされた構造を有するオキシムエステルの光開始剤 |
JP2005258254A (ja) | 2004-03-15 | 2005-09-22 | Sumitomo Chemical Co Ltd | 黒色感光性樹脂組成物 |
JP2007302836A (ja) | 2006-05-15 | 2007-11-22 | Mikuni Color Ltd | ブラックマトリックス形成用カーボンブラック分散液 |
JP2008292970A (ja) | 2006-09-27 | 2008-12-04 | Fujifilm Corp | 化合物及びその互変異性体、金属錯体化合物、感光性着色硬化性組成物、カラーフィルタ、及びその製造方法 |
JP4223071B2 (ja) | 2006-12-27 | 2009-02-12 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する光重合開始剤 |
JP2008203841A (ja) * | 2007-01-25 | 2008-09-04 | Mitsubishi Chemicals Corp | 感光性組成物、ブラックマトリックス、カラーフィルタ、及び画像表示装置 |
JP2008260927A (ja) | 2007-03-20 | 2008-10-30 | Toray Ind Inc | 黒色樹脂組成物、樹脂ブラックマトリクス、カラーフィルターおよび液晶表示装置 |
JP2008250074A (ja) | 2007-03-30 | 2008-10-16 | Fujifilm Corp | 感光性樹脂組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 |
JP2008266045A (ja) | 2007-04-17 | 2008-11-06 | Mitsubishi Materials Corp | 高抵抗黒色粉末およびその分散液、塗料、黒色膜 |
WO2008131313A2 (en) | 2007-04-18 | 2008-10-30 | Invisage Technologies, Inc. | Materials systems and methods for optoelectronic devices |
US20120037789A1 (en) | 2007-04-18 | 2012-02-16 | Invisage Technologies, Inc. | Materials, systems and methods for optoelectronic devices |
JP2010527339A (ja) | 2007-05-11 | 2010-08-12 | ビーエーエスエフ ソシエタス・ヨーロピア | オキシムエステル光重合開始剤 |
JP2010534726A (ja) | 2007-07-19 | 2010-11-11 | ビーエーエスエフ ソシエタス・ヨーロピア | ビス−オキソジヒドロインドリレン−ベンゾジフラノンを含むnir不活性基体 |
JP2009091205A (ja) | 2007-10-10 | 2009-04-30 | Tayca Corp | 微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体およびその製造方法 |
JP2009145884A (ja) * | 2007-11-21 | 2009-07-02 | Mitsubishi Chemicals Corp | インクジェット法カラーフィルター用ブラックマトリックス形成用組成物、およびこれを用いたブラックマトリックスの形成方法、ブラックマトリックス、カラーフィルターおよび液晶表示装置 |
JP2011524436A (ja) | 2008-06-06 | 2011-09-01 | ビーエーエスエフ ソシエタス・ヨーロピア | 光開始剤混合物 |
JP2010168539A (ja) | 2008-12-26 | 2010-08-05 | Nippon Shokubai Co Ltd | α−アリルオキシメチルアクリル酸系重合体及びその製造方法 |
JP2012515234A (ja) | 2009-01-19 | 2012-07-05 | ビーエーエスエフ ソシエタス・ヨーロピア | 有機黒色顔料およびその製造 |
JP2012515233A (ja) | 2009-01-19 | 2012-07-05 | ビーエーエスエフ ソシエタス・ヨーロピア | カラーフィルタ用のブラックマトリックス |
JP2010262028A (ja) | 2009-04-30 | 2010-11-18 | Nippon Steel Chem Co Ltd | ブラックマトリックス用感光性樹脂組成物 |
WO2011049090A1 (ja) | 2009-10-19 | 2011-04-28 | 富士フイルム株式会社 | チタンブラック分散物、感光性樹脂組成物、ウェハレベルレンズ、遮光膜及びその製造方法、並びに固体撮像素子 |
JP2011089090A (ja) | 2009-10-26 | 2011-05-06 | Toray Ind Inc | ポリエステル樹脂組成物、その製造方法、およびフィルム |
JP2012003225A (ja) | 2010-01-27 | 2012-01-05 | Fujifilm Corp | ソルダーレジスト用重合性組成物及びソルダーレジストパターンの形成方法 |
US20130034812A1 (en) | 2010-01-27 | 2013-02-07 | Fujifilm Corporation | Polymerizable composition for solder resist, and solder resist pattern formation method |
JP2013522445A (ja) | 2010-03-22 | 2013-06-13 | ヘンケル コーポレイション | マクロ光開始剤およびそれらの硬化性組成物 |
JP2011233983A (ja) | 2010-04-23 | 2011-11-17 | Panasonic Corp | 撮像装置 |
JP2012014052A (ja) | 2010-07-02 | 2012-01-19 | Fujifilm Corp | 着色感光性樹脂組成物、カラーフィルタ、カラーフィルタの製造方法、及び液晶表示装置 |
JP2014500852A (ja) | 2010-10-05 | 2014-01-16 | ビーエーエスエフ ソシエタス・ヨーロピア | ベンゾカルバゾール化合物のオキシムエステル誘導体ならびに前記誘導体の光重合性の組成物における光開始剤としての使用 |
JP2012208494A (ja) | 2011-03-17 | 2012-10-25 | Fujifilm Corp | 着色感放射線性組成物、着色硬化膜、カラーフィルタ及びカラーフィルタの製造方法、固体撮像素子、液晶表示装置、並びに、染料の製造方法 |
US20120235099A1 (en) | 2011-03-17 | 2012-09-20 | Fujifilm Corporation | Radiation-sensitive colored composition, colored cured film, color filter and method of producing the same, solid-state imaging device, liquid crystal display apparatus, and method of producing dye |
JP2012198408A (ja) | 2011-03-22 | 2012-10-18 | Fujifilm Corp | 着色感放射線性組成物、パターンの形成方法、カラーフィルタ及びそのカラーフィルタの製造方法、並びに、固体撮像素子 |
JP2012255128A (ja) | 2011-05-18 | 2012-12-27 | Fujifilm Corp | 組成物、並びに、これを用いた透明膜、マイクロレンズ、固体撮像素子、透明膜の製造方法、マイクロレンズの製造方法、及び、固体撮像素子の製造方法 |
JP2013029760A (ja) | 2011-07-29 | 2013-02-07 | Fujifilm Corp | 着色硬化性組成物、着色硬化膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子及び画像表示装置 |
JP2013043962A (ja) | 2011-08-26 | 2013-03-04 | Fujifilm Corp | 着色剤含有粒子、着色剤含有粒子分散液、及び高分子化合物 |
JP2014533890A (ja) | 2011-11-18 | 2014-12-15 | ルクスビュー テクノロジー コーポレイション | 電気的絶縁層を持つマイクロled構造体及びマイクロled構造体のアレイの形成方法 |
JP2015500562A (ja) | 2011-11-18 | 2015-01-05 | ルクスビュー テクノロジー コーポレイション | マイクロ発光ダイオード |
JP2013114249A (ja) | 2011-12-01 | 2013-06-10 | Toppan Printing Co Ltd | 黒色感光性樹脂組成物およびカラーフィルタ |
WO2013083505A1 (en) | 2011-12-07 | 2013-06-13 | Basf Se | Oxime ester photoinitiators |
JP2013164471A (ja) | 2012-02-09 | 2013-08-22 | Jsr Corp | 硬化性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子 |
JP2013195480A (ja) | 2012-03-16 | 2013-09-30 | Fujifilm Corp | 赤外線吸収性組成物および赤外線カットフィルタ |
WO2013167515A1 (en) | 2012-05-09 | 2013-11-14 | Basf Se | Oxime ester photoinitiators |
JP2017019766A (ja) | 2012-05-09 | 2017-01-26 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | オキシムエステル光開始剤 |
JP2013253145A (ja) | 2012-06-06 | 2013-12-19 | Mitsubishi Materials Corp | 低屈折率膜形成用組成物及びこれを用いた低屈折率膜の形成方法 |
JP2014130338A (ja) | 2012-11-29 | 2014-07-10 | Fujifilm Corp | 組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー |
JP2014130173A (ja) | 2012-12-27 | 2014-07-10 | Fujifilm Corp | カラーフィルタ用組成物、赤外線透過フィルタ及びその製造方法、並びに赤外線センサー |
JP2014137466A (ja) | 2013-01-16 | 2014-07-28 | Jsr Corp | 感放射線性着色組成物、着色硬化膜及び表示素子 |
JP6065596B2 (ja) | 2013-01-16 | 2017-01-25 | Jsr株式会社 | 感放射線性着色組成物、着色硬化膜及び表示素子 |
JP2016532675A (ja) | 2013-07-08 | 2016-10-20 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | オキシムエステル光開始剤 |
WO2015004565A1 (en) | 2013-07-08 | 2015-01-15 | Basf Se | Oxime ester photoinitiators |
WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
JP2015068893A (ja) | 2013-09-27 | 2015-04-13 | 東レ株式会社 | 樹脂ブラックマトリクス基板 |
JP6301489B2 (ja) | 2014-03-18 | 2018-03-28 | 常州強力電子新材料股▲ふん▼有限公司Cahngzhou Tronly New Electronic Materials Co.,Ltd. | ニトロ基含有ビスオキシムエステル系光重合開始剤及びその合成製造方法と応用 |
WO2015152153A1 (ja) | 2014-04-04 | 2015-10-08 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する光重合開始剤 |
WO2015166779A1 (ja) | 2014-05-01 | 2015-11-05 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサ |
JP2017523465A (ja) | 2014-07-15 | 2017-08-17 | 常州強力電子新材料股▲ふん▼有限公司Cahngzhou Tronly New Electronic Materials Co.,Ltd. | オキシムエステル類光開始剤含有感光性組成物及びその使用 |
WO2016034963A1 (en) | 2014-09-04 | 2016-03-10 | Basf Se | Polycyclic photoinitiators |
WO2016088645A1 (ja) | 2014-12-04 | 2016-06-09 | Jsr株式会社 | 固体撮像装置 |
WO2017033680A1 (ja) | 2015-08-26 | 2017-03-02 | パナソニックヘルスケアホールディングス株式会社 | 超低温フリーザ |
WO2017051680A1 (ja) | 2015-09-25 | 2017-03-30 | 株式会社Adeka | オキシムエステル化合物及び該化合物を含有する重合開始剤 |
JP2017151342A (ja) | 2016-02-26 | 2017-08-31 | 東洋インキScホールディングス株式会社 | 感光性着色組成物およびカラーフィルタ |
JP2017167399A (ja) | 2016-03-17 | 2017-09-21 | 株式会社Dnpファインケミカル | カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、表示装置 |
WO2017164127A1 (ja) | 2016-03-25 | 2017-09-28 | 東レ株式会社 | 着色樹脂組成物、カラーフィルタ基板、および液晶表示装置 |
JP2017198865A (ja) | 2016-04-27 | 2017-11-02 | 東京応化工業株式会社 | 感光性組成物 |
JP2017222559A (ja) | 2016-09-29 | 2017-12-21 | 三菱マテリアル電子化成株式会社 | 窒化ジルコニウム粉末及びその製造方法 |
JP2018087939A (ja) | 2016-11-30 | 2018-06-07 | 東洋インキScホールディングス株式会社 | 近赤外線吸収性組成物およびフィルタ |
WO2018230486A1 (ja) | 2017-06-13 | 2018-12-20 | 東洋インキScホールディングス株式会社 | スクアリリウム色素およびそれを含む組成物 |
WO2019059359A1 (ja) | 2017-09-25 | 2019-03-28 | 東レ株式会社 | 着色樹脂組成物、着色膜、カラーフィルターおよび液晶表示装置 |
JP2019078878A (ja) | 2017-10-24 | 2019-05-23 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性組成物、及びカラーフィルタ |
WO2019088055A1 (ja) | 2017-10-30 | 2019-05-09 | 株式会社Adeka | 化合物、組成物、硬化物及び硬化物の製造方法 |
WO2019130772A1 (ja) | 2017-12-26 | 2019-07-04 | 三菱マテリアル電子化成株式会社 | 黒色遮光膜形成用粉末及びその製造方法 |
JP2020158377A (ja) | 2019-03-28 | 2020-10-01 | 三菱マテリアル電子化成株式会社 | アルミナにより被覆された窒化ジルコニウム粉末及びその製造方法 |
WO2020203080A1 (ja) * | 2019-03-29 | 2020-10-08 | 富士フイルム株式会社 | 組成物、遮光膜、カラーフィルタ、光学素子、センサ、固体撮像素子、ヘッドライトユニット |
JP2020180036A (ja) | 2019-04-24 | 2020-11-05 | 三菱マテリアル電子化成株式会社 | 黒色材料及びその製造方法、黒色感光性組成物及びその製造方法、並びに黒色パターニング膜及びその形成方法 |
Non-Patent Citations (7)
Title |
---|
"The Chemical Daily", 13 November 2015, TOYO GOSEI CO |
A. J. LEO, CALCULATING LOGPOCT FROM STRUCTURE. CHEM. REV, vol. 93, 1993, pages 1281 - 1306 |
AKIO SASAKI: "Comprehensive Medicinal Chemistry", vol. 4, 1990, KOGYO CHOSAKAI PUBLISHING CO, pages: 295 |
J. C. S. PERKIN II, 1979, pages 156 - 1660 |
JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, 1995, pages 202 - 232 |
SUMIAKI IBUKI: "Ultraviolet Curing System", 1989, SANGYO TOSHO PUBLISHING CO, pages: 65 - 148 |
TATSUO UCHIDA: "Next-Generation Liquid Crystal Display Technology", 1994, KOGYO CHOSAKAI PUBLISHING CO |
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