WO2013180035A1 - Dispersion composition, polymerizable composition using same, light-blocking color filter, solid-state imaging element, liquid crystal display device, wafer-level lens, and imaging unit - Google Patents

Dispersion composition, polymerizable composition using same, light-blocking color filter, solid-state imaging element, liquid crystal display device, wafer-level lens, and imaging unit Download PDF

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WO2013180035A1
WO2013180035A1 PCT/JP2013/064515 JP2013064515W WO2013180035A1 WO 2013180035 A1 WO2013180035 A1 WO 2013180035A1 JP 2013064515 W JP2013064515 W JP 2013064515W WO 2013180035 A1 WO2013180035 A1 WO 2013180035A1
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group
polymer compound
structural unit
light
dispersion composition
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PCT/JP2013/064515
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French (fr)
Japanese (ja)
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渉 菊池
芳紀 玉田
祐継 室
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富士フイルム株式会社
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0037—Arrays characterized by the distribution or form of lenses
    • G02B3/0062—Stacked lens arrays, i.e. refractive surfaces arranged in at least two planes, without structurally separate optical elements in-between
    • G02B3/0068—Stacked lens arrays, i.e. refractive surfaces arranged in at least two planes, without structurally separate optical elements in-between arranged in a single integral body or plate, e.g. laminates or hybrid structures with other optical elements
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G02B3/0031—Replication or moulding, e.g. hot embossing, UV-casting, injection moulding
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix

Definitions

  • the present invention relates to a dispersion composition, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, a liquid crystal display device, a wafer level lens, and an imaging unit using the same.
  • a color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a black matrix is provided for the purpose of preventing noise and improving image quality.
  • the black matrix contains a dispersion composition in which a light-shielding black color material is dispersed, a polymerizable compound, a polymerization initiator, and other components to form a polymerizable composition, which is used for a photolithography method, etc. It is manufactured by forming a pattern.
  • a photosensitive resin composition containing a black color material such as carbon black or titanium black is known.
  • a black matrix for a liquid crystal display device As a black matrix for a liquid crystal display device, a black matrix having a high light shielding property is required in order to increase contrast and improve visibility.
  • a black matrix for a solid-state imaging device needs to have light shielding properties in the infrared region in addition to light shielding properties in the visible region.
  • carbon black has been widely used as a light-shielding black matrix.
  • a dispersion composition or a polymerizable composition having a high concentration of carbon black as a light shielding material is required for pattern formation of the light shielding layer.
  • the content of carbon black is increased in order to obtain a high light-shielding property, there has been a problem that the dispersibility of carbon black becomes difficult and the pattern formability deteriorates.
  • a black matrix for a liquid crystal display device As a black matrix for a liquid crystal display device, a light shielding property in the visible region is mainly required, whereas as a black matrix for a solid-state imaging device, in the infrared region from the back surface of the silicon substrate in addition to the light shielding property in the visible region. In order to prevent transmission, it is necessary to have light shielding properties in the infrared region. Further, the black matrix for liquid crystal display devices is required to be miniaturized, while the black matrix for solid-state imaging device (in particular, the surface opposite to the light-receiving element forming surface of the support (hereinafter also referred to as “back surface”)). As for the black matrix for shielding light, it is required to have a performance for uniformly shielding a larger area than the black matrix for liquid crystal display devices.
  • Such an image pickup unit generally includes a solid-state image sensor such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state image sensor.
  • a solid-state image sensor such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor
  • CMOS Complementary Metal-Oxide Semiconductor
  • a lens module is manufactured by manufacturing a wafer level lens having a configuration in which a plurality of lenses are molded on a substrate, and cutting the substrate to separate each of the plurality of lenses.
  • a method for mass production is known.
  • the imaging unit is obtained by integrally combining a substrate on which a plurality of lenses are formed and a sensor substrate on which a plurality of solid-state imaging elements are formed, and cutting the sensor substrate together with the substrate so as to include the lens and the solid-state imaging elements as a set.
  • a wafer level lens a multilayer wafer level lens configured by superposing substrates on which a plurality of lenses are formed has been described (for example, see Patent Document 1). Since the wafer level lens is made of a transparent material that allows light to pass through the substrate and the lens and can transmit light at any part, the wafer level lens is diced and mounted on the imaging device to In this case, if light is transmitted or reflected in a region other than the lens surface of the lens, there is a concern that optical performance problems such as ghost and flare are likely to occur during imaging. From the viewpoint of preventing such a problem, for example, a region other than the lens of the wafer level lens is subjected to processing such as providing a light shielding member.
  • the present invention has a high dispersibility, storage stability, and coating property, and when it is combined with a polymerizable compound to form a polymerizable composition, and pattern formation is performed using this polymerizable composition, in the unexposed area.
  • An object is to provide a liquid crystal display device, a wafer level lens, and an imaging unit.
  • Means for solving the above-mentioned problems are as follows. [1] (A) titanium black, (B) a polymer compound having a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain, and (C) a dispersion composition containing a solvent . [2] The dispersion composition according to [1], wherein the hydrophobic structural unit is a structural unit derived from a compound having a ClogP value of 1.2 or more. [3] [1] or [2], wherein the hydrophobic structural unit is one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii): The dispersion composition described.
  • R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
  • X represents an oxygen atom or an imino group.
  • L is a single bond or a divalent linking group.
  • Z represents an aliphatic group, an aromatic group, a heterocyclic group, or a combination thereof with an oxygen atom, a sulfur atom, an imino group, a substituted imino group or a carbonyl group.
  • R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, Z, or —LZ.
  • the polymer compound (B) is a polymer compound having one or more structural units selected from the structural units represented by the following formulas (1) to (4) as the structural unit having the graft chain.
  • the dispersion composition according to any one of [1] to [6] above.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
  • X 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a monovalent organic group
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group.
  • R 3 represents a branched or straight chain alkylene group
  • R 4 represents a hydrogen atom or a monovalent organic group.
  • n, m, p, and q each independently represents an integer of 1 to 500.
  • the polymer compound (B) has one or more structural units selected from the structural units represented by the formulas (1) to (4) in a mass relative to the total mass of the polymer compound (B).
  • a polymerizable composition comprising the dispersion composition according to any one of the above [1] to [11], (D) a polymerizable compound, and (E) a polymerization initiator. [13] The polymerizable composition as described in [12] above, wherein (E) the polymerization initiator is an oxime compound.
  • a solid-state imaging device comprising the light-shielding color filter according to [14].
  • a liquid crystal display device comprising the light-shielding color filter according to [14].
  • a wafer level lens comprising: a substrate on which a plurality of lenses are integrally formed; and the light-shielding color filter according to [14] provided in a region excluding the lens surface of the lens.
  • An imaging unit comprising the wafer level lens described in [17] above.
  • the dispersibility, the storage stability and the coating property are high.
  • a polymerizable composition is combined with a polymerizable compound and pattern formation is performed using this polymerizable composition, in the unexposed area.
  • a dispersion composition capable of forming a pattern in which a residue is suppressed and improving a development margin and development latitude in pattern formation, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, A liquid crystal display device, a wafer level lens, and an imaging unit can be provided.
  • FIG. 2 is a sectional view taken along line AA in FIG. 1. It is sectional drawing which shows the other structural example of a wafer level lens. It is sectional drawing which shows an example of a structure of an imaging unit.
  • the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “radiation” in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. To tell.
  • the dispersion composition of the present invention comprises (A) titanium black, (B) a polymer compound having a structural unit having a graft chain, and a hydrophobic structural unit different from the structural unit having the graft chain, and (C ) Contains a solvent.
  • the polymerizable composition of the present invention contains the dispersion of the present invention, (D) a polymerizable compound, and (E) a polymerization initiator. According to the dispersion composition of the present invention, a dispersion composition having high dispersibility, storage stability, and coatability can be obtained.
  • the polymerizable composition of the present invention when pattern formation is performed, it is possible to form a pattern in which residues in unexposed areas are suppressed, and to improve the development margin and development latitude in pattern formation.
  • the high development margin means that the exposed portion is likely to remain at the time of pattern formation because it is difficult to be peeled off by the developer, and a desired pattern is easily obtained.
  • a high development latitude means that a long time is required until the formed pattern is peeled off by the developer.
  • Titanium black in the present invention is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. is there.
  • Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), or ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method of reducing titanium in a reducing atmosphere containing hydrogen Japanese Patent Laid-Open No. 57-205322
  • a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610
  • a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at a high temperature in the presence of ammonia JP-A 61-201610), etc. is not.
  • the titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
  • the average primary particle diameter is preferably in the range of 10 nm to 45 nm, and more preferably in the range of 12 nm to 20 nm.
  • the particle diameter that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle.
  • the projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
  • the specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and therefore the value measured by the BET method is usually 5 m 2 / g to 150 m 2 / g or less, particularly preferably 20 m 2 / g to 100 m 2 / g.
  • titanium black products examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).
  • Titanium black particles can be modified on the particle surface as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • modification of the particle surface for example, coating treatment with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like is possible, and repellent properties as disclosed in JP-A-2007-302836 are also possible. Treatment with an aqueous material is also possible.
  • the dispersant of the present invention preferably contains titanium black as a dispersion to be dispersed containing titanium black and Si atoms.
  • titanium black is contained as a dispersion in the dispersion, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention exceeds 0.5, it tends to be difficult to produce a pigment dispersion using the dispersion.
  • the upper limit is preferably 0.5. If the Si / Ti of the dispersion is too small, a residue is likely to remain in the removed portion when the light shielding film using the dispersion in the present invention is patterned by photolithography or the like, and the Si / Ti of the dispersion If Ti is too large, the light shielding ability tends to decrease. Therefore, the Si / Ti of the dispersion is more preferably 0.05 or more and 0.5 or less, and 0.07 or more and 0.4 or less. Is more preferable.
  • a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly contained.
  • a dispersion containing Si and Ti can be obtained.
  • Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, is a method described in paragraphs [0005] and (6) and paragraphs [0016] to [0021] of JP-A-2008-266045, for example. Can be produced.
  • the present invention by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved.
  • a suitable range for example, 0.05 or more
  • the residue derived from the composition outside the region where the light-shielding film is formed is reduced.
  • the residue includes components derived from the photosensitive composition such as titanium black particles and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less).
  • the adsorptivity of the entire film with the undercoat is reduced, and this is presumed to contribute to the improvement of the development and removability of the uncured composition (particularly titanium black particles) in the formation of the light-shielding film. ing.
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet to infrared. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is 0 in terms of mass).
  • a light-shielding film formed using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
  • the content ratio (Si / Ti) between Si atoms and Ti atoms in the dispersion can be measured, for example, using the method (1-1) or the method (1-2) shown below.
  • the content ratio (Si / Ti) of Si atom in the to-be-dispersed material ) Is 0.05 or more, the following method (2) is used.
  • ⁇ Method (2)> By dividing the substrate on which the light-shielding film is formed, a cross section of the light-shielding film can be produced, and the amount of Si atoms and the amount of Ti atoms on the surface of the light-shielding film can be obtained with this energy dispersive X-ray fluorescence spectrometer. These quantitative ratios are evaluated as Si / Ti in the light shielding film.
  • the energy dispersive fluorescent X-ray analysis at this time includes S-4800 (trade name) manufactured by Hitachi High-Technology as the above-mentioned scanning electron microscope, and INCA Energy PentaFETx3 manufactured by Oxford as the energy dispersive fluorescent X-ray detector. (Product name) can be used similarly.
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline
  • Si-containing material such as silica
  • examples of the silica that can be used in the present invention include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
  • Silica is also available as a commercial product, for example, NS-101, HS-102, HS-103, HS-104, HS-105, HS-106, HS-107, HS-201, manufactured by Nippon Steel Materials.
  • HS-202, HS-203, HS-204, HS-205, HS-301, HS-302, HS-303, HS-304, HS-305 (trade name); Ube Nitto Kasei, High Plessica SS, High Plessica TS , High plesica BS, high plesica SP, high plesica FQ (trade name); manufactured by Cabot, CAB-O-SIL (registered trademark) LM-150, CAB-O-SIL (registered trademark) LM-150, CAB-O-SIL (registered) Silica particles such as S-17D can be used.
  • the particle size of the silica particles is about the same as the film thickness when the light-shielding film according to the present invention is formed, the light-shielding property is lowered, so that it is preferable to use fine particle type silica as the silica particles.
  • the fine particle type silica include, for example, AEROSIL (registered trademark) 90, AEROSIL (registered trademark) 130, AEROSIL (registered trademark) 150, AEROSIL (registered trademark) 200, AEROSIL (registered trademark) 300, AEROSIL (registered trademark).
  • AEROSIL registered trademark OX 50, AEROSIL (registered trademark) EG 50, AEROSIL (registered trademark) TT 600, AEROSIL (registered trademark) 200 SP, AEROSIL (registered trademark) 300 SP, AEROPERL (registered trademark) 300 / 30, AEROSIL (registered trademark) R 972, AEROSIL (registered trademark) R 974, AEROSIL (registered trademark) R 104, AEROSIL (registered trademark) R 106, AEROSIL (registered trademark) R 202, AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R 812, AEROSIL (registered trademark) R 812 S, AEROSIL (registered trademark) R 816, AEROSIL (registered trademark) R 7200, AEROSIL (registered trademark) R 8200, AEROSIL (registered trademark) R 9200
  • the dispersion composition and polymerizable composition of the present invention may contain only one type of titanium black, or may contain two or more types.
  • the content of titanium black is preferably in the range of 20% by mass to 94% by mass, more preferably in the range of 40% by mass to 92% by mass, with respect to the total solid content of the dispersion composition. More preferably, it is the range of 40 mass% or more and 80 mass% or less.
  • the content of titanium black is preferably in the range of 5% by mass to 80% by mass and more preferably in the range of 10% by mass to 70% by mass with respect to the total solid content of the polymerizable composition. More preferably, it is the range of 20 mass% or more and 60 mass% or less.
  • the content of titanium black is within the above range, the curability of the polymerizable composition of the present invention is improved, and a uniform film can be formed.
  • titanium black is contained at a high concentration, sufficient light shielding properties can be obtained, and a polymerizable composition containing titanium black can be suitably used for forming a light shielding color filter.
  • the dispersion composition and the polymerizable composition of the present invention may contain extender pigments as necessary in addition to titanium black.
  • extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more.
  • the amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of titanium black.
  • the titanium black and extender pigment can be used by modifying their surfaces with a polymer in some cases.
  • the dispersion composition and the polymerizable composition of the present invention may be used in combination with a pigment other than titanium black as a light shielding pigment.
  • a light-shielding pigment that can be mixed is not particularly limited as long as it has absorbance in the visible light region, and the above-mentioned extender pigment, carbon black, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, C.I. I. PigmentViolet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. And organic pigments such as Pigment Black 1 and 7.
  • Examples of mixing light-shielding pigments other than titanium black include a mixture of titanium black and carbon black in a ratio of 6: 1, and a mixture of titanium black and titanium oxide in a ratio of 3: 1.
  • the light-shielding pigment other than titanium black to be mixed can be used in the range of 0.01 to 99.99 parts by mass with respect to 100 parts by mass of titanium black. Preferably, it is in the range of 20 to 70 parts by mass.
  • the polymer compound (B) in the present invention has a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain.
  • polymer compound (B) in the present invention a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, and pigment derivatives.
  • the polymer compound (B) in the present invention can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from its structure.
  • the polymer compound (B) in the present invention acts to adsorb on the surface of a dispersion such as titanium black particles and a pigment to be used in combination, if desired, and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the adsorptivity of the polymer compound (B) to these can be promoted by modifying the surface of the titanium black particles or the above-mentioned dispersion material containing titanium black and Si atoms.
  • the polymer compound (B) has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”.
  • the polymer compound (B) having a structural unit having such a graft chain is excellent in the dispersibility of the titanium black particles and the dispersion stability after the lapse of time because it has an affinity for the solvent by the graft chain. is there.
  • the polymerizable composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably has a polymer structure, and examples of such a polymer structure include a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and Examples thereof include a polyether structure.
  • the graft chain has at least one selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure in order to improve the interaction between the graft site and the solvent and thereby increase the dispersibility. And a graft chain having at least one of a polyester structure and a polyether structure is more preferable.
  • the structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain portion and satisfies the requirements of the present invention.
  • a macromonomer having a reactive double bond group can be preferably used.
  • a commercially available macromonomer suitably used for the synthesis of the polymer compound (B) includes AA-6 (trade name, (trade name, Toa Synthesis Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (Toa Gosei Co., Ltd.), AN-6 (Trade name, manufactured by Toa Gosei Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei) Synthetic Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co.,
  • AA-6 produced by Toa Gosei Co., Ltd.
  • AA-10 trade name, Toa Gosei Co., Ltd.
  • AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • AS-6 trade name, Toa Gosei Co., Ltd.
  • AN-6 trade name, Toa Gosei Synthetic Co., Ltd.
  • Bremer PME-4000 trade name, manufactured by NOF Corporation
  • the polymer compound (B) preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain. 2A), a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4) is more preferable.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represents hydrogen.
  • An atom or a methyl group is more preferable, and a methyl group is particularly preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable.
  • n, m, p, and q are each an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 may be the same or different from each other.
  • the structural units represented by the formulas (1) to (4) are contained in a range of 10% to 90% in terms of mass with respect to the total mass of the polymer compound (B). Preferably, it is contained in the range of 30% to 70%.
  • the structural units represented by the formulas (1) to (4) are included within this range, the dispersibility of the titanium black particles is high and the developability when forming the light-shielding film is good.
  • the high molecular compound (B) can have a structural unit having a graft chain in which two or more kinds of structures are different. That is, in the molecule of the polymer compound (B), structural units represented by the formulas (1) to (4) having different structures may be included, and in the formulas (1) to (4), When n, m, p, and q each represent an integer of 2 or more, in the formula (1) and the formula (2), j and k may include structures different from each other in the side chain. In 3) and formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoints of dispersion stability and developability.
  • the polymer compound (B) has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain is preferably contained in a range of 10% to 90% in terms of mass with respect to the total mass of the polymer compound (B), and 30% to 70%. It is more preferable that it is included in the range.
  • the structural unit having a graft chain is contained within this range, the dispersibility of the titanium black particles is high, and the developability when forming the light-shielding film is good.
  • the polymer compound (B) has a hydrophobic structural unit different from the structural unit having the graft chain (that is, not corresponding to the structural unit having the graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 was used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound (B) may have one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units. preferable.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (the number of carbon atoms) 1 to 6 alkyl groups are preferable, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • R 1 , R 2 , and R 3 are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are particularly preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene groups divalent heterocyclic groups, and oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR 31 —, R 31 is an aliphatic group, aromatic group or heterocyclic group) or a combination with a carbonyl group (—CO—).
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle.
  • Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z includes aliphatic groups (eg, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (eg, arylene groups, substituted arylene groups), heterocyclic groups, and Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 is an aliphatic group, aromatic group or heterocyclic group) Or a combination with a carbonyl group (—CO—) and the like can be mentioned.
  • aliphatic groups eg, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups
  • aromatic groups eg, arylene groups, substituted arylene groups
  • heterocyclic groups and Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms.
  • a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group are included, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. .
  • bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
  • Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.02,6] decane, tricyclo [4.3.1.12,5] undecane ring, tetracyclo [4.
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (an alkyl having 1 to 6 carbon atoms).
  • a group for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L includes an alkylene group or an oxyalkylene structure 2
  • a compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group.
  • a compound in which Y is a methine group is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), (specifically, for example, benzyl acrylate, 4-biphenyl acrylate, butyl Acrylate, sec-butyl acrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, octyl acrylate, dodecyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate, trifluoromethyl methyl acrylate, tridecanefluorohexyl ethyl acrylate 4-cyano Benzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, Tyl acrylate, hexyl acrylate, isobornyl acrylate, cyan
  • Methacrylic acid esters for example, benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 4-alkyl methacrylate (preferably having 1 to 20 carbon atoms in the alkyl group)) t-butylphenyl methacrylate, octyl methacrylate, dodecyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, trifluoromethylmethyl methacrylate, tridecanefluorohexylethyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate, 2-ethoxy Ethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate , Heptyl methacrylate,
  • Styrenes such as styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogenated styren
  • methacrylic acid esters and styrenes are preferably used, and benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate are particularly preferably used.
  • Pentachlorophenyl methacrylate 4-cyanophenyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, Phenyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate,
  • Styrene methyl styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene , Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4- Fluoro-3-trifluoromethylstyrene, 1-vin
  • the following compounds are exemplified as the compound containing a heterocyclic group.
  • the hydrophobic structural unit is preferably contained in a range of 10% to 90% and in a range of 20% to 80% with respect to the total mass of the polymer compound (B) in terms of mass. It is more preferable that it is contained. When the content is in the above range, sufficient pattern formation can be obtained.
  • the polymer compound (B) can introduce a functional group capable of forming an interaction with titanium black.
  • the polymer compound (B) preferably further includes a structural unit having a functional group capable of forming an interaction with titanium black.
  • the functional group capable of forming an interaction with the titanium black particles include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound (B) has an acid group, a basic group, a coordination group, or a reactive functional group
  • the structural unit having an acid group, the structural unit having a basic group, and a coordination group respectively. It is preferable to have a structural unit having a coordinate group or a structural unit having reactivity.
  • the polymer compound (B) further has an alkali-soluble group such as a carboxylic acid group as an acid group, thereby imparting developability for pattern formation by alkali development to the polymer compound (B).
  • an alkali-soluble group such as a carboxylic acid group as an acid group
  • the dispersion composition of the present invention has the polymer compound (B) as a dispersant essential for dispersing the titanium black particles having alkali solubility. It will be.
  • the polymerizable composition containing such a dispersion composition has excellent light shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound (B) has a structural unit which has an acid group, a high molecular compound (B) becomes easy to become compatible with a solvent (C), and it exists in the tendency for applicability
  • the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • the acid group that is a functional group capable of forming an interaction with titanium black examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, preferably a carboxylic acid group, a sulfonic acid group, Among the phosphoric acid groups, at least one kind, and particularly preferred is a carboxylic acid group that has good adsorption power to titanium black particles and has high dispersibility. That is, the polymer compound (B) preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound (B) may have one or more structural units having an acid group.
  • the polymer compound (B) may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is, in terms of mass, the polymer compound (B). Is preferably 5% or more and 80% or less, and more preferably 10% or more and 60% or less from the viewpoint of suppressing damage of image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with titanium black include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Among them, particularly preferred is a tertiary amino group having a good adsorptive power to titanium black and a high dispersibility.
  • the polymer compound (B) can have one or more of these basic groups.
  • the polymer compound (B) may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is expressed in terms of mass in terms of a polymer compound ( Preferably it is 0.01% or more and 50% or less with respect to the gross mass of B), More preferably, it is 0.01% or more and 30% or less from a viewpoint of developability inhibition suppression.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with titanium black, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride, and the like. Is mentioned. Particularly preferred is an acetylacetoxy group that has good adsorption power to titanium black and high dispersibility.
  • the polymer compound (B) may have one or more of these groups.
  • the polymer compound (B) may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group.
  • the amount is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, in terms of mass, in terms of suppression of developability inhibition, with respect to the total mass of the polymer compound (B). is there.
  • the polymer compound (B) in the present invention has a functional group capable of interacting with titanium black in addition to the graft chain
  • the functional group capable of interacting with various titanium blacks as described above is provided.
  • the polymer compound (B) is a monomer represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from the body.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, methyl group, ethyl group, propyl group, etc.).
  • R 11 , R 12 and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, most preferably Are each independently a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group ( For example, an arylene group and a substituted arylene group), a divalent heterocyclic group and an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR) 31′- , where R 31 ′ is an aliphatic group, aromatic group or heterocyclic group) or a combination with one or more of carbonyl bonds (—CO—).
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of interacting with the titanium black particles in addition to the graft site, and is preferably a carboxylic acid group or a tertiary amino group. More preferably, it is a carboxylic acid group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, , methyl group, ethyl group, propyl group, etc.), - represents a Z 1, or -L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is methine. Compounds that are groups are preferred.
  • R 14 , R 15 and R 16 are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • monomer examples include a reaction product of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride, a molecule
  • a reaction product of a compound having an addition polymerizable double bond and hydroxyl group and trimellitic anhydride a reaction product of a compound having an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic Acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenyl methacrylate And the like.
  • the content of the functional group capable of forming an interaction with titanium black is based on the total mass of the polymer compound (B) from the viewpoint of interaction with titanium black, dispersion stability, and permeability to a developer.
  • 0.05 mass% to 90 mass% is preferable, 1.0 mass% to 80 mass% is more preferable, and 10 mass% to 70 mass% is still more preferable.
  • the polymer compound (B) is a structural unit having a graft chain, a hydrophobic structural unit, and titanium black particles as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength.
  • Other structural units having various functions different from structural units having a functional group capable of forming an interaction for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion.
  • Such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the content thereof is preferably in terms of mass with respect to the total mass of the polymer compound (B). It is 0% or more and 80% or less, and particularly preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound (B) is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably 20 mgKOH / g or more. It is the range of 120 mgKOH / g or less. If the acid value of the polymer compound (B) is 160 mgKOH / g or less, pattern peeling during development when forming the light-shielding film can be more effectively suppressed. Moreover, if the acid value of a high molecular compound (B) is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the polymer compound (B) is 20 mgKOH / g or more, it is possible to further suppress sedimentation of the dispersion containing titanium black and titanium black and Si atoms, thereby reducing the number of coarse particles.
  • the temporal stability of the dispersion composition and the polymerizable composition can be further improved.
  • the acid value of the polymer compound (B) can be calculated, for example, from the average content of acid groups in the polymer compound (B). Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound (B).
  • the weight average molecular weight of the polymer compound (B) in the present invention is 4,000 or more and 300,000 as a polystyrene conversion value by GPC method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. Is preferably 5,000 or more, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and is preferably 10,000 or more and 50,000 or less. Particularly preferred.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound (B) can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound (B) include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, and propanol.
  • Butanol ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide Dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These solvents may be used alone or in combination of two or more.
  • the numerical value written together with each structural unit represents the content of the structural unit [described as mass%: (wt%)].
  • the numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.
  • the content of the polymer compound (B) in the dispersion composition of the present invention is preferably 1% by mass to 90% by mass and more preferably 3% by mass to 70% by mass with respect to the total solid mass of the dispersion composition. .
  • the content of the polymer compound (B) in the polymerizable composition of the present invention is preferably 0.1% by mass to 50% by mass with respect to the total solid content mass of the polymerizable composition, A mass% to 30 mass% is more preferred.
  • the dispersion composition and the polymerizable composition of the present invention contain a polymer compound (B ′) different from the polymer compound (B) (that is, a polymer compound not corresponding to the polymer compound (B)). May be.
  • the preferred range of the weight average molecular weight of the polymer compound (B ′) is the same as that described for the polymer compound (B).
  • Specific examples of the polymer compound (B ′) include “Disperbyk-101 (trade name, polyamidoamine phosphate), 107 (trade name, carboxylic acid ester), 110 (trade name, acid group) manufactured by BYK Chemie.
  • the dispersion composition of the present invention may or may not contain the polymer compound (B ′), but when it is contained, the content of the polymer compound (B ′) is the total solid content of the dispersion composition. 1% by mass to 90% by mass is preferable with respect to the partial mass, and 3% by mass to 70% by mass is more preferable. Further, the polymerizable composition of the present invention may or may not contain the polymer compound (B ′), but when it is contained, the content of the polymer compound (B ′) is determined by the polymerizable composition. 0.1% by mass to 50% by mass is preferable and 0.5% by mass to 30% by mass is more preferable with respect to the total solid content mass of the product.
  • the dispersion composition and polymerizable composition of the present invention contain (C) a solvent.
  • the solvent is preferably an organic solvent.
  • organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • Acetylacetone, cyclohexanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, ethyl lactate and the like, but are not limited thereto.
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • the amount of the solvent (C) contained in the dispersion composition is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass with respect to the total amount of the dispersion composition. More preferably, it is 30 to 65% by mass.
  • the amount of the solvent (C) contained in the polymerizable composition is preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass with respect to the total amount of the polymerizable composition. Is more preferable, and it is still more preferable that it is 25 mass% to 75 mass%.
  • the polymerizable composition of the present invention contains (D) a polymerizable compound.
  • the polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.
  • Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Tetra, tri (acryl
  • dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferable.
  • These oligomer types can also be used.
  • urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained.
  • Commercially available products include urethane oligomers UAS-10, UAB-140 (trade names, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (trade names, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • ethylenically unsaturated compounds having an acid group are also suitable.
  • examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate.
  • TO-1382 and the like can be mentioned.
  • the polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination aspect can be suitably set according to the physical property etc. which are requested
  • a suitable combination mode of the polymerizable compound for example, a mode in which two or more polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
  • the content of the polymerizable compound (D) in the polymerizable composition of the present invention is preferably 3% by mass to 55% by mass, more preferably 10% by mass to 50% by mass with respect to the total solid content of the polymerizable composition. %.
  • the polymerizable composition of the present invention contains (E) a polymerization initiator (preferably a photopolymerization initiator).
  • a polymerization initiator preferably a photopolymerization initiator.
  • the polymerization initiator is a compound that is decomposed by light or heat to start and accelerate the polymerization of the above-mentioned (D) polymerizable compound, and has absorption for light in the wavelength region of 300 to 500 nm. Preferably there is.
  • polymerization initiator examples include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples thereof include organic boric acid compounds, disulfonic acid compounds, oxime compounds (particularly oxime ester compounds), onium salt compounds, and acylphosphine (oxide) compounds. More specific examples include polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749. Among the above polymerization initiators, an oxime compound (particularly an oxime ester compound) is more preferable from the viewpoint that the shape of the pattern to be obtained can be improved.
  • the content of the (E) polymerization initiator in the polymerizable composition of the present invention is preferably 0.1% by mass to 30% by mass in the total solid content of the polymerizable composition, and 1% by mass to 25% by mass. % Is more preferable, and 2% by mass to 20% by mass is still more preferable.
  • the polymerizable composition of the present invention may further contain (F-1) a binder polymer, if necessary, for the purpose of improving film properties.
  • F-1) A linear organic polymer is preferably used as the binder polymer.
  • a linear organic polymer a known one can be arbitrarily used.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development.
  • the linear organic polymer is selected and used not only as a film-forming agent but also according to a developer (developer) composed of water, weak alkaline water, or an organic solvent.
  • linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. No.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxyl styrene, and examples of the monomer having an acid anhydride include maleic anhydride.
  • An acid etc. are mentioned.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • Japanese Patent Publication No. 7-2004 Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Application Laid-Open No. 63-287944, Japanese Patent Application Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. Urethane binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and advantageous in terms of suitability for low exposure.
  • the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
  • the weight average molecular weight of the (F-1) binder polymer used in the polymerizable composition of the present invention is preferably 1,000 to 300,000 from the viewpoint of pattern peeling inhibition during development and developability. It is more preferably 1,500 to 250,000, further preferably 2,000 to 200,000, and particularly preferably 2,500 to 100,000.
  • the number average molecular weight of the binder polymer is preferably 1000 or more, and more preferably in the range of 1500 to 250,000.
  • the polydispersity (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 1 or more, more preferably in the range of 1.1 to 10.
  • the weight average molecular weight of the (F-1) binder polymer can be measured, for example, by GPC.
  • These (F-1) binder polymers may be random polymers, block polymers, graft polymers or the like.
  • the (F-1) binder polymer that can be used in the present invention can be synthesized by a conventionally known method.
  • the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.
  • the radical polymerization initiator used when synthesizing the binder polymer (F-1) include known compounds such as azo initiators and peroxide initiators.
  • an alkali-soluble resin having a double bond in the side chain as the (F-1) binder polymer, it is possible to improve both the curability of the exposed area and the alkali developability of the unexposed area. it can.
  • the alkali-soluble resin having a double bond in the side chain has a non-image area removability by having an acid group for making the resin alkali-soluble in the structure and at least one unsaturated double bond. Improve various performances.
  • the resin having such a structure is described in detail in JP-A No. 2003-262958, and the resin described therein can be used as the binder polymer in the present invention.
  • the content of the binder polymer in the polymerizable composition of the present invention is preferably 0.1% by mass to 25% by mass with respect to the total solid content of the composition. From the viewpoint of achieving both, it is more preferably 0.3% by mass to 20% by mass, and further preferably 1.0% by mass to 15% by mass.
  • the polymerizable composition of the present invention may be used in combination with a colorant (F-2) other than known inorganic pigments such as organic pigments and dyes in order to develop desired light-shielding properties. Is possible.
  • Colorants that can be used in combination include organic pigments such as pigments described in paragraphs [0030] to [0044] of JP-A-2008-224982, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the Cl substituent is changed to OH and the like.
  • pigments that can be preferably used include the following.
  • the colorant (F-2) applicable to the present invention is not limited to these.
  • examples of the dye that can be used as the colorant (F-2) are not particularly limited, and known dyes can be appropriately selected and used.
  • JP-A-8-62416 JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 Examples thereof include dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
  • the chemical structure of the dye includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole
  • Examples include chemical structures such as azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene.
  • the (F-2) colorant in the polymerizable composition of the present invention is an orange pigment from the viewpoint that when combined with titanium black particles that the composition essentially contains, both curability and light shielding properties can be achieved.
  • One or more organic pigments selected from the group consisting of red pigments and violet pigments are preferred, and most preferred are combinations with red pigments.
  • orange pigment, red pigment, and violet pigment examples include various pigments belonging to “CI Pigment Orange”, “CI Pigment Red”, and “CI Pigment Violet” exemplified above. What is necessary is just to select suitably according to light-shielding property. From the viewpoint of improving the light shielding property, C.I. I. Pigment Violet 29, C.I. I. Pigment Orange 36, 38, 62, 64, C.I. I. Pigment Red 177, 254, 255 and the like are preferable.
  • the polymerizable composition of the present invention contains (F-3) a sensitizer for the purpose of (E) improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. You may contain.
  • the (F-3) sensitizer one that sensitizes the polymerization initiator (E) used by an electron transfer mechanism or an energy transfer mechanism is preferable.
  • Preferable examples of (F-3) sensitizers include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
  • the content of (F-3) sensitizer is preferably in the range of 0.1% by mass to 30% by mass with respect to the total solid content of the polymerizable composition from the viewpoint of sensitivity and storage stability. The content is more preferably in the range of 1 to 20% by mass, and still more preferably in the range of 2 to 15% by mass.
  • the polymerizable composition of the present invention contains a small amount of (F-4) polymerization in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. It is desirable to add an inhibitor.
  • F-4) As the polymerization inhibitor a known thermal polymerization inhibitor can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl.
  • thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total solid content of the polymerizable composition.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and a higher fatty acid derivative is applied to the surface of the coating film during the drying process after coating. Etc. may be unevenly distributed.
  • the amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% by weight of the total composition.
  • (F-5) Adhesion improver In order to improve the adhesion to a hard surface such as a support, (F-5) an adhesion improver can be added to the polymerizable composition of the present invention.
  • adhesion improvers include silane coupling agents and titanium coupling agents.
  • Silane coupling agents include ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, and ⁇ -mercaptopropyltrimethoxy.
  • Silane, ⁇ -aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and ⁇ -methacryloxypropyltrimethoxysilane is preferable.
  • the content of (F-5) adhesion improver is preferably 0.5% by mass to 30% by mass and more preferably 0.7% by mass to 20% by mass in the total solid content of the polymerizable composition. preferable.
  • an adhesion improver may be added from the viewpoint of improving sensitivity. preferable.
  • (F-6) Surfactant
  • various surfactants may be added to the polymerizable composition of the present invention from the viewpoint of further improving coatability.
  • the surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the polymerizable composition of the present invention contains a fluorosurfactant
  • liquid properties (particularly fluidity) when prepared as a coating liquid are further improved.
  • the liquid-saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a polymerizable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
  • a fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the polymerizable composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 no. 95
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone-based surfactants examples include Toray Dow Corning (Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA. ”,“ Tole Silicone SH30PA ”,“ Tole Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF-4442 ”manufactured by Momentive Performance Materials, Inc.
  • the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the polymerizable composition of the present invention. It is.
  • the polymerizable composition is used for the purpose of further improving the sensitivity of the sensitizing dye or initiator to radiation, or suppressing the inhibition of polymerization of the photopolymerizable compound by oxygen.
  • a sensitizer may be contained.
  • the preparation mode of the dispersion composition of the present invention is not particularly limited.
  • (A) titanium black, (B) polymer compound, and (C) solvent are mixed with a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, although it can prepare by performing a dispersion process using a wet disperser etc., the method is not limited to these.
  • the dispersion process may be performed by two or more dispersion processes (multistage dispersion).
  • the light-shielding color filter having the colored pattern of the present invention is formed using the above-described polymerizable composition of the present invention.
  • the residue is suppressed and the flatness can be improved.
  • the thickness of the colored pattern is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less. 5 to 30 ⁇ m is more preferable, and 0.7 to 20 ⁇ m is even more preferable.
  • the size (length of one side) of the coloring pattern (for example, black matrix) is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less from the viewpoint of obtaining the effect of the present invention more effectively. More preferably, it is 0.1 mm or more and 3.5 mm or less.
  • the light-shielding color filter of the present invention is characterized by having a colored pattern (for example, a black matrix) formed using the polymerizable composition of the present invention on a substrate.
  • a light-shielding color filter having a colored pattern (for example, a black matrix) of the present invention will be described in detail through its manufacturing method.
  • the method for producing a light-shielding color filter of the present invention comprises a step of applying a polymerizable composition of the present invention on a substrate to form a polymerizable composition layer (hereinafter referred to as “polymerizable composition layer forming step” as appropriate).
  • a step of applying a polymerizable composition of the present invention on a substrate to form a polymerizable composition layer hereinafter referred to as “polymerizable composition layer forming step” as appropriate.
  • a step of exposing the polymerizable composition layer through a mask hereinafter abbreviated as “exposure step” as appropriate
  • development step as appropriate.
  • the polymerizable composition of the present invention is applied on a substrate directly or via another layer to form a polymerizable composition layer (polymerizable composition layer forming step), and a predetermined mask.
  • a polymerizable composition layer forming step By exposing only the coating film portion exposed through the pattern and curing the light (exposure process) and developing with a developer (development process), a pattern-like film composed of pixels is formed, and the light-shielding property of the present invention A color filter can be manufactured.
  • exposure process Exposure process
  • development process developing with a developer
  • a color filter can be manufactured.
  • each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.
  • Polymerizable composition layer forming step In the polymerizable composition layer forming step, the polymerizable composition layer of the present invention is coated on the substrate to form a polymerizable composition layer.
  • the substrate examples include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, solid-state imaging devices, and the like.
  • examples thereof include a photoelectric conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS).
  • CMOS complementary metal oxide semiconductor
  • an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
  • various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, spray coating, screen printing method, etc. can be applied. it can.
  • the coating thickness of the polymerizable composition is preferably from 0.35 ⁇ m to 1.5 ⁇ m from the viewpoint of resolution and developability. More preferably, it is 40 ⁇ m or more and 1.0 ⁇ m or less.
  • the polymerizable composition applied on the substrate is usually dried at 70 ° C. or more and 110 ° C. or less for about 2 minutes or more and 4 minutes or less to form a polymerizable composition layer.
  • the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable.
  • Irradiation intensity 5 mJ / cm 2 or more 1500 mJ / cm 2 or less is preferably 10 mJ / cm 2 or more 1000 mJ / cm 2 and more preferably less, 10 mJ / cm 2 or more 800 mJ / cm 2 or less is most preferable.
  • an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
  • the developer when producing a light-shielding color filter having a black matrix for a solid-state imaging device, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable.
  • the development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.
  • alkaline aqueous solution examples include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as an inorganic developer, ammonia water, ethylamine as an organic alkali developer.
  • Alkaline compounds such as diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, with a concentration of 0
  • An alkaline aqueous solution dissolved in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • a colored pattern for example, a black matrix formed as necessary after the above-described polymerizable composition layer forming step, exposure step, and development step is performed.
  • a curing step of curing by heating and / or exposure may be included.
  • the formed colored pattern (for example, a black matrix) exhibits high adhesion to the support substrate, and the cured composition is resistant to Since the developability is excellent, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD (Charge Coupled Device), and particularly suitable for a high-resolution CCD device exceeding 1 million pixels, a CMOS (Complementary Metal Oxide Semiconductor), or the like. is there.
  • a solid-state imaging device such as a liquid crystal display device or a CCD (Charge Coupled Device)
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • the light-shielding color filter provided with the black matrix of the present invention is preferably applied to a solid-state image sensor.
  • the light-shielding color filter of the present invention can be used, for example, as a black matrix disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.
  • the solid-state imaging device of the present invention includes a color filter having the light-shielding color filter (for example, a black matrix) of the present invention described above and a patterned film composed of pixels of other colors (three colors or four colors) as necessary. Configured. Since the solid-state imaging device of the present invention includes the light-shielding color filter of the present invention (for example, a black matrix) in which a decrease in light-shielding ability at the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved. Can do.
  • the solid-state imaging device of the present invention has a configuration including the light-shielding color filter (for example, a black matrix) of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. It has a light receiving element composed of a plurality of photodiodes and polysilicon forming a light receiving area of an element (CCD image sensor, CMOS image sensor, etc.), and the light shielding property of the present invention is provided on the surface opposite to the light receiving element forming surface of the substrate. Examples include a configuration provided with a color filter (for example, a black matrix).
  • a color filter for example, a black matrix
  • One of the liquid crystal display devices of the present invention includes at least a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of substrates that are light transmissive.
  • a color filter a light-shielding color filter (for example, a black matrix) having a plurality of pixel groups as described above, wherein each pixel constituting the pixel group is made of the polymerizable composition of the present invention. ; The same applies to the following) is used. Since the light-shielding color filter has high flatness, a liquid crystal display device including the light-shielding color filter does not cause cell gap unevenness between the color filter and the substrate, and causes display defects such as color unevenness. There is nothing.
  • At least one includes a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is active.
  • a light-shielding color filter for example, a black matrix
  • the elements for example, TFTs.
  • the wafer level lens of the present invention is configured by providing a color filter having the light-shielding color filter (for example, black matrix) of the present invention described above.
  • FIG. 1 is a plan view showing an example of the configuration of a wafer level lens
  • FIG. 2 is a cross-sectional view taken along line AA of FIG.
  • the wafer level lens includes a substrate 1 and a plurality of lenses 10 arranged on the substrate 1.
  • the plurality of lenses 10 are arranged one-dimensionally or two-dimensionally with respect to the substrate 1.
  • FIG. 1 a configuration in which a plurality of lenses 10 are two-dimensionally arranged on the substrate 1 will be described as an example.
  • the lens 10 is made of the same material as the substrate 1 and is formed on the substrate 1.
  • the lens 10 has a concave lens surface 10a and a lens edge 10b around the lens surface 10a.
  • the lens surface 10a has an optical characteristic that condenses or diverges light incident on the lens 10 in a desired direction, and is a part of a portion where the curvature and the surface shape are designed in consideration of this optical characteristic. It shall mean a surface.
  • the height of the lens edge 10b relative to the substrate 1 is configured to be higher than the center of the lens surface 10a.
  • the shape of the lens 10 is not particularly limited.
  • the lens 10 may be a so-called convex lens in which the lens surface 10a protrudes in a convex shape, or may be an aspherical lens.
  • a configuration in which a plurality of lenses 10 are provided on one surface of the substrate 1 is illustrated, but a configuration in which a plurality of lenses 10 are provided on both surfaces of the substrate 1 may be employed.
  • the lens is molded so that the optical axis of each lens on one surface coincides with the optical axis of each lens on the other surface.
  • the wafer level lens is configured to have one layer of the substrate 1 on which a plurality of lenses 10 are molded, but may be configured to stack two or more layers.
  • the wafer level lens is provided with a light shielding layer 14 so as to cover the surface of the lens edge 10b of the lens 10 and the surface of the substrate 1 between the lenses 10.
  • the light shielding layer 14 is patterned in a region of the substrate 1 excluding the lens surface 10a of the lens. In the configuration in which the wafer level lens has one or more substrates, the light shielding layer 14 is provided on the surface of at least one substrate.
  • the light shielding layer 14 is composed of a black resist layer. Since the black resist layer has a lower light reflectance than a metal layer or the like, it is possible to reduce inconveniences such as ghost and flare caused by light reflection.
  • the black resist layer contains a black resist composition.
  • FIG. 3 is a cross-sectional view showing another configuration example of the wafer level lens.
  • a lens 10 having the same shape as that shown in FIG. 2 is molded on one surface of the substrate 1, and a convex lens 20 is molded on the other surface.
  • a spacer is formed for securing a distance when overlapping with another wafer lens array.
  • the spacer 12 is a lattice-like member in plan view, and is joined to the other surface of the substrate 1.
  • the substrate 1 is separated by dicing so that a lens 10 and a lens 20 are provided.
  • the spacer 12 may be formed integrally with the substrate 1 as a part of the substrate 1.
  • FIG. 4 is a cross-sectional view illustrating an example of the configuration of the imaging unit.
  • the imaging unit includes a lens module obtained by dicing a wafer level lens and separating each lens, an imaging element (here, a solid-state imaging element) D, and a sensor substrate W provided with the solid-state imaging element D.
  • an imaging element here, a solid-state imaging element
  • a sensor substrate W provided with the solid-state imaging element D.
  • three lens modules LM1, LM2, and LM3 are stacked in this order from the light incident side (upper side in FIG. 4).
  • a convex lens 10A is molded on the upper surface of the substrate 1A, and a lens 20A having a concave lens surface is molded on the lower surface.
  • a light shielding layer 14 patterned in a region excluding the lens surface of the lens 10A is provided on the upper surface of the substrate 1A.
  • the lens 20A is provided with a light shielding layer 14 patterned in a region excluding the lens surface.
  • a concave lens 10B is molded on the upper surface of the substrate 1B, and a lens 20B having a convex lens surface is molded on the lower surface.
  • This lens module LM2 is basically the same as the configuration shown in FIG.
  • a light shielding layer 14 patterned in a region excluding the lens surface of the lens 10A, that is, a lens edge and a region of the substrate surface is provided on the upper surface of the substrate 1A.
  • the light shielding layer 14 is not provided on the lower surface of the substrate 1B, but the patterned light shielding layer 14 may be provided in a region other than the lens surface of the lens 20B.
  • an aspherical lens 10C is molded on the upper surface of the substrate 1C, and a lens 20C having an aspherical lens surface is molded on the lower surface.
  • the lens 10C and the lens 20C are provided with a light shielding layer 14 patterned in a region excluding the lens surface.
  • the light shielding layer 14 is formed using the dispersion composition or the polymerizable composition of the present invention.
  • the lenses 10A, 10B, 10C, 20A, 20B, and 20C are all provided in a shape that is rotationally symmetric with respect to the optical axis.
  • the lens modules LM1, LM2, and LM3 are joined via the spacer 12 so that the optical axes of all the lenses 10A, 10B, 10C, 20A, 20B, and 20C coincide.
  • the lens modules LM1, LM2, and LM3 are bonded to the sensor substrate W through the spacer 12.
  • the lenses 10A, 10B, 10C, 20A, 20B, and 20C of the lens modules LM1, LM2, and LM3 form a subject image on the solid-state imaging device D provided on the sensor substrate W.
  • the sensor substrate W is formed by cutting a wafer formed of a semiconductor material such as silicon into a substantially rectangular shape in plan view.
  • the solid-state imaging device D is provided at a substantially central portion of the sensor substrate W.
  • the solid-state image sensor D is, for example, a CCD image sensor or a CMOS image sensor.
  • the solid-state imaging device D can be configured to be bonded on a semiconductor substrate on which wirings and the like are formed after being formed into a chip.
  • the solid-state imaging device D performs a well-known film formation process, photolithography process, etching process, impurity addition process, etc. on the sensor substrate W, and forms electrodes, insulating films, wirings, etc. on the sensor substrate W. It may be configured.
  • the spacer 12 of the lens module LM3 and the sensor substrate W are bonded using, for example, an adhesive.
  • Each spacer 12 is designed such that the lenses 10A, 10B, 10C, 20A, 20B, and 20C of the lens modules LM1, LM2, and LM3 form a subject image on the solid-state imaging device D. Further, each spacer 12 is arranged so that the lenses 10A, 10B, 10C, 20A, 20B, and 20C are not in contact with each other, or the lens modules LM3 and LM3 are not in contact with each other. It is formed with a thickness separating a predetermined distance therebetween.
  • the spacer 12 is a range in which the lens modules LM1, LM2, and LM3 can be held between each other, or the distance between the lens module LM3 and the sensor substrate W can be held in a positional relationship with a predetermined distance therebetween. can do.
  • the spacer 12 may be a columnar member provided at each of the four corners of the substrates 1A, 1B, and 1C.
  • the spacer 12 may be a frame-shaped member that surrounds the solid-state imaging device D. If the solid-state image pickup device D is isolated from the outside by being surrounded by the frame-shaped spacer 12, the solid-state image pickup device D can be shielded from light other than the light passing through the lens. Moreover, it can prevent that dust adheres to the solid-state image sensor D by sealing the solid-state image sensor D from the outside.
  • a reflective layer is provided on the surface of the uppermost substrate closest to the light incident side instead of the light shielding layer 14. May be.
  • the reflective layer includes a reflective material having a small transmittance of 0.01% or less with respect to light and a high reflectance of (4%) or more.
  • a metal such as chromium (Cr) or a metal material.
  • the imaging unit configured as described above is reflow-mounted on a circuit board (not shown) built in a portable terminal or the like.
  • the circuit board is preliminarily printed with paste-like solder at a position where the imaging unit is mounted, and the imaging unit is mounted on the circuit board.
  • the circuit board including the imaging unit is irradiated with infrared rays or hot air is blown. Heat treatment is performed, and the imaging unit is welded to the circuit board.
  • Precursor M1 80.0 g, isobutyl methacrylate 20.0 g, dodecyl mercaptan 2.3 g and propylene glycol monomethyl ether acetate 233.3 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). ) And heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours.
  • a stirrer Shinto Kagaku Co., Ltd .: Three-One Motor
  • the ClogP value added to the left structural unit of the specific resin 1 represents the ClogP value in the compound (monomer) corresponding to the structural unit.
  • Example 1 ⁇ Preparation of titanium black dispersion> -Production of Titanium Black A-1- 100 g of titanium oxide MT-150A (trade name: manufactured by Teika Co., Ltd.) having an average particle size of 15 nm, 25 g of silica particles AROPERL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m 2 / g, and dispersion 100 g of the agent Disperbyk 190 (trade name: manufactured by Big Chemie), add 71 g of ion-exchange water, and use MURASTAR KK-400W manufactured by KURABO for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm.
  • Gave a homogeneous aqueous mixture.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing. After the completion, the collected powder was pulverized in a mortar to obtain titanium black A-1 [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
  • composition 1 -Titanium black (A-1) obtained as described above-25 parts-30% by weight propylene glycol monomethyl ether acetate solution of specific resin 1-25 parts-Propylene glycol monomethyl ether acetate (PGMEA) ( solvent) ... 50 copies
  • the obtained dispersion a was subjected to a dispersion treatment using the Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a titanium black dispersion of Example 1.
  • Examples 2 to 14, Comparative Example 1 In the preparation of the titanium black dispersion of Example 1, the specific resin 1 was replaced with the specific resin and the comparative resin shown in Table 2, respectively, to prepare the titanium black dispersions of Examples 2 to 14 and Comparative Example 1. .
  • the titanium black dispersion of Example 1 was replaced with the above titanium black dispersion having the specific resin shown in Table 2, and the polymerization initiator was changed to Table 2.
  • the polymerizable compositions of Examples 2 to 14 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the polymerization initiators shown in Table 1 were used.
  • ⁇ Preparation of color filter having black matrix for solid-state image sensor> Using each polymerizable composition prepared as described above, a spine coater was applied onto the undercoat layer of the silicon wafer with the undercoat layer, and then allowed to stand for 10 minutes and heated for 120 seconds using a hot plate at 100 ° C. By performing the treatment (pre-baking), a coating film having a dry film thickness of 0.7 ⁇ m was formed. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 1000 mJ / cm 2 through an Island pattern mask having a pattern of 2 ⁇ m square at a wavelength of 365 nm.
  • FPA-3000i5 + manufactured by Canon Inc.
  • the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film). Paddle development was performed for 90 seconds at 23 ° C. using Electronics Materials Co., Ltd.
  • the silicon wafer on which the coating film is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center.
  • the wafer was supplied in a shower form and rinsed, and then spray-dried to form a wafer having a black matrix.
  • the polymerization initiators listed in Table 2 are as follows.
  • Viscosity of dispersion composition The viscosity of the dispersion composition at 25 ° C was measured using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). The smaller the viscosity of the dispersion composition, the higher the dispersibility.
  • -Criteria- The allowable value is 3 or more. Sedimentation of 5: 0% or more and less than 2% of titanium black was observed. 4: Sedimentation of titanium black of 2% or more and less than 3% was observed. 3: Titanium black sedimentation of 3% or more and less than 4% was observed. 2: Sedimentation of 4% or more and less than 5% of titanium black was observed. Sedimentation of titanium black of 1: 5% or more was observed.
  • each polymerizable composition was applied on an 8-inch silicon wafer with a spin coater so that the film thickness after drying was 1 ⁇ m, and observed with an optical microscope to evaluate the uniform coating property.
  • the evaluation criteria are as follows.
  • the substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and D1030 (tetramethylammonium hydroxide) is placed.
  • Paddle development was performed at 23 ° C. for 120 seconds using a 0.31 mass% aqueous solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.).
  • the line-and-space pattern having the line widths of 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, and 200 ⁇ m formed as described above was observed with an optical microscope, and it was confirmed whether or not the line portion of each line width remained.
  • the generation (resolution) of the pattern is determined by visual observation, and the time from the start of development to the generation (resolution) of the line portion having a line width of 20 ⁇ m, that is, “pattern occurs (time for resolution)”. was measured. Further, at the time points of 30 seconds, 60 seconds, 120 seconds, 150 seconds, 180 seconds, 210 seconds, and 240 seconds after the start of development, a 20 ⁇ m line portion remains by observation with an optical microscope.
  • the time when the line part having a line width of 20 ⁇ m was finally confirmed was defined as “the time from the start of development until the last line part having a line width of 20 ⁇ m remained” (ie, for example, the line width If the 20 ⁇ m line portion was confirmed 120 seconds after the start of development but not 150 seconds after the start of development, the line portion with a line width of 20 ⁇ m from the start of development remained. "Time to do” was 120 seconds). Based on the “pattern generation (resolution time)” and “time from the start of development to the last remaining line portion having a line width of 20 ⁇ m” measured as described above, the development latitude was evaluated according to the following evaluation criteria. evaluated.
  • Examples 15 to 23, Comparative Example 2 ⁇ Preparation of black matrix for liquid crystal display device>
  • a color filter having a black matrix for a liquid crystal display device was produced and evaluated. That is, using the same polymerizable composition as that used in the production of the color filter for the solid-state image sensor, slitting was applied to a 250 mm ⁇ 350 mm glass substrate under the following conditions, and then waiting for 10 minutes as it was. Drying and pre-baking (100 ° C., 80 seconds) were carried out to form a polymerizable composition coating film.
  • an i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
  • exposure was performed at a wavelength of 365 nm through a hole pattern mask having a diameter of 200 ⁇ m at an exposure amount of 1000 mJ / cm 2 .
  • the exposed coating film was covered with a 1% aqueous solution of an alkaline developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds. Thereafter, pure water was sprayed in a shower to wash away the developer.
  • an alkaline developer trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.
  • the polymerizable composition of the present invention has a good uniform coating property when applied to a substrate, and a residue in an unexposed part is present. It was found to be suppressed.
  • a mixed liquid consisting of 50 parts and 110 parts of propylene glycol monomethyl ether as a solvent was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
  • the pigment dispersion (P1) that has been subjected to the dispersion treatment is stirred and mixed so that the following composition ratios are obtained, and the colored polymerizable composition R-1 for red (R) and the colored polymerizable composition G for green (G), respectively.
  • compositions B-1 and a colored polymerizable composition B-1 for blue (B) were prepared.
  • ⁇ Composition> -Colorant (pigment dispersion (P1)) 350 parts-Polymerization initiator (oxime photopolymerization initiator) (CGI-124, manufactured by BASF) 30 parts-TO-1382 25 parts (polymerizable compound Toa Gosei Chemical ( Co., Ltd. Carboxyl group-containing pentafunctional acrylate) ⁇ Dipentaerythritol hexaacrylate 30 parts ⁇ Solvent (PGMEA) 200 parts ⁇
  • Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 copy
  • the coloring polymerizable composition for green (G) and the coloring polymerizable composition for blue (B) prepared for the production of the color filter for the solid-state imaging device described above, respectively.
  • the polymerizable composition G-1 and the colored polymerizable composition B-1 for blue (B) were used.
  • the light-shielding filter prepared in Example 1 was used as a black matrix, and the above-described (Preparation of color filter for solid-state imaging device) was performed on the black matrix using the colored polymerizable composition R-2 for red (R).
  • a red (R) colored pattern of 80 ⁇ 80 ⁇ m was formed in the same manner as described.
  • a green (G) chromatic coloring pattern is obtained using the green (G) colored polymerizable composition G-1, and a blue color using the blue (B) colored polymerizable composition B-1.
  • a chromatic color pattern of (B) was sequentially formed to produce a color filter having a black matrix for a liquid crystal display device.
  • the full color liquid crystal display device color filter prepared as described above was processed with an ITO transparent electrode, an alignment film and the like to provide a liquid crystal display device.
  • the polymerizable composition of the present invention had good uniformity on the coated surface, the liquid crystal display device had no display unevenness, and the image quality was good.
  • a wafer level lens provided with a light shielding layer was prepared by applying the polymerizable composition prepared in Example 1 onto a silicon wafer provided with a lens.
  • the produced wafer level lens was cut, and a lens module was produced thereon, and then an imaging device and a sensor substrate were attached to produce an imaging unit.
  • the wafer level lens of the present invention has high uniformity of the coating surface of the light shielding layer portion and high light shielding properties, and the image quality when using this imaging unit was good.
  • the dispersibility, the storage stability and the coating property are high.
  • a polymerizable composition is combined with a polymerizable compound and pattern formation is performed using this polymerizable composition, in the unexposed area.
  • a dispersion composition capable of forming a pattern in which a residue is suppressed and improving a development margin and development latitude in pattern formation, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, A liquid crystal display device, a wafer level lens, and an imaging unit can be provided.

Abstract

Provided are: a dispersion composition which has high dispersibility, storage stability and coatability, which is capable of forming a pattern that is suppressed in the residue in an unexposed portion in cases where a polymerizable composition is obtained by combining the dispersion composition with a polymerizable compound and a pattern is formed using this polymerizable composition, and which is capable of improving development margin and development latitude in the pattern formation; a polymerizable composition which uses this dispersion composition; a light-blocking color filter; a solid-state imaging element; a liquid crystal display device; a wafer-level lens; and an imaging unit. A dispersion composition which contains (A) titanium black, (B) a polymer compound that has a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having a graft chain, and (C) a solvent; a polymerizable composition which uses this dispersion composition; a light-blocking color filter; a solid-state imaging element; a liquid crystal display device; a wafer-level lens; and an imaging unit.

Description

分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニットDispersion composition, and polymerizable composition, light-shielding color filter, solid-state imaging device, liquid crystal display device, wafer level lens, and imaging unit using the same
　本発明は、分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニットに関する。 The present invention relates to a dispersion composition, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, a liquid crystal display device, a wafer level lens, and an imaging unit using the same.
　液晶表示装置に用いられるカラーフィルタには着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ブラックマトリクスと呼ばれる遮光膜が備えられている。また、固体撮像素子においてもノイズ発生防止、画質の向上等を目的としてブラックマトリックスが設けられている。ブラックマトリクスは、遮光性の黒色色材を分散させた分散組成物と、重合性化合物と、重合開始剤と、その他の成分とを含有して重合性組成物とし、これを用いてフォトリソ法などによりパターン形成することで製造されている。
　液晶表示装置用や固体撮像素子用のブラックマトリクスを形成するための組成物としては、カーボンブラックやチタンブラック等の黒色色材を含有する感光性樹脂組成物が知られている。 A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a black matrix is provided for the purpose of preventing noise and improving image quality. The black matrix contains a dispersion composition in which a light-shielding black color material is dispersed, a polymerizable compound, a polymerization initiator, and other components to form a polymerizable composition, which is used for a photolithography method, etc. It is manufactured by forming a pattern.
As a composition for forming a black matrix for a liquid crystal display device or a solid-state imaging device, a photosensitive resin composition containing a black color material such as carbon black or titanium black is known.
　液晶表示装置用ブラックマトリクスとしては、コントラストを高め、視認性を向上させるため遮光性の高いブラックマトリクスが要求される。一方、固体撮像素子用ブラックマトリクスとしては、可視域における遮光性に加え、赤外域における遮光性をも備える必要がある。
　従来、遮光性のブラックマトリクスとしては、専らカーボンブラックが多用されてきたが、カーボンブラックで遮光性を高めようとすると、カーボンブラックの充填量を高めることが必要となる。このため遮光材であるカーボンブラックの濃度の高い分散組成物、あるいは重合性組成物が遮光層のパターン成形に必要となる。しかしながら高い遮光性を得るためにカーボンブラックの含有量を増やすと、カーボンブラックの分散性が困難になり、またパターン成形性が悪化するといったような問題も発生していた。 As a black matrix for a liquid crystal display device, a black matrix having a high light shielding property is required in order to increase contrast and improve visibility. On the other hand, a black matrix for a solid-state imaging device needs to have light shielding properties in the infrared region in addition to light shielding properties in the visible region.
Conventionally, carbon black has been widely used as a light-shielding black matrix. However, if the light-shielding property is to be improved with carbon black, it is necessary to increase the filling amount of carbon black. For this reason, a dispersion composition or a polymerizable composition having a high concentration of carbon black as a light shielding material is required for pattern formation of the light shielding layer. However, when the content of carbon black is increased in order to obtain a high light-shielding property, there has been a problem that the dispersibility of carbon black becomes difficult and the pattern formability deteriorates.
　液晶表示装置用ブラックマトリクスとしては、主に可視域における遮光性が要求されるのに対し、固体撮像素子用ブラックマトリックスとしては、可視域における遮光性に加え、シリコン基板の裏面からの赤外域における透過を防ぐために、赤外域における遮光性をも備える必要がある。
　また、液晶表示装置用ブラックマトリクスについては微細化が要求されている一方、固体撮像素子用ブラックマトリクス（特に、支持体の受光素子形成面に対し反対側の面（以下、「裏面」ともいう）を遮光するためのブラックマトリックス）については、液晶表示装置用ブラックマトリクスよりも広い面積を均一に遮光する性能が要求されている。 As a black matrix for a liquid crystal display device, a light shielding property in the visible region is mainly required, whereas as a black matrix for a solid-state imaging device, in the infrared region from the back surface of the silicon substrate in addition to the light shielding property in the visible region. In order to prevent transmission, it is necessary to have light shielding properties in the infrared region.
Further, the black matrix for liquid crystal display devices is required to be miniaturized, while the black matrix for solid-state imaging device (in particular, the surface opposite to the light-receiving element forming surface of the support (hereinafter also referred to as “back surface”)). As for the black matrix for shielding light, it is required to have a performance for uniformly shielding a larger area than the black matrix for liquid crystal display devices.
　また、高い遮光性を得るために黒色色材の含有量を増やすと遮光膜周辺部の残渣の発生しやすくなり、感度も低下するという問題を有していた。更に、感度を向上させるため、重合開始剤量を増やすと経時安定性が低下してしまう問題を有していた。 Further, when the content of the black color material is increased in order to obtain a high light shielding property, there is a problem that a residue around the light shielding film is easily generated and the sensitivity is also lowered. Furthermore, when the amount of the polymerization initiator is increased in order to improve the sensitivity, there is a problem that the temporal stability is lowered.
　また、近年、携帯電話やＰＤＡ（Ｐｅｒｓｏｎａｌ　Ｄｉｇｉｔａｌ　Ａｓｓｉｓｔａｎｔ）など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。このような撮像ユニットは、一般に、ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）イメージセンサやＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）イメージセンサなどの固体撮像素子と、固体撮像素子上に被写体像を形成するためのレンズとを備えている。 In recent years, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an image pickup unit generally includes a solid-state image sensor such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state image sensor. I have.
　携帯端末の小型化・薄型化に伴って撮像ユニットの小型化・薄型化が要請されている。また、携帯端末のコストの低下を図るため、製造工程の効率化が望まれている。このような小型かつ多数のレンズを製造する方法としては、基板に複数のレンズを成形した構成であるウエハレベルレンズを製造し、基板を切断して複数のレンズをそれぞれ分離させることでレンズモジュールを量産する方法が知られている。 As the mobile terminal becomes smaller and thinner, there is a demand for smaller and thinner imaging units. Moreover, in order to reduce the cost of the portable terminal, it is desired to increase the efficiency of the manufacturing process. As a method for manufacturing such a small number of lenses, a lens module is manufactured by manufacturing a wafer level lens having a configuration in which a plurality of lenses are molded on a substrate, and cutting the substrate to separate each of the plurality of lenses. A method for mass production is known.
　また、複数のレンズが形成された基板と複数の固体撮像素子が形成されたセンサ基板とを一体に組み合わせ、レンズと固体撮像素子をセットとして含むように基板とともにセンサ基板を切断することで撮像ユニットを量産する方法が知られている。 In addition, the imaging unit is obtained by integrally combining a substrate on which a plurality of lenses are formed and a sensor substrate on which a plurality of solid-state imaging elements are formed, and cutting the sensor substrate together with the substrate so as to include the lens and the solid-state imaging elements as a set. There are known methods for mass production.
　従来、ウエハレベルレンズとしては、複数のレンズが成形された基板を重ね合わせて構成された多層のウエハレベルレンズが記載されている（例えば、特許文献１参照）。ウエハレベルレンズは、基板とレンズとが光を透過させる透明な材料で構成され、いずれの部位でも光を透過させ得るものであるため、ウエハレベルレンズをダイシングし撮像素子に搭載して撮像ユニットとした場合に、レンズのレンズ面以外の領域で光の透過や反射が生じると、撮像時にゴーストやフレアといった光学性能上の不具合が生じやすくなることが懸念される。このような不具合の防止の観点から、例えばウエハレベルレンズのレンズ以外の領域には、遮光部材を設ける等の加工が施されている。 Conventionally, as a wafer level lens, a multilayer wafer level lens configured by superposing substrates on which a plurality of lenses are formed has been described (for example, see Patent Document 1). Since the wafer level lens is made of a transparent material that allows light to pass through the substrate and the lens and can transmit light at any part, the wafer level lens is diced and mounted on the imaging device to In this case, if light is transmitted or reflected in a region other than the lens surface of the lens, there is a concern that optical performance problems such as ghost and flare are likely to occur during imaging. From the viewpoint of preventing such a problem, for example, a region other than the lens of the wafer level lens is subjected to processing such as providing a light shielding member.
　上記したようなブラックマトリクスや、ウエハレベルレンズにおける遮光部材の品質要求に応えるため、遮光性の高いチタンブラックの有用性が高まり、チタンブラックを含有する組成物の性能を向上させることが種々提案されているが、例えば、チタンブラックとグラフト共重合体とを含有する分散組成物を使用する技術が知られており、この技術によれば、分散組成物の分散性及び保存安定性に優れ、また、パターン形成した場合には未露光部における残渣が抑制される等の効果が得られるとされている（特許文献２及び３参照）。 In order to meet the quality requirements of the light shielding member in the black matrix and wafer level lens as described above, the usefulness of titanium black having high light shielding properties is increased, and various proposals have been made to improve the performance of a composition containing titanium black. However, for example, a technique using a dispersion composition containing titanium black and a graft copolymer is known. According to this technique, the dispersion composition has excellent dispersibility and storage stability, and In the case of pattern formation, it is said that effects such as suppression of residues in unexposed portions can be obtained (see Patent Documents 2 and 3).
日本国特表２００５－５３９２７６号公報Japanese National Table 2005-539276 日本国特開２０１０－１０６２６８号公報Japanese Unexamined Patent Publication No. 2010-106268 日本国特開２０１１－８９０１５号公報Japanese Unexamined Patent Publication No. 2011-89015
　しかしながら、撮像ユニットの更なる小型化・薄型化等の要請により、ブラックマトリクスや、ウエハレベルレンズにおける遮光部材に対して、更なる微細化や形状の特殊化が求められつつあり、分散性及び保存安定性を有するのみならず、得られるパターンが現像条件の変動によって影響を受けにくいことにより、上記要望を達成可能な分散組成物が求められている。 However, due to demands for further downsizing and thinning of the imaging unit, further miniaturization and specialization of the shape of the black matrix and the light shielding member in the wafer level lens are being demanded. There is a need for a dispersion composition that not only has stability but also can achieve the above-mentioned demand because the pattern obtained is not easily affected by variations in development conditions.
　本発明は、上記従来の状況に鑑みなされたものであり、以下の目的を達成することを課題とする。
　即ち、本発明は、分散性、保存安定性及び塗布性が高く、重合性化合物と組み合わせて重合性組成物とし、この重合性組成物を用いてパターン形成を行った場合に、未露光部における残渣が抑制されたパターンを形成可能であり、また、パターン形成における現像マージン及び現像ラチチュードを向上できる分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニットを提供することを目的とする。 This invention is made | formed in view of the said conventional condition, and makes it a subject to achieve the following objectives.
That is, the present invention has a high dispersibility, storage stability, and coating property, and when it is combined with a polymerizable compound to form a polymerizable composition, and pattern formation is performed using this polymerizable composition, in the unexposed area. A dispersion composition capable of forming a pattern in which a residue is suppressed and improving a development margin and development latitude in pattern formation, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, An object is to provide a liquid crystal display device, a wafer level lens, and an imaging unit.
　前記課題を解決するための手段は以下の通りである。
〔１〕
　（Ａ）チタンブラック、（Ｂ）グラフト鎖を有する構造単位と、前記グラフト鎖を有する構造単位とは異なる疎水性構造単位とを有する高分子化合物、及び、（Ｃ）溶媒を含有する分散組成物。
〔２〕
　前記疎水性構造単位は、ＣｌｏｇＰ値が１．２以上の化合物に由来する構造単位である、上記〔１〕に記載の分散組成物。
〔３〕
　前記疎水性構造単位が、下記一般式（ｉ）～（ｉｉｉ）で表される単量体に由来する構造単位から選択される１種以上の構造単位である、〔１〕又は〔２〕に記載の分散組成物。 Means for solving the above-mentioned problems are as follows.
[1]
(A) titanium black, (B) a polymer compound having a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain, and (C) a dispersion composition containing a solvent .
[2]
The dispersion composition according to [1], wherein the hydrophobic structural unit is a structural unit derived from a compound having a ClogP value of 1.2 or more.
[3]
[1] or [2], wherein the hydrophobic structural unit is one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii): The dispersion composition described.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記一般式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に、水素原子、ハロゲン原子、又はアルキル基を表す。
　Ｘは、酸素原子又はイミノ基を表す。
　Ｌは、単結合又は２価の連結基である。
　Ｚは、脂肪族基、芳香族基、複素環基、又はそれらと酸素原子、硫黄原子、イミノ基、置換イミノ基若しくはカルボニル基との組合せを表す。
　Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子、又はアルキル基、Ｚ、又は－Ｌ－Ｚを表す。
〔４〕
　前記高分子化合物（Ｂ）の重量平均分子量が、６，０００～１００，０００である、上記〔１〕～〔３〕のいずれか１項に記載の分散組成物。
〔５〕
　前記グラフト鎖を構成する原子の内、水素原子を除いた原子の数が４０～１００００の範囲である、上記〔１〕～〔４〕のいずれか１項に記載の分散組成物。
〔６〕
　前記グラフト鎖が、ポリエステル構造、ポリエーテル構造、及びポリ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種を有するグラフト鎖である、上記〔１〕～〔５〕のいずれか１項に記載の分散組成物。
〔７〕
　前記高分子化合物（Ｂ）が、前記グラフト鎖を有する構造単位として、下記式（１）～式（４）で表される構造単位から選択された１種以上の構造単位を有する高分子化合物である、上記〔１〕～〔６〕のいずれか１項に記載の分散組成物。 In the general formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
X represents an oxygen atom or an imino group.
L is a single bond or a divalent linking group.
Z represents an aliphatic group, an aromatic group, a heterocyclic group, or a combination thereof with an oxygen atom, a sulfur atom, an imino group, a substituted imino group or a carbonyl group.
R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, Z, or —LZ.
[4]
The dispersion composition according to any one of [1] to [3] above, wherein the polymer compound (B) has a weight average molecular weight of 6,000 to 100,000.
[5]
The dispersion composition according to any one of the above [1] to [4], wherein the number of atoms excluding hydrogen atoms among the atoms constituting the graft chain is in the range of 40 to 10,000.
[6]
The dispersion according to any one of [1] to [5], wherein the graft chain is a graft chain having at least one selected from the group consisting of a polyester structure, a polyether structure, and a polyacrylate structure. Composition.
[7]
The polymer compound (B) is a polymer compound having one or more structural units selected from the structural units represented by the following formulas (1) to (4) as the structural unit having the graft chain. The dispersion composition according to any one of [1] to [6] above.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔式（１）～式（４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４はそれぞれ独立に酸素原子或いはＮＨを表し、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５はそれぞれ独立に水素原子又は１価の有機基を表し、Ｙ１、Ｙ２、Ｙ３、及びＹ４はそれぞれ独立に２価の連結基を表し、Ｚ１、Ｚ２、Ｚ３、及びＺ４はそれぞれ独立に１価の有機基を表す。Ｒ３は分岐又は直鎖のアルキレン基を表し、Ｒ４は水素原子又は１価の有機基を表す。ｎ、ｍ、ｐ、及びｑはそれぞれ独立に１から５００の整数を表す。ｊ及びｋはそれぞれ独立に２～８の整数を表す。式（３）において、ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。式（４）において、ｑが２～５００のとき、複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。〕
〔８〕
　前記高分子化合物（Ｂ）が、前記式（１）～式（４）で表される構造単位から選択された１種以上の構造単位を、前記高分子化合物（Ｂ）の総質量に対し質量換算で、１０％～９０％の範囲で含む高分子化合物である、上記〔７〕に記載の分散組成物。
〔９〕
　前記高分子化合物（Ｂ）が、前記チタンブラックと相互作用を形成しうる官能基を有する構造単位を更に有する高分子化合物である、上記〔１〕～〔８〕のいずれか１項に記載の分散組成物。
〔１０〕
　前記高分子化合物（Ｂ）が、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種を有する構造単位を更に有する高分子化合物である、上記〔１〕～〔９〕のいずれか１項に記載の分散組成物。
〔１１〕
　前記高分子化合物（Ｂ）の酸価が、１０～１４０ｍｇＫＯＨ／ｇである、上記〔１〕～〔１０〕のいずれか１項に記載の分散組成物。
〔１２〕
　上記〔１〕～〔１１〕のいずれか１項に記載の分散組成物、（Ｄ）重合性化合物、及び（Ｅ）重合開始剤を含む、重合性組成物。
〔１３〕
　前記（Ｅ）重合開始剤が、オキシム化合物である、上記〔１２〕に記載の重合性組成物。
〔１４〕
　基板上に、上記〔１２〕又は〔１３〕に記載の重合性組成物を用いて形成された着色パターンを有する遮光性カラーフィルタ。
〔１５〕
　上記〔１４〕に記載の遮光性カラーフィルタを備えた固体撮像素子。
〔１６〕
　上記〔１４〕に記載の遮光性カラーフィルタを備えた液晶表示装置。
〔１７〕
　複数のレンズが一体に成形された基板と、該基板の前記レンズのレンズ面を除く領域に設けられた上記〔１４〕に記載の遮光性カラーフィルタと、を備えたウエハレベルレンズ。
〔１８〕
　上記〔１７〕に記載のウエハレベルレンズを備えた撮像ユニット。 [In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, and X 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a monovalent organic group, Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group. R 3 represents a branched or straight chain alkylene group, and R 4 represents a hydrogen atom or a monovalent organic group. n, m, p, and q each independently represents an integer of 1 to 500. j and k each independently represents an integer of 2 to 8. In the formula (3), when p is 2 to 500, a plurality of R 3 may be the same or different from each other. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 may be the same or different from each other. ]
[8]
The polymer compound (B) has one or more structural units selected from the structural units represented by the formulas (1) to (4) in a mass relative to the total mass of the polymer compound (B). The dispersion composition as described in [7] above, which is a polymer compound contained in a range of 10% to 90% in terms of conversion.
[9]
The polymer compound (B) according to any one of the above [1] to [8], wherein the polymer compound (B) is a polymer compound further having a structural unit having a functional group capable of interacting with the titanium black. Dispersion composition.
[10]
Any of [1] to [9] above, wherein the polymer compound (B) is a polymer compound further having a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The dispersion composition according to claim 1.
[11]
The dispersion composition according to any one of [1] to [10] above, wherein the polymer compound (B) has an acid value of 10 to 140 mgKOH / g.
[12]
A polymerizable composition comprising the dispersion composition according to any one of the above [1] to [11], (D) a polymerizable compound, and (E) a polymerization initiator.
[13]
The polymerizable composition as described in [12] above, wherein (E) the polymerization initiator is an oxime compound.
[14]
A light-shielding color filter having a colored pattern formed on the substrate using the polymerizable composition according to [12] or [13].
[15]
A solid-state imaging device comprising the light-shielding color filter according to [14].
[16]
A liquid crystal display device comprising the light-shielding color filter according to [14].
[17]
A wafer level lens comprising: a substrate on which a plurality of lenses are integrally formed; and the light-shielding color filter according to [14] provided in a region excluding the lens surface of the lens.
[18]
An imaging unit comprising the wafer level lens described in [17] above.
　本発明によれば、分散性、保存安定性及び塗布性が高く、重合性化合物と組み合わせて重合性組成物とし、この重合性組成物を用いてパターン形成を行った場合に、未露光部における残渣が抑制されたパターンを形成可能であり、また、パターン形成における現像マージン及び現像ラチチュードを向上できる分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニットを提供できる。 According to the present invention, the dispersibility, the storage stability and the coating property are high. When a polymerizable composition is combined with a polymerizable compound and pattern formation is performed using this polymerizable composition, in the unexposed area. A dispersion composition capable of forming a pattern in which a residue is suppressed and improving a development margin and development latitude in pattern formation, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, A liquid crystal display device, a wafer level lens, and an imaging unit can be provided.
ウエハレベルレンズの構成の一例を示す平面図である。It is a top view which shows an example of a structure of a wafer level lens. 図１のＡ－Ａ線断面図である。FIG. 2 is a sectional view taken along line AA in FIG. 1. ウエハレベルレンズの他の構成例を示す断面図である。It is sectional drawing which shows the other structural example of a wafer level lens. 撮像ユニットの構成の一例を示す断面図である。It is sectional drawing which shows an example of a structure of an imaging unit.
　以下、本発明を詳細に説明する。
　なお、本明細書に於ける基（原子団）の表記に於いて、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　また本明細書中における「放射線」は、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を含むものを意味する。
　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ことがあるが、本発明はそのような実施態様に限定されるものではない。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む範囲を意味する。
　なお、本明細書において、“（メタ）アクリレート”はアクリレート及びメタアクリレートを表し、“（メタ）アクリルはアクリル及びメタアクリルを表し、“（メタ）アクリロイル”は、アクリロイル及びメタクリロイルを表す。また、本明細書中において、“単量体”と“モノマー”とは同義である。本発明における単量体は、オリゴマー及びポリマーと区別され、質量平均分子量が２，０００以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基を言う。 Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomer and polymer, and refers to a compound having a mass average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. To tell.
　本発明の分散組成物は、（Ａ）チタンブラック、（Ｂ）グラフト鎖を有する構造単位と、前記グラフト鎖を有する構造単位とは異なる疎水性構造単位とを有する高分子化合物、及び、（Ｃ）溶媒を含有する。
　また、本発明の重合性組成物は、上記の本発明の分散物、（Ｄ）重合性化合物、及び（Ｅ）重合開始剤を含有する。
　本発明の分散組成物によれば、分散性、保存安定性及び塗布性が高い分散組成物が得られる。
　また、本発明の重合性組成物によれば、パターン形成を行った場合に、未露光部における残渣が抑制されたパターンを形成可能であり、また、パターン形成における現像マージン及び現像ラチチュードを向上できる。
　ここで、現像マージンが高いとは、パターン形成時に、露光部が、現像液によって剥離しにくい等の理由により残存しやすく、所望のパターンが得られやすいことを意味する。
　また、現像ラチチュードが高いとは、形成されたパターンが現像液によって剥離するまでの時間が長いことを意味する。 The dispersion composition of the present invention comprises (A) titanium black, (B) a polymer compound having a structural unit having a graft chain, and a hydrophobic structural unit different from the structural unit having the graft chain, and (C ) Contains a solvent.
The polymerizable composition of the present invention contains the dispersion of the present invention, (D) a polymerizable compound, and (E) a polymerization initiator.
According to the dispersion composition of the present invention, a dispersion composition having high dispersibility, storage stability, and coatability can be obtained.
Further, according to the polymerizable composition of the present invention, when pattern formation is performed, it is possible to form a pattern in which residues in unexposed areas are suppressed, and to improve the development margin and development latitude in pattern formation. .
Here, the high development margin means that the exposed portion is likely to remain at the time of pattern formation because it is difficult to be peeled off by the developer, and a desired pattern is easily obtained.
Further, a high development latitude means that a long time is required until the formed pattern is peeled off by the developer.
　以下、本発明の分散組成物、及び、重合性組成物が含有し得る各成分について詳細に説明する。 Hereinafter, each component that the dispersion composition of the present invention and the polymerizable composition may contain will be described in detail.
＜（Ａ）チタンブラック＞
　本発明におけるチタンブラックとは、チタン原子を有する黒色粒子である。好ましくは低次酸化チタンや酸窒化チタン等である。チタンブラック粒子は、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。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、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。 <(A) Titanium black>
Titanium black in the present invention is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. is there.
　チタンブラックの製造方法としては、二酸化チタンと金属チタンの混合体を還元雰囲気で加熱し還元する方法（特開昭４９－５４３２号公報）、四塩化チタンの高温加水分解で得られた超微細二酸化チタンを水素を含む還元雰囲気中で還元する方法（特開昭５７－２０５３２２号公報）、二酸化チタン又は水酸化チタンをアンモニア存在下で高温還元する方法（特開昭６０－６５０６９号公報、特開昭６１－２０１６１０号公報）、二酸化チタン又は水酸化チタンにバナジウム化合物を付着させ、アンモニア存在下で高温還元する方法（特開昭６１－２０１６１０号公報）などがあるが、これらに限定されるものではない。 Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), or ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at a high temperature in the presence of ammonia (JP-A 61-201610), etc. is not.
　チタンブラックは、典型的には、チタンブラック粒子であり、個々の粒子の一次粒径及び平均一次粒径のいずれもが小さいものであることが好ましい。
　具体的には、平均一次粒径で１０ｎｍ～４５ｎｍの範囲のものが好ましく、より好ましくは１２ｎｍ～２０ｎｍの範囲である。なお、本発明における粒径、即ち、粒子直径とは、粒子の外表面の投影面積と等しい面積をもつ円の直径である。粒子の投影面積は、電子顕微鏡写真での撮影により得られた面積を測定し、撮影倍率を補正することにより得られる。 The titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
Specifically, the average primary particle diameter is preferably in the range of 10 nm to 45 nm, and more preferably in the range of 12 nm to 20 nm. In the present invention, the particle diameter, that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
　チタンブラックの比表面積は、特に限定がないが、かかるチタンブラックを撥水化剤で表面処理した後の撥水性が所定の性能となるために、ＢＥＴ法にて測定した値が通常５ｍ２／ｇ以上１５０ｍ２／ｇ以下程度、特に２０ｍ２／ｇ以上１００ｍ２／ｇ以下であることが好ましい。 The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and therefore the value measured by the BET method is usually 5 m 2 / g to 150 m 2 / g or less, particularly preferably 20 m 2 / g to 100 m 2 / g.
　チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名：以上、三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名：赤穂化成（株）製）などが挙げられる。 Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).
　チタンブラック粒子は、分散性向上、凝集性抑制などの目的で必要に応じ、粒子表面を修飾することが可能である。粒子表面の修飾としては、例えば、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、酸化ジルコニウム等で被覆処理が可能であり、また、特開２００７－３０２８３６号公報に示されるような撥水性物質での処理も可能である。 Titanium black particles can be modified on the particle surface as necessary for the purpose of improving dispersibility and suppressing aggregation. As modification of the particle surface, for example, coating treatment with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like is possible, and repellent properties as disclosed in JP-A-2007-302836 are also possible. Treatment with an aqueous material is also possible.
　更に、本発明の分散剤は、チタンブラックを、チタンブラック及びＳｉ原子を含む被分散体として含有することも好ましい。
　この形態において、チタンブラックは、分散物中において被分散体として含有されるものであり、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５以上であることが好ましい。
　ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体（二次粒子）の状態であるものの双方を包含する。 Furthermore, the dispersant of the present invention preferably contains titanium black as a dispersion to be dispersed containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the dispersion, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. It is preferable that
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
　なお、本発明における被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、０．５を超えると被分散体を使用した顔料分散液の製造が困難な傾向となるため、その上限は０．５であることが好ましい。
　また、被分散体のＳｉ／Ｔｉが小さすぎると、本発明における被分散体を使用した遮光膜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やすくなり、被分散体のＳｉ／Ｔｉは大きすぎると遮光能が低下する傾向となるため、被分散体のＳｉ／Ｔｉは、０．０５以上０．５以下であることがより好ましく、０．０７以上０．４以下であることが更に好ましい。 If the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention exceeds 0.5, it tends to be difficult to produce a pigment dispersion using the dispersion. The upper limit is preferably 0.5.
If the Si / Ti of the dispersion is too small, a residue is likely to remain in the removed portion when the light shielding film using the dispersion in the present invention is patterned by photolithography or the like, and the Si / Ti of the dispersion If Ti is too large, the light shielding ability tends to decrease. Therefore, the Si / Ti of the dispersion is more preferably 0.05 or more and 0.5 or less, and 0.07 or more and 0.4 or less. Is more preferable.
　被分散体のＳｉ／Ｔｉを変更する（例えば０．０５以上とする）ためには、以下のような手段を用いることができる。
　先ず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この混合物を高温（例えば、８５０～１０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含有する被分散体を得ることができる。 In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly contained. Thus, a dispersion containing Si and Ti can be obtained.
　ここで、被分散体のＳｉ／Ｔｉを変更するための具体的な態様について説明する。
　Ｓｉ／Ｔｉが例えば０．０５以上等に調整されたチタンブラックは、例えば、特開２００８－２６６０４５公報の段落番号〔０００５〕（６）及び同段落番号〔００１６〕～〔００２１〕に記載の方法により作製することができる。 Here, the specific aspect for changing Si / Ti of a to-be-dispersed body is demonstrated.
Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, is a method described in paragraphs [0005] and (6) and paragraphs [0016] to [0021] of JP-A-2008-266045, for example. Can be produced.
　本発明においては、チタンブラック及びＳｉ原子を含む被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）を好適な範囲（例えば０．０５以上）に調整することで、この被分散体を含む本発明の組成物を用いて遮光膜を形成した際に、遮光膜の形成領域外における組成物由来の残渣物が低減される。なお、残渣物は、チタンブラック粒子、樹脂成分等の感光性組成物に由来する成分を含むものである。
　残渣物が低減される理由は未だ明確ではないが、上記のような被分散体は小粒径となる傾向があり（例えば、粒径が３０ｎｍ以下）、更に、この被分散体のＳｉ原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減され、これが、遮光膜の形成における未硬化の組成物（特に、チタンブラック粒子）の現像除去性の向上に寄与すると推測している。 In the present invention, by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved. When the light-shielding film is formed using the composition of the present invention containing the dispersion, the residue derived from the composition outside the region where the light-shielding film is formed is reduced. The residue includes components derived from the photosensitive composition such as titanium black particles and a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less). By increasing the amount of components contained, the adsorptivity of the entire film with the undercoat is reduced, and this is presumed to contribute to the improvement of the development and removability of the uncured composition (particularly titanium black particles) in the formation of the light-shielding film. ing.
　また、チタンブラックは、紫外から赤外までの広範囲に亘る波長領域の光に対する遮光性に優れることから、上記したチタンブラック及びＳｉ原子を含む被分散体（好ましくはＳｉ／Ｔｉが質量換算で０．０５以上であるもの）を用いて形成された遮光膜は優れた遮光性を発揮する。 In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet to infrared. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is 0 in terms of mass). A light-shielding film formed using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
　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、下記に示す方法（１－１）又は方法（１－２）を用いて測定できる。 The content ratio (Si / Ti) between Si atoms and Ti atoms in the dispersion can be measured, for example, using the method (1-1) or the method (1-2) shown below.
＜方法（１－１）＞
　チタンブラック分散物、又は、チタンブラック分散液と重合性化合物とを含有する重合性組成物を、酸素雰囲気中で加熱処理し、（Ａ）チタンブラック及びＳｉ原子を含む被分散体を取り出した。
　チタンブラック分散物又は重合性組成物を、２０ｍｇ秤量し、ここに、ＨＦ　０．１ｍＬ、ＨＮＯ３（１０％ａｑ．）１ｍＬ、Ｈ２ＳＯ４（５％ａｑ．）１ｍＬ、及びＨＣＬ（３％ａｑ．）１ｍＬを添加し、マイクロウェーブ溶解を行った。この時の液温は１８０℃であった。
　その後、この混合液に、Ｈ２Ｏを１００ｍｌになるまで加え、これをＩＣＰ－ＯＥＳ（Ａｔｔｏｍ、商品名：ＳＩＩ社製）に供し、元素分析を行う。得られた結果より、Ｓｉ／Ｔｉの質量比を算出する。
＜方法（１－２）＞
　チタンブラック分散液、又は、チタンブラック分散液と重合性化合物とを含有する重合性組成物を、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で７００℃に加熱し、３０分間保持した後に冷却し、粉体を２ｇ得て、得られた粉体を厚さ０．２ｍｍのタングステン板上にのせ、これを、電子線加熱機構を具備した真空チャンバ内に設置し、真空度を１０－５Ｔｏｒｒ以下として電子線加熱により１０００℃で３０秒加熱処理する。加熱処理した粉体について、電界放出型走査電子顕微鏡Ｓ－４８００（商品名、日立テクノロジーズ社製）及び、エネルギー分散型蛍光Ｘ線検出器　ＩＮＣＡ　Ｅｎｅｒｇｙ　ＰｅｎｔａＦＥＴｘ３（商品名、Ｏｘｆｏｒｄ社製）を用いて、Ｓｉ原子量、Ｔｉ原子量を求め、Ｓｉ／Ｔｉ比を算出する。 <Method (1-1)>
A titanium black dispersion or a polymerizable composition containing a titanium black dispersion and a polymerizable compound was heat-treated in an oxygen atmosphere, and (A) a dispersion containing titanium black and Si atoms was taken out.
Titanium black dispersion or polymerizable composition was weighed 20 mg, where HF 0.1 mL, HNO 3 (10% aq.) 1 mL, H 2 SO 4 (5% aq.) 1 mL, and HCL (3% aq.) 1 mL was added and microwave dissolution was performed. The liquid temperature at this time was 180 degreeC.
Thereafter, H 2 O is added to this mixed solution until it becomes 100 ml, and this is subjected to ICP-OES (Atom, trade name: manufactured by SII), and elemental analysis is performed. From the obtained results, the mass ratio of Si / Ti is calculated.
<Method (1-2)>
A polymerizable composition containing a titanium black dispersion or a titanium black dispersion and a polymerizable compound was heated to 700 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.) and held for 30 minutes. After cooling, 2 g of powder was obtained, and the obtained powder was placed on a 0.2 mm thick tungsten plate and placed in a vacuum chamber equipped with an electron beam heating mechanism. -5 Torr or less, heat treatment at 1000 ° C. for 30 seconds by electron beam heating. About the heat-treated powder, using a field emission scanning electron microscope S-4800 (trade name, manufactured by Hitachi Technologies) and an energy dispersive X-ray fluorescence detector INCA Energy PentAFETx3 (trade name, manufactured by Oxford) The Si atomic weight and Ti atomic weight are obtained, and the Si / Ti ratio is calculated.
　また、本発明の重合性組成物を硬化して得られた硬化膜（遮光膜）に含有される被分散体について、その被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が０．０５以上か否かを判断するには、下記に示す方法（２）を用いる。 Moreover, about the to-be-dispersed material contained in the cured film (light-shielding film) obtained by hardening | curing polymeric composition of this invention, the content ratio (Si / Ti) of Si atom in the to-be-dispersed material ) Is 0.05 or more, the following method (2) is used.
＜方法（２）＞
　遮光膜が形成された基板を割ることで、遮光膜の断面を作製し、この断面についてエネルギー分散型蛍光Ｘ線分析装置により、遮光膜表面におけるＳｉ原子量とＴｉ原子量を得ることができる。これらの量比を、遮光膜中のＳｉ／Ｔｉとして評価する。
　この際のエネルギー分散型蛍光Ｘ線分析としては、前記の走査型電子顕微鏡として日立ハイテクノロジー社製Ｓ－４８００（商品名）、及び、エネルギー分散型蛍光Ｘ線検出器としてＯｘｆｏｒｄ社製ＩＮＣＡ　Ｅｎｅｒｇｙ　ＰｅｎｔａＦＥＴｘ３（商品名）を同様に用いることができる。 <Method (2)>
By dividing the substrate on which the light-shielding film is formed, a cross section of the light-shielding film can be produced, and the amount of Si atoms and the amount of Ti atoms on the surface of the light-shielding film can be obtained with this energy dispersive X-ray fluorescence spectrometer. These quantitative ratios are evaluated as Si / Ti in the light shielding film.
The energy dispersive fluorescent X-ray analysis at this time includes S-4800 (trade name) manufactured by Hitachi High-Technology as the above-mentioned scanning electron microscope, and INCA Energy PentaFETx3 manufactured by Oxford as the energy dispersive fluorescent X-ray detector. (Product name) can be used similarly.
　チタンブラック及びＳｉ原子を含む被分散体において、チタンブラックは、上記したものを使用できる。
　また、この被分散体においては、チタンブラックと共に、分散性、着色性等を調整する目的で、Ｃｕ、Ｆｅ、Ｍｎ、Ｖ、Ｎｉ等の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、アニリンブラック等からなる黒色顔料を、１種又は２種以上を組み合わせて、被分散体として併用してもよい。
　この場合、全被分散体中の５０質量％以上をチタンブラックからなる被分散体が占めることが好ましい。 In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Further, in this dispersion, in addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline You may use together the black pigment which consists of black etc. by combining 1 type (s) or 2 or more types as a to-be-dispersed body.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
　また、この被分散体においては、遮光性の調整等を目的として、本発明の効果を損なわない限りにおいて、チタンブラックと共に、他の着色剤（有機顔料や染料など）を所望により併用してもよい。 In addition, in this dispersion, for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
　以下、被分散体にＳｉ原子を導入する際に用いられる材料について述べる。被分散体にＳｉ原子を導入する際には、シリカなどのＳｉ含有物質を用いればよい。
　本発明に用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、合成シリカなどを挙げることができ、これらを適宜選択して使用すればよい。
　シリカは市販品としても入手可能であり、例えば、新日鉄マテリアルズ製、ＨＳ－１０１，ＨＳ－１０２，ＨＳ－１０３，ＨＳ－１０４，ＨＳ－１０５，ＨＳ－１０６，ＨＳ－１０７，ＨＳ－２０１，ＨＳ－２０２，ＨＳ－２０３，ＨＳ－２０４，ＨＳ－２０５，ＨＳ－３０１，ＨＳ－３０２，ＨＳ－３０３，ＨＳ－３０４，ＨＳ－３０５（商品名）；宇部日東化成製、ハイプレシカＳＳ，ハイプレシカＴＳ，ハイプレシカＢＳ，ハイプレシカＳＰ，ハイプレシカＦＱ（商品名）；キャボット製、ＣＡＢ－Ｏ－ＳＩＬ（登録商標）ＬＭ－１５０，ＣＡＢ－Ｏ－ＳＩＬ（登録商標）ＬＭ－１５０，ＣＡＢ－Ｏ－ＳＩＬ（登録商標）Ｓ－１７Ｄなどのシリカ粒子を用いることができる。 Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of the silica that can be used in the present invention include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Silica is also available as a commercial product, for example, NS-101, HS-102, HS-103, HS-104, HS-105, HS-106, HS-107, HS-201, manufactured by Nippon Steel Materials. HS-202, HS-203, HS-204, HS-205, HS-301, HS-302, HS-303, HS-304, HS-305 (trade name); Ube Nitto Kasei, High Plessica SS, High Plessica TS , High plesica BS, high plesica SP, high plesica FQ (trade name); manufactured by Cabot, CAB-O-SIL (registered trademark) LM-150, CAB-O-SIL (registered trademark) LM-150, CAB-O-SIL (registered) Silica particles such as S-17D can be used.
　更に、シリカ粒子の粒径が本発明による遮光膜を形成した際に膜厚と同程度の粒径であると遮光性の低下を引き起こすため、シリカ粒子として微粒子タイプのシリカを用いることが好ましい。微粒子タイプのシリカの例としては、例えば、ＡＥＲＯＳＩＬ（登録商標）９０，ＡＥＲＯＳＩＬ（登録商標）１３０，ＡＥＲＯＳＩＬ（登録商標）１５０，ＡＥＲＯＳＩＬ（登録商標）２００，ＡＥＲＯＳＩＬ（登録商標）３００，ＡＥＲＯＳＩＬ（登録商標）３８０，ＡＥＲＯＳＩＬ（登録商標）ＯＸ　５０，ＡＥＲＯＳＩＬ（登録商標）ＥＧ　５０，ＡＥＲＯＳＩＬ（登録商標）ＴＴ　６００，ＡＥＲＯＳＩＬ（登録商標）２００　ＳＰ，ＡＥＲＯＳＩＬ（登録商標）３００　ＳＰ，ＡＥＲＯＰＥＲＬ（登録商標）３００／３０，ＡＥＲＯＳＩＬ（登録商標）Ｒ　９７２　，ＡＥＲＯＳＩＬ（登録商標）Ｒ　９７４，ＡＥＲＯＳＩＬ（登録商標）Ｒ　１０４　，ＡＥＲＯＳＩＬ（登録商標）Ｒ　１０６，ＡＥＲＯＳＩＬ（登録商標）Ｒ　２０２，ＡＥＲＯＳＩＬ（登録商標）Ｒ８０５，ＡＥＲＯＳＩＬ（登録商標）Ｒ　８１２，ＡＥＲＯＳＩＬ（登録商標）Ｒ　８１２　Ｓ，ＡＥＲＯＳＩＬ（登録商標）Ｒ　８１６，ＡＥＲＯＳＩＬ（登録商標）Ｒ　７２００，ＡＥＲＯＳＩＬ（登録商標）Ｒ　８２００，ＡＥＲＯＳＩＬ（登録商標）Ｒ　９２００，ＡＥＲＯＳＩＬ（登録商標）ＭＯＸ　８０，　ＡＥＲＯＳＩＬ（登録商標）ＭＯＸ　１７０，ＡＥＲＯＳＩＬ（登録商標）ＣＯＫ　８４，ＡＥＲＯＳＩＬ（登録商標）ＲＹ　５０，　ＡＥＲＯＳＩＬ（登録商標）ＮＹ　５０，　ＡＥＲＯＳＩＬ（登録商標）ＲＹ　２００，　ＡＥＲＯＳＩＬ（登録商標）ＲＹ　２００，　ＡＥＲＯＳＩＬ（登録商標）ＲＸ　５０　，　ＡＥＲＯＳＩＬ（登録商標）ＮＡＸ　５０　，　ＡＥＲＯＳＩＬ（登録商標）ＲＸ　２００，　ＡＥＲＯＳＩＬ（登録商標）ＲＸ　３００，　ＡＥＲＯＳＩＬ（登録商標）Ｒ　５０４　，　ＡＥＲＯＰＥＲＬ（登録商標）３００／３０，　ＶＰＡＥＲＯＰＥＲＬ（登録商標）Ｐ　２５／２０Ｍ０５；触媒化成製Ｓ６、ＭＡ１００４（商品名、以下同様）、ＭＡ１００６、ＭＡ１０１０、ＭＡ１０１３、ＭＸ０３０Ｗ、ＭＸ０５０Ｗ、　ＭＸ１００Ｗ、ＫＥ－Ｅ３０、ＫＥ－Ｅ４０、ＫＥ－Ｅ５０、ＫＥ－Ｅ７０、ＫＥ－Ｅ１５０、ＫＥ－Ｐ１０、ＫＥ－Ｐ３０、ＫＥ－Ｐ５０、ＫＥ－Ｐ１００、ＫＥ－Ｐ１５０、ＫＥ－Ｐ２５０；新日鉄マテリアルズ製ＨＳ－１０１（商品名、以下同様）、ＨＳ－１０２、ＨＳ－１０３　、ＨＳ－１０４　、ＨＳ－１０５　、ＨＳ－１０６　、ＨＳ－１０７、ＨＳ－２０１、ＨＳ－２０２、ＨＳ－２０３、ＨＳ－２０４　、ＨＳ－２０５、ＨＳ－３０１、ＨＳ－３０２、ＨＳ－３０３、ＨＳ－３０４、及びＨＳ－３０５；宇部日東化成製、ハイプレシカＳＳ（商品名、以下同様）、ハイプレシカＴＳ、ハイプレシカＢＳ、ハイプレシカＳＰ、及びハイプレシカＦＱ；キャボット製、ＣＡＢ－Ｏ－ＳＩＬ（登録商標、以下同様）　ＬＭ－１５０、ＣＡＢ－Ｏ－ＳＩＬ　ＬＭ－１５０、及びＣＡＢ－Ｏ－ＳＩＬ　Ｓ－１７Ｄなどを用いることができるがこれらに限定されない。 Furthermore, if the particle size of the silica particles is about the same as the film thickness when the light-shielding film according to the present invention is formed, the light-shielding property is lowered, so that it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include, for example, AEROSIL (registered trademark) 90, AEROSIL (registered trademark) 130, AEROSIL (registered trademark) 150, AEROSIL (registered trademark) 200, AEROSIL (registered trademark) 300, AEROSIL (registered trademark). ) 380, AEROSIL (registered trademark) OX 50, AEROSIL (registered trademark) EG 50, AEROSIL (registered trademark) TT 600, AEROSIL (registered trademark) 200 SP, AEROSIL (registered trademark) 300 SP, AEROPERL (registered trademark) 300 / 30, AEROSIL (registered trademark) R 972, AEROSIL (registered trademark) R 974, AEROSIL (registered trademark) R 104, AEROSIL (registered trademark) R 106, AEROSIL (registered trademark) R 202, AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R 812, AEROSIL (registered trademark) R 812 S, AEROSIL (registered trademark) R 816, AEROSIL (registered trademark) R 7200, AEROSIL (registered trademark) R 8200, AEROSIL (registered trademark) R 9200, AEROSIL (registered trademark) MOX 80, AEROSIL (registered trademark) MOX 170, AEROSIL (registered trademark) COK 84, AEROSIL (registered trademark) RY 50, AEROSIL (registered trademark) NY 50, AEROSIL ( (Registered trademark) RY 200, AEROSIL (registered trademark) RY 200, AEROSIL (registered trademark) RX 50, AEROSIL (registered trademark) NAX 50, AERO IL (registered trademark) RX 200, AEROSIL (registered trademark) RX 300, AEROSIL (registered trademark) R 504, AEROPERL (registered trademark) 300/30, VPAERPERL (registered trademark) P 25 / 20M05; Product name, the same applies below), MA1006, MA1010, MA1013, MX030W, MX050W, MX100W, KE-E30, KE-E40, KE-E50, KE-E70, KE-E150, KE-P10, KE-P30, KE-P50 KE-P100, KE-P150, KE-P250; NS-HS HS-101 (trade name, the same applies hereinafter), HS-102, HS-103, HS-104, HS-105, HS-106, HS- 107, HS-2 01, HS-202, HS-203, HS-204, HS-205, HS-301, HS-302, HS-303, HS-304, and HS-305; manufactured by Ube Nitto Kasei, High Plessica SS (trade name, The same shall apply hereinafter), high plesica TS, high plesica BS, high plesica SP, and high plesica FQ; CABOT, CAB-O-SIL (registered trademark, the same shall apply hereinafter) LM-150, CAB-O-SIL LM-150, and CAB-O- SIL S-17D can be used, but is not limited thereto.
　本発明の分散組成物、及び、重合性組成物は、チタンブラックを１種のみを含有するものであってもよく、２種以上を含有してもよい。 The dispersion composition and polymerizable composition of the present invention may contain only one type of titanium black, or may contain two or more types.
　チタンブラックの含有量は、分散組成物の全固形分に対して、好ましくは２０質量％以上９４質量％以下の範囲であり、より好ましくは、４０質量％以上９２質量％以下の範囲であり、更に好ましくは４０質量％以上８０質量％以下の範囲である。
　また、チタンブラックの含有量は、重合性組成物の全固形分に対して、好ましくは５質量％以上８０質量％以下の範囲であり、より好ましくは、１０質量％以上７０質量％以下の範囲であり、更に好ましくは２０質量％以上６０質量％以下の範囲である。
　チタンブラックの含有量が前記範囲内であると、本発明の重合性組成物の硬化性が良好となり、かつ均一な膜を形成することができる。
　また、チタンブラックを高濃度に含有することから、充分な遮光性が得られ、チタンブラックを含有する重合性組成物を遮光性カラーフィルタの形成に好適に用いることができる。 The content of titanium black is preferably in the range of 20% by mass to 94% by mass, more preferably in the range of 40% by mass to 92% by mass, with respect to the total solid content of the dispersion composition. More preferably, it is the range of 40 mass% or more and 80 mass% or less.
The content of titanium black is preferably in the range of 5% by mass to 80% by mass and more preferably in the range of 10% by mass to 70% by mass with respect to the total solid content of the polymerizable composition. More preferably, it is the range of 20 mass% or more and 60 mass% or less.
When the content of titanium black is within the above range, the curability of the polymerizable composition of the present invention is improved, and a uniform film can be formed.
In addition, since titanium black is contained at a high concentration, sufficient light shielding properties can be obtained, and a polymerizable composition containing titanium black can be suitably used for forming a light shielding color filter.
＜（Ａ’）チタンブラック以外の顔料＞
　本発明の分散組成物、及び、重合性組成物は、チタンブラックに加えて、必要に応じて体質顔料を添加してもよい。このような体質顔料としては、例えば、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、塩基性炭酸マグネシウム、アルミナ白、グロス白、チタンホワイト、ハイドロタルサイト等を挙げることができる。これらの体質顔料は、単独で又は２種以上を混合して使用することができる。体質顔料の使用量は、チタンブラック１００質量部に対して、通常、０～１００質量部、好ましくは５～５０質量部、更に好ましくは１０～４０質量部である。本発明において、前記チタンブラック及び体質顔料は、場合により、それらの表面をポリマーで改質して使用することができる。 <(A ′) Pigments other than Titanium Black>
The dispersion composition and the polymerizable composition of the present invention may contain extender pigments as necessary in addition to titanium black. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of titanium black. In the present invention, the titanium black and extender pigment can be used by modifying their surfaces with a polymer in some cases.
　また、本発明の分散組成物、及び、重合性組成物は、遮光用顔料として、チタンブラック以外のものを混合して使用してもよい。
　このような混合可能な遮光用顔料としては、可視光領域に吸光度を有するものであれば特に限定はされず、上記した体質顔料、カーボンブラック、Ｃ．Ｉ．ＰｉｇｍｅｎｔＢｌｕｅ １，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０、Ｃ．Ｉ．ＰｉｇｍｅｎｔＶｉｏｌｅｔ １，１９，２３，２７，３２，３７，４２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｒｏｗｎ ２５，２８、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌａｃｋ １，７等の有機顔料等を挙げることができる。
　チタンブラック以外の遮光用顔料を混合する例として、チタンブラックとカーボンブラックを６：１で混合した物、チタンブラックと酸化チタンを３：１で混合した物などが挙げられる。
　混合するチタンブラック以外の遮光用顔料は、チタンブラック１００質量部に対して、０．０１～９９．９９質量部の範囲で用いることができる。好ましくは、２０～７０質量部の範囲である。 In addition, the dispersion composition and the polymerizable composition of the present invention may be used in combination with a pigment other than titanium black as a light shielding pigment.
Such a light-shielding pigment that can be mixed is not particularly limited as long as it has absorbance in the visible light region, and the above-mentioned extender pigment, carbon black, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, C.I. I. PigmentViolet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. And organic pigments such as Pigment Black 1 and 7.
Examples of mixing light-shielding pigments other than titanium black include a mixture of titanium black and carbon black in a ratio of 6: 1, and a mixture of titanium black and titanium oxide in a ratio of 3: 1.
The light-shielding pigment other than titanium black to be mixed can be used in the range of 0.01 to 99.99 parts by mass with respect to 100 parts by mass of titanium black. Preferably, it is in the range of 20 to 70 parts by mass.
＜（Ｂ）グラフト鎖を有する構造単位と、前記グラフト鎖を有する構造単位とは異なる疎水性構造単位とを有する高分子化合物＞
　本発明における高分子化合物（Ｂ）は、グラフト鎖を有する構造単位と、前記グラフト鎖を有する構造単位とは異なる疎水性構造単位とを有している。 <(B) Polymer compound having a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain>
The polymer compound (B) in the present invention has a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain.
　本発明における高分子化合物（Ｂ）としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン、及び顔料誘導体等を挙げることができる。
　本発明における高分子化合物（Ｂ）は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及びブロック型高分子に分類することができる。 As the polymer compound (B) in the present invention, a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, and pigment derivatives.
The polymer compound (B) in the present invention can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from its structure.
　本発明における高分子化合物（Ｂ）は、チタンブラック粒子及び所望により併用する顔料等の被分散体の表面に吸着し、再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を有する末端変性型高分子、グラフト型高分子、ブロック型高分子が好ましい構造として挙げることができる。
　一方で、チタンブラック粒子や、上記したチタンブラック及びＳｉ原子を含む被分散体の表面を改質することにより、これらに対する高分子化合物（Ｂ）の吸着性を促進させることもできる。 The polymer compound (B) in the present invention acts to adsorb on the surface of a dispersion such as titanium black particles and a pigment to be used in combination, if desired, and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the adsorptivity of the polymer compound (B) to these can be promoted by modifying the surface of the titanium black particles or the above-mentioned dispersion material containing titanium black and Si atoms.
　高分子化合物（Ｂ）は、上記したように、グラフト鎖を有する構造単位を有する。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を有する構造単位を有する高分子化合物（Ｂ）は、グラフト鎖によって溶媒との親和性を有するために、チタンブラック粒子の分散性、及び経時後の分散安定性に優れるものである。また、重合性組成物においては、グラフト鎖の存在により重合性化合物又はその他の併用可能な樹脂などとの親和性を有するので、アルカリ現像で残渣を生じにくくなる。 As described above, the polymer compound (B) has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
The polymer compound (B) having a structural unit having such a graft chain is excellent in the dispersibility of the titanium black particles and the dispersion stability after the lapse of time because it has an affinity for the solvent by the graft chain. is there. In addition, since the polymerizable composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
　グラフト鎖が長くなると立体反発効果が高くなり分散性は向上するが、一方グラフト鎖が長すぎるとチタンブラックへの吸着力が低下して分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が４０～１００００の範囲であるものが好ましく、水素原子を除いた原子数が５０～２０００であるものがより好ましく、水素原子を除いた原子数が６０～５００であるものが更に好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to titanium black decreases and the dispersibility tends to decrease. Therefore, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
　グラフト鎖は、ポリマー構造を有することが好ましく、このようなポリマー構造としては、例えば、ポリアクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、及び、ポリエーテル構造などを挙げることができる。
　グラフト部位と溶媒との相互作用性を向上させ、それにより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有するグラフト鎖であることがより好ましい。 The graft chain preferably has a polymer structure, and examples of such a polymer structure include a polyacrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and Examples thereof include a polyether structure.
The graft chain has at least one selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure in order to improve the interaction between the graft site and the solvent and thereby increase the dispersibility. And a graft chain having at least one of a polyester structure and a polyether structure is more preferable.
　このようなポリマー構造をグラフト鎖として有するマクロモノマーの構造としては、ポリマー主鎖部と反応可能な置換基を有し、かつ本発明の要件を満たしていれば、特に限定されないが、好ましくは、反応性二重結合性基を有するマクロモノマーを好適に使用することができる。 The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain portion and satisfies the requirements of the present invention. A macromonomer having a reactive double bond group can be preferably used.
　高分子化合物（Ｂ）が有するグラフト鎖を有する構造単位に対応し、高分子化合物（Ｂ）の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６（商品名、（商品名、東亜合成（株））、ＡＡ－１０（商品名、東亜合成（株）製）、ＡＢ－６（商品名、東亜合成（株）製）、ＡＳ－６（東亜合成（株））、ＡＮ－６（商品名、東亜合成（株）製）、ＡＷ－６（商品名、東亜合成（株）製）、ＡＡ－７１４（商品名、東亜合成（株）製）、ＡＹ－７０７（商品名、東亜合成（株）製）、ＡＹ－７１４（商品名、東亜合成（株）製）、ＡＫ－５（商品名、東亜合成（株）製）、ＡＫ－３０（商品名、東亜合成（株）製）、ＡＫ－３２（商品名、東亜合成（株）製）、ブレンマーＰＰ－１００（商品名、日油（株）製）、ブレンマーＰＰ－５００（商品名、日油（株）製）、ブレンマーＰＰ－８００（商品名、日油（株）製）、ブレンマーＰＰ－１０００（商品名、日油（株）製）、ブレンマー５５－ＰＥＴ－８００（日油（株）製）、ブレンマーＰＭＥ－４０００（商品名、日油（株）製）、ブレンマーＰＳＥ－４００（商品名、日油（株）製）、ブレンマーＰＳＥ－１３００（商品名、日油（株）製）、ブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油（株）製）、などが用いられる。このなかでも、好ましくは、ＡＡ－６（東亜合成（株）製）、ＡＡ－１０（商品名、東亜合成（株））、ＡＢ－６（商品名、東亜合成（株）製）、ＡＳ－６商品名、東亜合成（株））、ＡＮ－６（商品名、東亜合成（株）製）、ブレンマーＰＭＥ－４０００（商品名、日油（株）製）などが用いられる。 Corresponding to the structural unit having a graft chain of the polymer compound (B), a commercially available macromonomer suitably used for the synthesis of the polymer compound (B) includes AA-6 (trade name, (trade name, Toa Synthesis Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (Toa Gosei Co., Ltd.), AN-6 (Trade name, manufactured by Toa Gosei Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei) Synthetic Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.) ), AK-32 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer P-500 (trade name, manufactured by NOF Corporation), BREMMER PP-800 (trade name, manufactured by NOF Corporation), BREMMER PP-1000 (trade name, manufactured by NOF Corporation), Blemmer 55- PET-800 (manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation), BLEMMER PSE-400 (trade name, manufactured by NOF Corporation), BLEMMER PSE-1300 (commodity) Name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation), etc. Among them, AA-6 (produced by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, Toa Gosei) Synthetic Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) Such as is used.
　高分子化合物（Ｂ）は、グラフト鎖を有する構造単位として、下記式（１）～式（４）のいずれかで表される構造単位を含むことが好ましく、下記式（１Ａ）、下記式（２Ａ）、下記式（３Ａ）、下記式（３Ｂ）、及び下記（４）のいずれかで表される構造単位を含むことがより好ましい。 The polymer compound (B) preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain. 2A), a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4) is more preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（１）～式（４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４はそれぞれ独立に酸素原子或いはＮＨを表す。Ｗ１、Ｗ２、Ｗ３、及びＷ４は酸素原子であることが好ましい。
　式（１）～式（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５としては、合成上の制約の観点からは、好ましくはそれぞれ独立に水素原子又は炭素数１～１２のアルキル基であり、それぞれ独立に水素原子又はメチル基であることがより好ましく、メチル基が特に好ましい。 In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represents hydrogen. An atom or a methyl group is more preferable, and a methyl group is particularly preferable.
　式（１）～式（４）において、Ｙ１、Ｙ２、Ｙ３、及びＹ４は、それぞれ独立に、２価の連結基を表し、該連結基は特に構造上制約されない。Ｙ１、Ｙ２、Ｙ３、及びＹ４で表される２価の連結基として、具体的には、下記の（Ｙ－１）～（Ｙ－２１）の連結基などが例として挙げられる。下記に示した構造において、Ａ、Ｂはそれぞれ、式（１）～式（４）における左末端基、右末端基との結合部位を意味する。下記に示した構造のうち、合成の簡便性から、(Ｙ－２)又は（Ｙ－１３）であることがより好ましい。 In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups. . In the structures shown below, A and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（１）～式（４）において、Ｚ１、Ｚ２、Ｚ３、及びＺ４は、それぞれ独立に１価の有機基を表す。該有機基の構造は、特に限定されないが、具体的には、アルキル基、水酸基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、及びアミノ基などが挙げられる。これらの中でも、Ｚ１、Ｚ２、Ｚ３、及びＺ４で表される有機基としては、特に分散性向上の観点から、立体反発効果を有するものが好ましく、各々独立に炭素数５から２４のアルキル基が好ましく、その中でも、特に各々独立に炭素数５から２４の分岐アルキル基或いは炭素数５から２４の環状アルキル基が好ましい。 In the formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group. Although the structure of the organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc. Among these, as the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Among them, a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable.
　式（１）～式（４）において、ｎ、ｍ、ｐ、及びｑは、それぞれ１から５００の整数である。
　また、式（１）及び式（２）において、ｊ及びｋは、それぞれ独立に、２～８の整数を表す。式（１）及び式（２）におけるｊ及びｋは、分散安定性、現像性の観点から、４～６の整数が好ましく、５が最も好ましい。 In the formulas (1) to (4), n, m, p, and q are each an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
　式（３）中、Ｒ３は分岐若しくは直鎖のアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２又は３のアルキレン基であることがより好ましい。ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。
　式（４）中、Ｒ４は水素原子又は１価の有機基を表し、この１価の有機基としては特に構造上限定はされない。Ｒ４として好ましくは、水素原子、アルキル基、アリール基、及びヘテロアリール基が挙げられ、更に好ましくは、水素原子、又はアルキル基である。該Ｒ４がアルキル基である場合、該アルキル基としては、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐状アルキル基、又は炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基が特に好ましい。式（４）において、ｑが２～５００のとき、複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。 In the formula (3), R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 may be the same or different from each other.
　高分子化合物（Ｂ）において、式（１）～式（４）で表される構造単位は、質量換算で、高分子化合物（Ｂ）の総質量に対し１０％～９０％の範囲で含まれることが好ましく、３０％～７０％の範囲で含まれることがより好ましい。式（１）～式（４）で表される構造単位が、この範囲内で含まれるとチタンブラック粒子の分散性が高く、遮光膜を形成する際の現像性が良好である。 In the polymer compound (B), the structural units represented by the formulas (1) to (4) are contained in a range of 10% to 90% in terms of mass with respect to the total mass of the polymer compound (B). Preferably, it is contained in the range of 30% to 70%. When the structural units represented by the formulas (1) to (4) are included within this range, the dispersibility of the titanium black particles is high and the developability when forming the light-shielding film is good.
　また、高分子化合物（Ｂ）は、２種以上の構造が異なる、グラフト鎖を有する構造単位を有することができる。即ち、高分子化合物（Ｂ）の分子中に、互いに構造の異なる式（１）～式（４）で示される構造単位を含んでいてもよく、また、式（１）～式（４）においてｎ、ｍ、ｐ、及びｑがそれぞれ２以上の整数を表す場合、式（１）及び式（２）においては、側鎖中にｊ及びｋが互いに異なる構造を含んでいてもよく、式（３）及び式（４）においては、分子内に複数存在するＲ３、Ｒ４及びＸ５は互いに同じであっても異なっていてもよい。 Moreover, the high molecular compound (B) can have a structural unit having a graft chain in which two or more kinds of structures are different. That is, in the molecule of the polymer compound (B), structural units represented by the formulas (1) to (4) having different structures may be included, and in the formulas (1) to (4), When n, m, p, and q each represent an integer of 2 or more, in the formula (1) and the formula (2), j and k may include structures different from each other in the side chain. In 3) and formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
　前記式（１）で表される構造単位としては、分散安定性、現像性の観点から、下記式（１Ａ）で表される構造単位であることがより好ましい。
　また、前記式（２）で表される構造単位としては、分散安定性、現像性の観点から、下記式（２Ａ）で表される構造単位であることがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（１Ａ）中、Ｘ１、Ｙ１、Ｚ１及びｎは、前記式（１）におけるＸ１、Ｙ１、Ｚ１及びｎと同義であり、好ましい範囲も同様である。式（２Ａ）中、Ｘ２、Ｙ２、Ｚ２及びｍは、前記式（２）におけるＸ２、Ｙ２、Ｚ２及びｍと同義であり、好ましい範囲も同様である。 Wherein (1A), X 1, Y 1, Z 1 and n, the equation (1) is X 1, Y 1, synonymous with Z 1 and n in, and preferred ranges are also the same. Wherein (2A), X 2, Y 2, Z 2 and m is the formula (2) have the same meanings as X 2, Y 2, Z 2 and m in the preferred range is also the same.
　また、前記式（３）で表される構造単位としては、分散安定性、現像性の観点から、下記式（３Ａ）又は式（３Ｂ）で表される構造単位であることがより好ましい。 Further, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoints of dispersion stability and developability.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（３Ａ）又は（３Ｂ）中、Ｘ３、Ｙ３、Ｚ３及びｐは、前記式（３）におけるＸ３、Ｙ３、Ｚ３及びｐと同義であり、好ましい範囲も同様である。 Wherein (3A) or (3B), X 3, Y 3, Z 3 and p, the formula (3) X 3, Y 3 , have the same meaning as Z 3 and p in, preferred ranges are also the same.
　高分子化合物（Ｂ）は、グラフト鎖を有する構造単位として、前記式（１Ａ）で表される構造単位を有することがより好ましい。 It is more preferable that the polymer compound (B) has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
　高分子化合物（Ｂ）において、グラフト鎖を有する構造単位は、質量換算で、高分子化合物（Ｂ）の総質量に対し１０％～９０％の範囲で含まれることが好ましく、３０％～７０％の範囲で含まれることがより好ましい。グラフト鎖を有する構造単位が、この範囲内で含まれるとチタンブラック粒子の分散性が高く、遮光膜を形成する際の現像性が良好である。 In the polymer compound (B), the structural unit having a graft chain is preferably contained in a range of 10% to 90% in terms of mass with respect to the total mass of the polymer compound (B), and 30% to 70%. It is more preferable that it is included in the range. When the structural unit having a graft chain is contained within this range, the dispersibility of the titanium black particles is high, and the developability when forming the light-shielding film is good.
　また、高分子化合物（Ｂ）は、上記したように、前記グラフト鎖を有する構造単位とは異なる（すなわち、前記グラフト鎖を有する構造単位には相当しない）疎水性構造単位を有する。ただし、本発明において、疎水性構造単位は、酸基（例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基等）を有さない構造単位である。 Further, as described above, the polymer compound (B) has a hydrophobic structural unit different from the structural unit having the graft chain (that is, not corresponding to the structural unit having the graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
　疎水性構造単位は、好ましくは、ＣｌｏｇＰ値が１．２以上の化合物（モノマー）に由来する（対応する）構造単位であり、より好ましくは、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位である。これにより、本発明の効果をより確実に発現することができる。 The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
　ＣｌｏｇＰ値は、Ｄａｙｌｉｇｈｔ　Ｃｈｅｍｉｃａｌ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍ，　Ｉｎｃ．から入手できるプログラム“ＣＬＯＧＰ”で計算された値である。このプログラムは、Ｈａｎｓｃｈ，　Ｌｅｏのフラグメントアプローチ（下記文献参照）により算出される“計算ｌｏｇＰ”の値を提供する。フラグメントアプローチは化合物の化学構造に基づいており、化学構造を部分構造（フラグメント）に分割し、そのフラグメントに対して割り当てられたｌｏｇＰ寄与分を合計することにより化合物のｌｏｇＰ値を推算している。その詳細は以下の文献に記載されている。本発明では、プログラムＣＬＯＧＰ　ｖ４．８２により計算したＣｌｏｇＰ値を用いた。
　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． ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 was used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.
　ｌｏｇＰは、分配係数Ｐ（Ｐａｒｔｉｔｉｏｎ　Ｃｏｅｆｆｉｃｉｅｎｔ）の常用対数を意味し、ある有機化合物が油（一般的には１－オクタノール）と水の２相系の平衡でどのように分配されるかを定量的な数値として表す物性値であり、以下の式で示される。
　　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すことを意味し、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。 log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
　高分子化合物（Ｂ）は、疎水性構造単位として、下記一般式（ｉ）～（ｉｉｉ）で表される単量体に由来する構造単位から選択される１種以上の構造単位を有することが好ましい。 The polymer compound (B) may have one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units. preferable.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記一般式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、又はアルキル基（炭素原子数１～６のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基等）を表す。
　Ｒ１、Ｒ２、及びＲ３は、より好ましくは水素原子、又は炭素原子数が１～３のアルキル基であり、最も好ましくは、水素原子又はメチル基である。Ｒ２及びＲ３は、水素原子であることが特に好ましい。
　Ｘは、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。 In the general formulas (i) to (iii), R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (the number of carbon atoms) 1 to 6 alkyl groups are preferable, and examples thereof include a methyl group, an ethyl group, and a propyl group.
R 1 , R 2 , and R 3 are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R 2 and R 3 are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
　Ｌは、単結合又は２価の連結基である。２価の連結基としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、置換アリーレン基）、２価の複素環基、及び、これらと酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）又はカルボニル基（－ＣＯ－）との組合せ等が挙げられる。 L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene groups), divalent heterocyclic groups, and oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR 31 —, R 31 is an aliphatic group, aromatic group or heterocyclic group) or a combination with a carbonyl group (—CO—).
　前記２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。前記脂肪族基の炭素原子数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基であっても飽和脂肪族基であっても良いが、飽和脂肪族基であることが好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基等が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
　前記２価の芳香族基の炭素原子数は、６～２０が好ましく、６～１５が更に好ましく、６～１０が最も好ましい。また、前記芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基等が挙げられる。 The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
　前記２価の複素環基は、複素環として５員環又は６員環を有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基を挙げられる。 The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
　Ｌは、単結合、アルキレン基又はオキシアルキレン構造を含む２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造であることがより好ましい。また、Ｌはオキシアルキレン構造を２以上繰り返して含むポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としてはポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　Ｚとしては、脂肪族基（例えば、アルキル基、置換アルキル基、不飽和アルキル基、置換不飽和アルキル基、）、芳香族基（例えば、アリーレン基、置換アリーレン基）、複素環基及びそれらと酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）又はカルボニル基（－ＣＯ－）との組合せ等が挙げられる。 Z includes aliphatic groups (eg, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (eg, arylene groups, substituted arylene groups), heterocyclic groups, and Oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 is an aliphatic group, aromatic group or heterocyclic group) Or a combination with a carbonyl group (—CO—) and the like can be mentioned.
　前記脂肪族基は、環状構造又は分岐構造を有していてもよい。前記脂肪族基の炭素原子数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。更に環集合炭化水素基、架橋環式炭化水素基が含まれ、環集合炭化水素基の例としては、ビシクロヘキシル基、パーヒドロナフタレニル基、ビフェニル基、４－シクロヘキシルフェニル基などが含まれる。架橋環式炭化水素環として、例えば、ピナン、ボルナン、ノルピナン、ノルボルナン、ビシクロオクタン環（ビシクロ［２．２．２］オクタン環、ビシクロ［３．２．１］オクタン環等）などの２環式炭化水素環及び、ホモブレダン、アダマンタン、トリシクロ［５．２．１．０２，６］デカン、トリシクロ［４．３．１．１２，５］ウンデカン環などの３環式炭化水素環、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカン、パーヒドロ－１，４－メタノ－５，８－メタノナフタレン環などの４環式炭化水素環などが挙げられる。また、架橋環式炭化水素環には、縮合環式炭化水素環、例えば、パーヒドロナフタレン（デカリン）、パーヒドロアントラセン、パーヒドロフェナントレン、パーヒドロアセナフテン、パーヒドロフルオレン、パーヒドロインデン、パーヒドロフェナレン環などの５～８員シクロアルカン環が複数個縮合した縮合環も含まれる。
　脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms. Furthermore, a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group are included, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. . As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.02,6] decane, tricyclo [4.3.1.12,5] undecane ring, tetracyclo [4. 4.0.12, 5.17,10] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
　前記芳香族基の炭素原子数は、６～２０が好ましく、６～１５が更に好ましく、６～１０が最も好ましい。また、前記芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基を挙げられる。ただし、芳香族基は、置換基として酸基を有さない。 The number of carbon atoms of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
　前記複素環基は、複素環として５員環又は６員環を有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基を挙げられる。ただし、複素環基は、置換基として酸基を有さない。 The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
　上記式（ｉｉｉ）中、Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、又はアルキル基（炭素原子数１～６のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基等）、Ｚ、又は－Ｌ－Ｚを表す。ここでＬ及びＺは、上記におけるものと同義である。Ｒ４、Ｒ５、及びＲ６としては、水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In the above formula (iii), R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (an alkyl having 1 to 6 carbon atoms). A group, for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　本発明においては、上記一般式（ｉ）で表される単量体として、Ｒ１、Ｒ２、及びＲ３が水素原子又はメチル基であって、Ｌがアルキレン基又はオキシアルキレン構造を含む２価の連結基であって、Ｘが酸素原子又はイミノ基であって、Ｚが脂肪族基、複素環基又は芳香族基である化合物が好ましい。
　また、上記一般式（ｉｉ）で表される単量体として、Ｒ１が水素原子又はメチル基であって、Ｌがアルキレン基であって、Ｚが脂肪族基、複素環基又は芳香族基であって、Ｙがメチン基である化合物が好ましい。また、上記一般式（ｉｉｉ）で表される単量体として、Ｒ４、Ｒ５、及びＲ６が水素原子又はメチル基であって、Ｚが脂肪族基、複素環基又は芳香族基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L includes an alkylene group or an oxyalkylene structure 2 A compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. A compound in which Y is a methine group is preferred. Further, as the monomer represented by the general formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
　式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、アクリル酸エステル類、メタクリル酸エステル類、スチレン類などから選ばれるラジカル重合性化合物が挙げられる。 Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
　具体的には、例えば、アルキルアクリレート（該アルキル基の炭素原子数は１～２０のものが好ましい）等のアクリル酸エステル類、（具体的には、例えば、ベンジルアクリレート、４－ビフェニルアクリレート、ブチルアクリレート、ｓｅｃ－ブチルアクリレート、ｔ－ブチルアクリレート、４－ｔ－ブチルフェニルアクリレート、オクチルアクリレート、ドデシルアクリレート、４－クロロフェニルアクリレート、ペンタクロロフェニルアクリレート、トリフルオロメチルメチルアクリレート、トリデカンフルオロヘキシルエチルアクリレート４－シアノベンジルアクリレート、シアノメチルアクリレート、シクロヘキシルアクリレート、２－エトキシエチルアクリレート、エチルアクリレート、２－エチルヘキシルアクリレート、ヘプチルアクリレート、ヘキシルアクリレート、イソボロニルアクリレート、イソプロピルアクリレート、メチルアクリレート、３，５－ジメチルアダマンチルアクリレート、２－ナフチルアクリレート、ネオペンチルアクリレート、フルオレニルアクリレート、フェネチルアクリレート、フェニルアクリレート、プロピルアクリレート、トリルアクリレート、アミルアクリレート、テトラヒドロフルフリルアクリレート、アリルアクリレート、２－アリロキシエチルアクリレート、プロパギルアクリレート、アダマンチルアクリレートなど） Specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), (specifically, for example, benzyl acrylate, 4-biphenyl acrylate, butyl Acrylate, sec-butyl acrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, octyl acrylate, dodecyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate, trifluoromethyl methyl acrylate, tridecanefluorohexyl ethyl acrylate 4-cyano Benzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, Tyl acrylate, hexyl acrylate, isobornyl acrylate, isopropyl acrylate, methyl acrylate, 3,5-dimethyladamantyl acrylate, 2-naphthyl acrylate, neopentyl acrylate, fluorenyl acrylate, phenethyl acrylate, phenyl acrylate, propyl acrylate, tolyl acrylate Amyl acrylate, tetrahydrofurfuryl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, adamantyl acrylate, etc.)
　アルキルメタクリレート（該アルキル基の炭素原子は１～２０のものが好ましい）等のメタクリル酸エステル類（例えば、ベンジルメタクリレート、４－ビフェニルメタクリレート、ブチルメタクリレート、ｓｅｃ－ブチルメタクリレート、ｔ－ブチルメタクリレート、４－ｔ－ブチルフェニルメタクリレート、オクチルメタクリレート、ドデシルメタクリレート、４－クロロフェニルメタクリレート、ペンタクロロフェニルメタクリレート、トリフルオロメチルメチルメタクリレート、トリデカンフルオロヘキシルエチルメタクリレート、４－シアノフェニルメタクリレート、シアノメチルメタクリレート、シクロヘキシルメタクリレート、２－エトキシエチルメタクリレート、エチルメタクリレート、２－エチルヘキシルメタクリレート、ヘプチルメタクリレート、ヘキシルメタクリレート、イソボロニルメタクリレート、イソプロピルメタクリレート、メチルメタクリレート、３，５－ジメチルアダマンチルメタクリレート、２－ナフチルメタクリレート、ネオペンチルメタクリレート、フルオレニルメタクリレート、フェネチルメタクリレート、フェニルメタクリレート、プロピルメタクリレート、トリルメタクリレート、アミルメタクリレート、テトラヒドロフルフリルメタクリレート、アリルメタクリレート、２－アリロキシエチルメタクリレート、プロパギルメタクリレート、アダマンチルメタクリレートなど、 Methacrylic acid esters (for example, benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 4-alkyl methacrylate (preferably having 1 to 20 carbon atoms in the alkyl group)) t-butylphenyl methacrylate, octyl methacrylate, dodecyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, trifluoromethylmethyl methacrylate, tridecanefluorohexylethyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate, 2-ethoxy Ethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate , Heptyl methacrylate, hexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, fluorenyl methacrylate, phenethyl methacrylate, phenyl methacrylate, propyl methacrylate, tolyl Methacrylate, amyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, adamantyl methacrylate, etc.
　スチレン、アルキルスチレン等のスチレン類（例えば、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブチルスチレン、ヘキシルスチレン、シクロへキシルスチレン、デシルスチレン、ベンジルスチレン、クロルメチルスチレン、トリフルオロメチルスチレン、エトキシメチルスチレン、アセトキシメチルスチレンなど）、アルコキシスチレン（例えばメトキシスチレン、４－メトキシ－３－メチルスチレン、ジメトキシスチレンなど）、ハロゲン化スチレン（例えばクロルスチレン、ジクロルスチレン、トリクロルスチレン、テトラクロルスチレン、ペンタクロルスチレン、ブロムスチレン、ジブロムスチレン、ヨードスチレン、フルオルスチレン、トリフルオロスチレン、２－ブロム－４－トリフルオルメチルスチレン、４－フルオル－３－トリフルオルメチルスチレンなど）等が挙げられる。 Styrenes such as styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogenated styrene (eg chloro styrene, dichloro styrene, trichloro styrene) , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluoro Styrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), and the like.
　これらラジカル重合性化合物のうち、好適に使用されるのは、メタクリル酸エステル類、スチレン類であり、特に好適に使用されるのは、ベンジルメタクリレート、ｔ－ブチルメタクリレート、４－ｔ－ブチルフェニルメタクリレート、ペンタクロロフェニルメタクリレート、４－シアノフェニルメタクリレート、シクロヘキシルメタクリレート、エチルメタクリレート、２－エチルヘキシルメタクリレート、イソボロニルメタクリレート、イソプロピルメタクリレート、メチルメタクリレート、３，５－ジメチルアダマンチルメタクリレート、２－ナフチルメタクリレート、ネオペンチルメタクリレート、フェニルメタクリレート、テトラヒドロフルフリルメタクリレート、アリルメタクリレート、 Among these radical polymerizable compounds, methacrylic acid esters and styrenes are preferably used, and benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate are particularly preferably used. , Pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, Phenyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate,
　スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、イソプロピルスチレン、ブチルスチレン、シクロへキシルスチレン、クロルメチルスチレン、トリフルオルメチルスチレン、エトキシメチルスチレン、アセトキシメチルスチレン、メトキシスチレン、４－メトキシ－３－メチルスチレン、クロルスチレン、ジクロルスチレン、トリクロルスチレン、テトラクロルスチレン、ペンタクロルスチレン、ブロムスチレン、ジブロムスチレン、ヨードスチレン、フルオルスチレン、トリフルオルスチレン、２－ブロム－４－トリフルオルメチルスチレン、４－フルオル－３－トリフルオルメチルスチレン、１－ビニルナフタレン、２－ビニルナフタレンである。 Styrene, methyl styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene , Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4- Fluoro-3-trifluoromethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene.
　また、疎水性構造単位に対応する単量体の内、複素環基を含有する化合物としては以下に示す化合物が挙げられる。 In addition, among the monomers corresponding to the hydrophobic structural unit, the following compounds are exemplified as the compound containing a heterocyclic group.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　高分子化合物（Ｂ）において、疎水性構造単位は、質量換算で、高分子化合物（Ｂ）の総質量に対し１０％～９０％の範囲で含まれることが好ましく、２０％～８０％の範囲で含まれることがより好ましい。含有量が前記の範囲において十分なパターン形成が得られる。 In the polymer compound (B), the hydrophobic structural unit is preferably contained in a range of 10% to 90% and in a range of 20% to 80% with respect to the total mass of the polymer compound (B) in terms of mass. It is more preferable that it is contained. When the content is in the above range, sufficient pattern formation can be obtained.
　高分子化合物（Ｂ）は、チタンブラックと相互作用を形成しうる官能基を導入することができる。ここで、高分子化合物（Ｂ）は、チタンブラックと相互作用を形成しうる官能基を有する構造単位を更に有することが好ましい。
　このチタンブラック粒子と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、反応性を有する官能基等があげられる。
　高分子化合物（Ｂ）が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を有する場合、それぞれ、酸基を有する構造単位、塩基性基を有する構造単位、配位性基を有する構造単位、又は、反応性を有する構造単位を有することが好ましい。
　特に、高分子化合物（Ｂ）が、更に、酸基として、カルボン酸基などのアルカリ可溶性基を有することで、高分子化合物（Ｂ）に、アルカリ現像によるパターン形成のための現像性を付与することができる。
　すなわち、高分子化合物（Ｂ）に、アルカリ可溶性基を導入することで、本発明の分散組成物は、チタンブラック粒子の分散に不可欠の分散剤としての高分子化合物（Ｂ）がアルカリ可溶性を有することになる。このような分散組成物を含有する重合性組成物は、露光部の遮光性に優れたものとなり、かつ、未露光部のアルカリ現像性が向上される。
　また、高分子化合物（Ｂ）が酸基を有する構造単位を有することにより、高分子化合物（Ｂ）が溶媒（Ｃ）となじみやすくなり、塗布性も向上する傾向となる。 The polymer compound (B) can introduce a functional group capable of forming an interaction with titanium black. Here, the polymer compound (B) preferably further includes a structural unit having a functional group capable of forming an interaction with titanium black.
Examples of the functional group capable of forming an interaction with the titanium black particles include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound (B) has an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit having an acid group, the structural unit having a basic group, and a coordination group, respectively. It is preferable to have a structural unit having a coordinate group or a structural unit having reactivity.
In particular, the polymer compound (B) further has an alkali-soluble group such as a carboxylic acid group as an acid group, thereby imparting developability for pattern formation by alkali development to the polymer compound (B). be able to.
That is, by introducing an alkali-soluble group into the polymer compound (B), the dispersion composition of the present invention has the polymer compound (B) as a dispersant essential for dispersing the titanium black particles having alkali solubility. It will be. The polymerizable composition containing such a dispersion composition has excellent light shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound (B) has a structural unit which has an acid group, a high molecular compound (B) becomes easy to become compatible with a solvent (C), and it exists in the tendency for applicability | paintability to improve.
　ただし、酸基としてのアルカリ可溶性基を有する構造単位は、上記したグラフト鎖を有する構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、酸基としてのアルカリ可溶性基を有する構造単位は、上記した疎水性構造単位とは異なる構造単位である（すなわち、上記した疎水性構造単位には相当しない）。 However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
　チタンブラックと相互作用を形成しうる官能基である酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基などがあり、好ましくは、カルボン酸基、スルホン酸基、リン酸基のうち少なくとも１種であり、特に好ましいものは、チタンブラック粒子への吸着力が良好で、かつ、その分散性が高いカルボン酸基である。
　すなわち、高分子化合物（Ｂ）は、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種を有する構造単位を更に有することが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with titanium black include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, preferably a carboxylic acid group, a sulfonic acid group, Among the phosphoric acid groups, at least one kind, and particularly preferred is a carboxylic acid group that has good adsorption power to titanium black particles and has high dispersibility.
That is, the polymer compound (B) preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
　高分子化合物（Ｂ）は、酸基を有する構造単位を１種或いは２種以上有してもよい。
　高分子化合物（Ｂ）は、酸基を有する構造単位を含有してもしなくても良いが、含有する場合、酸基を有する構造単位の含有量は、質量換算で、高分子化合物（Ｂ）の総質量に対して、好ましくは５％以上８０％以下であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、１０％以上６０％以下である。 The polymer compound (B) may have one or more structural units having an acid group.
The polymer compound (B) may or may not contain a structural unit having an acid group, but when it is contained, the content of the structural unit having an acid group is, in terms of mass, the polymer compound (B). Is preferably 5% or more and 80% or less, and more preferably 10% or more and 60% or less from the viewpoint of suppressing damage of image strength due to alkali development.
　チタンブラックと相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含むヘテロ環、アミド基などがあり、特に好ましいものは、チタンブラックへの吸着力が良好で、かつ、その分散性が高い第３級アミノ基である。高分子化合物（Ｂ）は、これらの塩基性基を１種或いは１種以上、有することができる。
　高分子化合物（Ｂ）は、塩基性基を有する構造単位を含有してもしなくても良いが、含有する場合、塩基性基を有する構造単位の含有量は、質量換算で、高分子化合物（Ｂ）の総質量に対して、好ましくは０．０１％以上５０％以下であり、より好ましくは、現像性阻害抑制という観点から、０．０１％以上３０％以下である。 Examples of the basic group that is a functional group capable of forming an interaction with titanium black include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Among them, particularly preferred is a tertiary amino group having a good adsorptive power to titanium black and a high dispersibility. The polymer compound (B) can have one or more of these basic groups.
The polymer compound (B) may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is expressed in terms of mass in terms of a polymer compound ( Preferably it is 0.01% or more and 50% or less with respect to the gross mass of B), More preferably, it is 0.01% or more and 30% or less from a viewpoint of developability inhibition suppression.
　チタンブラックと相互作用を形成しうる官能基である配位性基、及び反応性を有する官能基としては、例えば、アセチルアセトキシ基、トリアルコキシシリル基、イソシアネート基、酸無水物、酸塩化物などが挙げられる。特に好ましいものは、チタンブラックへの吸着力が良好で分散性が高いアセチルアセトキシ基である。高分子化合物（Ｂ）は、これらの基を１種あるいは１種以上有してもよい。
　高分子化合物（Ｂ）は、配位性基を有する構造単位、又は、反応性を有する官能基を有する構造単位を含有してもしなくても良いが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物（Ｂ）の総質量に対して、好ましくは１０％以上８０％以下であり、より好ましくは、現像性阻害抑制という観点から、２０％以上６０％以下である。 Examples of the coordinating group, which is a functional group capable of forming an interaction with titanium black, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride, and the like. Is mentioned. Particularly preferred is an acetylacetoxy group that has good adsorption power to titanium black and high dispersibility. The polymer compound (B) may have one or more of these groups.
The polymer compound (B) may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group. The amount is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, in terms of mass, in terms of suppression of developability inhibition, with respect to the total mass of the polymer compound (B). is there.
　本発明における高分子化合物（Ｂ）が、グラフト鎖以外に、チタンブラックと相互作用を形成しうる官能基を有する場合、上述したような、各種のチタンブラックと相互作用を形成しうる官能基を含有していればよく、これらの官能基がどのように導入されているかは特に限定はされないが、高分子化合物（Ｂ）は、下記一般式（ｉｖ）～（ｖｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を有することが好ましい。 When the polymer compound (B) in the present invention has a functional group capable of interacting with titanium black in addition to the graft chain, the functional group capable of interacting with various titanium blacks as described above is provided. There is no particular limitation on how these functional groups are introduced as long as they are contained, but the polymer compound (B) is a monomer represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from the body.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、又は炭素原子数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、より好ましくは、それぞれ独立に水素原子、又は炭素原子数が１～３のアルキル基であり、最も好ましくは、それぞれ独立に水素原子又はメチル基である。一般式（ｉｖ）中、Ｒ１２及びＲ１３は、それぞれ水素原子であることが特に好ましい。 In general formula (iv) to general formula (vi), R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (iv) to general formula (vi), R 11 , R 12 and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, most preferably Are each independently a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are each particularly preferably a hydrogen atom.
　一般式（ｉｖ）中のＸ１は、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。
　また、一般式（ｖ）中のＹは、メチン基又は窒素原子を表す。 X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.
　また、一般式（ｉｖ）～一般式（ｖ）中のＬ１は、単結合又は２価の連結基を表す。該２価の連結基の例としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、及び置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、及び置換アリーレン基）、２価の複素環基及びそれらと酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ結合（－ＮＲ３１’－、ここでＲ３１’は脂肪族基、芳香族基又は複素環基）又はカルボニル結合（－ＣＯ－）のうちの一つ以上との組合せ等が挙げられる。 In the general formulas (iv) to (v), L 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group ( For example, an arylene group and a substituted arylene group), a divalent heterocyclic group and an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR) 31′- , where R 31 ′ is an aliphatic group, aromatic group or heterocyclic group) or a combination with one or more of carbonyl bonds (—CO—).
　前記２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。前記脂肪族基の炭素原子数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシル基、芳香族基及び複素環基が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
　前記２価の芳香族基の炭素原子数は、６～２０が好ましく、６～１５が更に好ましく、６～１０が最も好ましい。また、前記芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、ヒドロキシル基、脂肪族基、芳香族基及び複素環基を挙げられる。 The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
　前記２価の複素環基は、複素環として５員環又は６員環を有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環のうち１つ以上が縮合していてもよい。また、複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基を挙げられる。 The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
　Ｌ１は、単結合、アルキレン基又はオキシアルキレン構造を含む２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造であることがより好ましい。また、Ｌはオキシアルキレン構造を２以上繰り返して含むポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としてはポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　一般式（ｉｖ）～一般式（ｖｉ）中、Ｚ１は、グラフト部位以外にチタンブラック粒子と相互作用を形成しうる官能基を表し、カルボン酸基、第三級アミノ基であることが好ましく、カルボン酸基であることがより好ましい。 In the general formulas (iv) to (vi), Z 1 represents a functional group capable of interacting with the titanium black particles in addition to the graft site, and is preferably a carboxylic acid group or a tertiary amino group. More preferably, it is a carboxylic acid group.
　一般式（ｖｉ）中、Ｒ１４、Ｒ１５、及びＲ１６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、炭素原子数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、－Ｚ１、又は－Ｌ１－Ｚ１を表す。ここでＬ１及びＺ１は、上記におけるＬ１及びＺ１と同義であり、好ましい例も同様である。Ｒ１４、Ｒ１５、及びＲ１６としては、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In general formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, , methyl group, ethyl group, propyl group, etc.), - represents a Z 1, or -L 1 -Z 1. Wherein L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples. R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　本発明においては、一般式（ｉｖ）で表される単量体として、Ｒ１１、Ｒ１２、及びＲ１３がそれぞれ独立に水素原子又はメチル基であって、Ｌ１がアルキレン基又はオキシアルキレン構造を含む２価の連結基であって、Ｘが酸素原子又はイミノ基であって、Ｚがカルボン酸基である化合物が好ましい。
　また、一般式（ｖ）で表される単量体として、Ｒ１１が水素原子又はメチル基であって、Ｌ１がアルキレン基であって、Ｚ１がカルボン酸基であって、Ｙがメチン基である化合物が好ましい。
　更に、一般式（ｖｉ）で表される単量体として、Ｒ１４、Ｒ１５、及びＲ１６がそれぞれ独立に水素原子又はメチル基であって、Ｌが単結合又はアルキレン基であって、Ｚがカルボン酸基である化合物が好ましい。 In the present invention, as the monomer represented by the general formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as a monomer represented by the general formula (vi), R 14 , R 15 and R 16 are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid group is preferred.
　以下に、一般式（ｉｖ）～一般式（ｖｉ）で表される単量体（化合物）の代表的な例を示す。
　該単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合と水酸基を有する化合物（例えば、メタクリル酸２－ヒドロキシエチル）とコハク酸無水物の反応物、分子内に付加重合性二重結合と水酸基を有する化合物とフタル酸無水物の反応物、分子内に付加重合性二重結合と水酸基を有する化合物とテトラヒドロキシフタル酸無水物の反応物、分子内に付加重合性二重結合と水酸基を有する化合物と無水トリメリット酸の反応物、分子内に付加重合性二重結合と水酸基を有する化合物とピロメリット酸無水物の反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、４－ビニル安息香酸、ビニルフェノール、４－ヒドロキシフェニルメタクリルアミドなどが挙げられる。 The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
Examples of the monomer include a reaction product of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride, a molecule A reaction product of a compound having an addition polymerizable double bond and hydroxyl group and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic Acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenyl methacrylate And the like.
　チタンブラックと相互作用を形成しうる官能基の含有量は、チタンブラックとの相互作用、分散安定性、及び現像液への浸透性の観点から、高分子化合物（Ｂ）の全質量に対して０．０５質量％～９０質量％が好ましく、１．０質量％～８０質量％がより好ましく、１０質量％～７０質量％が更に好ましい。 The content of the functional group capable of forming an interaction with titanium black is based on the total mass of the polymer compound (B) from the viewpoint of interaction with titanium black, dispersion stability, and permeability to a developer. 0.05 mass% to 90 mass% is preferable, 1.0 mass% to 80 mass% is more preferable, and 10 mass% to 70 mass% is still more preferable.
　更に、高分子化合物（Ｂ）は、画像強度などの諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を有する構造単位、疎水性構造単位、及び、チタンブラック粒子と相互作用を形成しうる官能基を有する構造単位とは異なる、種々の機能を有する他の構造単位（例えば、分散物に用いられる分散媒との親和性を有する官能基などを有する構造単位）を更に有していても良い。 Furthermore, the polymer compound (B) is a structural unit having a graft chain, a hydrophobic structural unit, and titanium black particles as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. Other structural units having various functions different from structural units having a functional group capable of forming an interaction (for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion) Furthermore, you may have.
　このような、他の構造単位としては、例えば、アクリロニトリル類、メタクリロニトリル類などから選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。 Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
　高分子化合物（Ｂ）は、これらの他の構造単位を１種或いは２種以上用いることができ、その含有量は、質量換算で、高分子化合物（Ｂ）の総質量に対して、好ましくは０％以上８０％以下であり、特に好ましくは、１０％以上６０％以下である。含有量が前記の範囲において十分なパターン形成性が維持される。 In the polymer compound (B), one or more of these other structural units can be used, and the content thereof is preferably in terms of mass with respect to the total mass of the polymer compound (B). It is 0% or more and 80% or less, and particularly preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
　高分子化合物（Ｂ）の酸価は、０ｍｇＫＯＨ／ｇ以上１６０ｍｇＫＯＨ／ｇ以下の範囲であることが好ましく、より好ましくは１０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下の範囲であり、更に好ましくは２０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫＯＨ／ｇ以下の範囲である。
　高分子化合物（Ｂ）の酸価が１６０ｍｇＫＯＨ／ｇ以下であれば、遮光膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物（Ｂ）の酸価が１０ｍｇＫＯＨ／ｇ以上であればアルカリ現像性がより良好となる。また、高分子化合物（Ｂ）の酸価が２０ｍｇＫＯＨ／ｇ以上であれば、チタンブラックや、チタンブラック及びＳｉ原子を含む被分散体の沈降をより抑制でき、粗大粒子数をより少なくすることができ、分散組成物及び重合性組成物の経時安定性をより向上できる。 The acid value of the polymer compound (B) is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably 20 mgKOH / g or more. It is the range of 120 mgKOH / g or less.
If the acid value of the polymer compound (B) is 160 mgKOH / g or less, pattern peeling during development when forming the light-shielding film can be more effectively suppressed. Moreover, if the acid value of a high molecular compound (B) is 10 mgKOH / g or more, alkali developability will become more favorable. In addition, when the acid value of the polymer compound (B) is 20 mgKOH / g or more, it is possible to further suppress sedimentation of the dispersion containing titanium black and titanium black and Si atoms, thereby reducing the number of coarse particles. In addition, the temporal stability of the dispersion composition and the polymerizable composition can be further improved.
　本発明において、高分子化合物（Ｂ）の酸価は、例えば、高分子化合物（Ｂ）中における酸基の平均含有量から算出することができる。また、高分子化合物（Ｂ）の構成成分である酸基を含有する構造単位の含有量を変化させることで所望の酸価を有する樹脂を得ることができる。 In the present invention, the acid value of the polymer compound (B) can be calculated, for example, from the average content of acid groups in the polymer compound (B). Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound (B).
　本発明における高分子化合物（Ｂ）の重量平均分子量は、遮光膜を形成する際において、現像時のパターン剥離抑制と現像性の観点から、ＧＰＣ法によるポリスチレン換算値として、４，０００以上３００，０００以下であることが好ましく、５，０００以上２００，０００以下であることがより好ましく、６，０００以上１００，０００以下であることが更に好ましく、１０，０００以上５０，０００以下であることが特に好ましい。
　ＧＰＣ法は、ＨＬＣ－８０２０ＧＰＣ（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ２０００（東ソー（株）製、４．６ｍｍＩＤ×１５ｃｍ）を、溶離液としてＴＨＦ（テトラヒドロフラン）を用いる方法に基づく。 The weight average molecular weight of the polymer compound (B) in the present invention is 4,000 or more and 300,000 as a polystyrene conversion value by GPC method from the viewpoint of pattern peeling inhibition during development and developability when forming a light shielding film. Is preferably 5,000 or more, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and is preferably 10,000 or more and 50,000 or less. Particularly preferred.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
　高分子化合物（Ｂ）は、公知の方法に基づいて合成でき、高分子化合物（Ｂ）を合成する際に用いられる溶媒としては、例えば、エチレンジクロリド、シクロヘキサノン、メチルエチルケトン、アセトン、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２－メトキシエチルアセテート、１－メトキシ－２－プロパノール、１－メトキシ－２－プロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、トルエン、酢酸エチル、乳酸メチル、乳酸エチルなどが挙げられる。これらの溶媒は単独で用いても２種以上混合して用いてもよい。 The polymer compound (B) can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound (B) include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, and propanol. , Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide Dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These solvents may be used alone or in combination of two or more.
　本発明に用いうる高分子化合物（Ｂ）の具体例としては、ＢＹＫ　Ｃｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１６１、１６２、１６３、１６４、１６５、１６６、１７０（商品名、高分子共重合物）」、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０、４０１０、４１６５（商品名、ポリウレタン系）、ＥＦＫＡ４３３０、４３４０（商品名、ブロック共重合体）等が挙げられる。
　これらの高分子化合物（Ｂ）は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Specific examples of the polymer compound (B) that can be used in the present invention include “Disperbyk-161, 162, 163, 164, 165, 166, 170 (trade name, polymer copolymer)” manufactured by BYK Chemie, EFKA “EFKA 4047, 4050, 4010, 4165 (trade name, polyurethane-based), EFKA 4330, 4340 (trade name, block copolymer), etc., manufactured by the company are listed.
These polymer compounds (B) may be used alone or in combination of two or more.
　以下、高分子化合物（Ｂ）の具体例を示すが、本発明はこれらに限定されるものではない。なお、下記例示化合物中、各構造単位に併記される数値（主鎖繰り返し単位に併記される数値）は、当該構造単位の含有量〔質量％：（ｗｔ％）と記載〕を表す。側鎖の繰り返し部位に併記される数値は、当該繰り返し部位の繰り返し数を示す。 Hereinafter, although the specific example of a high molecular compound (B) is shown, this invention is not limited to these. In addition, in the following exemplary compounds, the numerical value written together with each structural unit (the numerical value written together with the main chain repeating unit) represents the content of the structural unit [described as mass%: (wt%)]. The numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　本発明の分散組成物における高分子化合物（Ｂ）の含有量は、分散組成物の全固形分質量に対して、１質量％～９０質量％が好ましく、３質量％～７０質量％がより好ましい。
　また、本発明の重合性組成物における高分子化合物（Ｂ）の含有量としては、重合性組成物の全固形分質量に対して、０．１質量％～５０質量％が好ましく、０．５質量％～３０質量％がより好ましい。 The content of the polymer compound (B) in the dispersion composition of the present invention is preferably 1% by mass to 90% by mass and more preferably 3% by mass to 70% by mass with respect to the total solid mass of the dispersion composition. .
The content of the polymer compound (B) in the polymerizable composition of the present invention is preferably 0.1% by mass to 50% by mass with respect to the total solid content mass of the polymerizable composition, A mass% to 30 mass% is more preferred.
＜（Ｂ’）樹脂（Ｂ）とは異なる樹脂＞
　本発明の分散組成物、及び、重合性組成物は、高分子化合物（Ｂ）とは異なる高分子化合物（Ｂ’）（すなわち、高分子化合物（Ｂ）には相当しない高分子化合物）を含有してもよい。
　高分子化合物（Ｂ’）の重量平均分子量の好ましい範囲は、高分子化合物（Ｂ）で説明したものと同様である。
　高分子化合物（Ｂ’）の具体例としては、ＢＹＫ　Ｃｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１０１（商品名、ポリアミドアミン燐酸塩）、１０７（商品名、カルボン酸エステル）、１１０（商品名、酸基を含む共重合物）、１３０（商品名、ポリアミド）、１８０（商品名、高分子共重合物）」、「ＢＹＫ－Ｐ１０４、Ｐ１０５（商品名、高分子量不飽和ポリカルボン酸）、ＥＦＫＡ社製「ＥＦＫＡ４４００、４４０２（商品名、変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（商品名、高分子量ポリカルボン酸塩）、６２２０（商品名、脂肪酸ポリエステル）、６７４５（商品名、フタロシアニン誘導体）、６７５０（商品名、アゾ顔料誘導体）」、味の素ファインテクノ（株）製「アジスパーＰＢ８２１、ＰＢ８２２」、共栄社化学（株）製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（商品名、アクリル系共重合体）」、楠本化成（株）製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（商品名、脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王（株）製「デモールＲＮ、Ｎ（商品名、ナフタレンスルホン酸ホルマリン重縮合物）、デモールＭＳ、Ｃ、ＳＮ－Ｂ（商品名、芳香族スルホン酸ホルマリン重縮合物）」、「ホモゲノールＬ－１８（商品名、高分子ポリカルボン酸）」、「エマルゲン９２０、９３０、９３５、９８５（商品名、ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、ルーブリゾール社製「ソルスパース５０００（フタロシアニン誘導体）、２２０００（商品名、アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１７０００、２７０００（商品名、末端部に機能部を有する高分子）、２４０００、２８０００、３２０００、３８５００（グラフト型高分子）」、日光ケミカル者製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレート）、ＭＹＳ－ＩＥＸ（商品名、ポリオキシエチレンモノステアレート）」等が挙げられる。
　また、川研ファインケミカル（株）製　ヒノアクトＴ－８０００Ｅなどの両性分散剤も挙げられる。 <(B ′) Resin Different from Resin (B)>
The dispersion composition and the polymerizable composition of the present invention contain a polymer compound (B ′) different from the polymer compound (B) (that is, a polymer compound not corresponding to the polymer compound (B)). May be.
The preferred range of the weight average molecular weight of the polymer compound (B ′) is the same as that described for the polymer compound (B).
Specific examples of the polymer compound (B ′) include “Disperbyk-101 (trade name, polyamidoamine phosphate), 107 (trade name, carboxylic acid ester), 110 (trade name, acid group) manufactured by BYK Chemie. Copolymer)), 130 (trade name, polyamide), 180 (trade name, polymer copolymer) "," BYK-P104, P105 (trade name, high molecular weight unsaturated polycarboxylic acid) "," EFKA4400 manufactured by EFKA Corporation. 4402 (trade name, modified polyacrylate), 5010 (polyester amide), 5765 (trade name, high molecular weight polycarboxylate), 6220 (trade name, fatty acid polyester), 6745 (trade name, phthalocyanine derivative), 6750 ( Product name, azo pigment derivative) ", Ajinomoto Fine Techno Co., Ltd." Azisper PB821, PB8 2 ”,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (trade name, acrylic copolymer) ”,“ Disparon KS manufactured by Enomoto Kasei Co., Ltd. ” -860, 873SN, 874, # 2150 (trade name, aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", manufactured by Kao Corporation Demol RN, N (trade name, naphthalenesulfonic acid formalin polycondensate), Demol MS, C, SN-B (trade name, aromatic sulfonic acid formalin polycondensate), “Homogenol L-18 (trade name, high Molecular polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (trade name, polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (trade name, azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (trade name, functional part at the end) 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (trade name, polyoxyethylene monostearate) "manufactured by Nikko Chemicals ) "And the like.
In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. may also be mentioned.
　本発明の分散組成物は、高分子化合物（Ｂ’）を含有しても含有しなくてもよいが、含有する場合、高分子化合物（Ｂ’）の含有量は、分散組成物の全固形分質量に対して、１質量％～９０質量％が好ましく、３質量％～７０質量％がより好ましい。
　また、本発明の重合性組成物は、高分子化合物（Ｂ’）を含有しても含有しなくてもよいが、含有する場合、高分子化合物（Ｂ’）の含有量は、重合性組成物の全固形分質量に対して、０．１質量％～５０質量％が好ましく、０．５質量％～３０質量％がより好ましい。 The dispersion composition of the present invention may or may not contain the polymer compound (B ′), but when it is contained, the content of the polymer compound (B ′) is the total solid content of the dispersion composition. 1% by mass to 90% by mass is preferable with respect to the partial mass, and 3% by mass to 70% by mass is more preferable.
Further, the polymerizable composition of the present invention may or may not contain the polymer compound (B ′), but when it is contained, the content of the polymer compound (B ′) is determined by the polymerizable composition. 0.1% by mass to 50% by mass is preferable and 0.5% by mass to 30% by mass is more preferable with respect to the total solid content mass of the product.
＜（Ｃ）溶媒＞
　本発明の分散組成物、及び、重合性組成物は、（Ｃ）溶媒を含有する。（Ｃ）溶媒は、有機溶媒であることが好ましい。
　有機溶媒の例としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチルなどが挙げられるが、これらに限定されない。 <(C) Solvent>
The dispersion composition and polymerizable composition of the present invention contain (C) a solvent. (C) The solvent is preferably an organic solvent.
Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate , Methyl lactate, ethyl lactate and the like, but are not limited thereto.
　溶媒は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　溶媒を２種以上組みあわせて用いる場合、特に好ましくは、上記の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－３－エトキシプロピオネート）、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－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、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メチルエーテル、及びプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される。
　分散組成物に含まれる（Ｃ）溶媒の量としては、分散組成物の全量に対し、１０質量％～８０質量％であることが好ましく、２０質量％～７０質量％であることがより好ましく、３０質量％～６５質量％であることが更に好ましい。また、重合性組成物に含まれる（Ｃ）溶媒の量としては、重合性組成物の全量に対し、１０質量％～９０質量％であることが好ましく、２０質量％～８０質量％であることがより好ましく、２５質量％～７５質量％であることが更に好ましい。 A solvent may be used individually by 1 type and may be used in combination of 2 or more type.
When two or more solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (ethyl-3-ethoxypropionate), ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether , Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The amount of the solvent (C) contained in the dispersion composition is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass with respect to the total amount of the dispersion composition. More preferably, it is 30 to 65% by mass. The amount of the solvent (C) contained in the polymerizable composition is preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass with respect to the total amount of the polymerizable composition. Is more preferable, and it is still more preferable that it is 25 mass% to 75 mass%.
＜（Ｄ）重合性化合物＞
　本発明の重合性組成物は、上記したように、（Ｄ）重合性化合物を含有する。
　（Ｄ）重合性化合物は、少なくとも１個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で１００℃以上である化合物が好ましい。 <(D) Polymerizable compound>
As described above, the polymerizable composition of the present invention contains (D) a polymerizable compound.
(D) The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.
　少なくとも１個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で１００℃以上である化合物としては、例えば、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能のアクリレートやメタアクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、ペンタエリスリトール又はジペンタエリスリトールのポリ（メタ）アクリレート化したもの、特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号の各公報に記載のウレタンアクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号の各公報に記載のポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタアクリレートを挙げることができる。
　更に、日本接着協会誌Ｖｏｌ．２０、Ｎｏ.７、３００～３０８頁に光硬化性モノマー及びオリゴマーとして紹介されているものも使用できる。 Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Tetra, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylol ethane, and then (meth) acrylated after addition of ethylene oxide or propylene oxide, poly (pentaerythritol or dipentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49- And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, as described in JP-A-43191 and JP-B-52-30490. it can.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.
　また、特開平１０－６２９８６号公報において一般式（１）及び一般式（２）としてその具体例と共に記載の、前記多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も用いることができる。 In addition, in JP-A-10-62986, general formula (1) and general formula (2) are described together with specific examples thereof, and after adding ethylene oxide or propylene oxide to the polyfunctional alcohol, (meth) acrylate formation was performed. Compounds can also be used.
　なかでも、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、及びこれらのアクリロイル基がエチレングリコール、プロピレングリコール残基を介してジペンタエリスリトールに連結している構造が好ましい。これらのオリゴマータイプも使用できる。 Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
　また、特公昭４８－４１７０８号、特開昭５１－３７１９３号、特公平２－３２２９３号、及び特公平２－１６７６５号の各公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号、特公昭５６－１７６５４号、特公昭６２－３９４１７号、及び特公昭６２－３９４１８号の各公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、特開昭６３－２７７６５３号、特開昭６３－２６０９０９号、及び特開平１－１０５２３８号の各公報に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類を用いることによっては、非常に感光スピードに優れた光重合性組成物を得ることができる。市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（商品名、日本製紙ケミカル（株）製）、ＵＡ－７２００」(新中村化学工業（株）製、ＤＰＨＡ－４０Ｈ（商品名、日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（商品名、共栄社化学（株）製）などが挙げられる。 Further, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the situation, a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained. Commercially available products include urethane oligomers UAS-10, UAB-140 (trade names, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (trade names, Nippon Kasei) Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
　また、酸基を有するエチレン性不飽和化合物類も好適であり、市販品としては、例えば、東亞合成株式会社製のカルボキシル基含有３官能アクリレートであるＴＯ－７５６、及びカルボキシル基含有５官能アクリレートであるＴＯ－１３８２などが挙げられる。
　本発明に用いられる重合性化合物としては、４官能以上のアクリレート化合物がより好ましい。 Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.
　（Ｄ）重合性化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　２種以上の重合性化合物を組み合わせて用いる場合、その組み合わせ態様は、重合性組成物に要求される物性等に応じて適宜設定することができる。重合性化合物の好適な組み合わせ態様の一つとしては、例えば、前掲した多官能のアクリレート化合物から選択した２種以上の重合性化合物を組み合わせる態様が挙げられ、その一例としては、ジペンタエリスリトールヘキサアクリレート及びペンタエリスリトールトリアクリレートの組み合わせが挙げられる。
　本発明の重合性組成物における（Ｄ）重合性化合物の含有量は、重合性組成物の全固形分に対して、３質量％～５５質量％が好ましく、より好ましくは１０質量％～５０質量％である。 (D) A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When using in combination of 2 or more types of polymeric compounds, the combination aspect can be suitably set according to the physical property etc. which are requested | required of polymeric composition. As one suitable combination mode of the polymerizable compound, for example, a mode in which two or more polymerizable compounds selected from the above-mentioned polyfunctional acrylate compounds are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
The content of the polymerizable compound (D) in the polymerizable composition of the present invention is preferably 3% by mass to 55% by mass, more preferably 10% by mass to 50% by mass with respect to the total solid content of the polymerizable composition. %.
＜（Ｅ）重合開始剤＞
　本発明の重合性組成物は、上記したように、（Ｅ）重合開始剤（好ましくは光重合開始剤）を含有する。
　（Ｅ）重合開始剤は、光や熱により分解し、前述した（Ｄ）重合性化合物の重合を開始、促進する化合物であり、波長３００～５００ｎｍの領域の光に対して吸収を有するものであることが好ましい。 <(E) Polymerization initiator>
As described above, the polymerizable composition of the present invention contains (E) a polymerization initiator (preferably a photopolymerization initiator).
(E) The polymerization initiator is a compound that is decomposed by light or heat to start and accelerate the polymerization of the above-mentioned (D) polymerizable compound, and has absorption for light in the wavelength region of 300 to 500 nm. Preferably there is.
　（Ｅ）重合開始剤の具体的な例としては、有機ハロゲン化化合物、オキシジアゾール化合物、カルボニル化合物、ケタール化合物、ベンゾイン化合物、有機過酸化化合物、アゾ化合物、クマリン化合物、アジド化合物、メタロセン化合物、有機ホウ酸化合物、ジスルホン酸化合物、オキシム化合物（特にオキシムエステル化合物）、オニウム塩化合物、アシルホスフィン（オキシド）化合物が挙げられる。より具体的な例としては、例えば、特開２００６－７８７４９号公報の段落番号［００８１］～［０１００］、［０１０１］～［０１３９］等に記載される重合開始剤が挙げられる。上記の重合開始剤の中でも、得られるパターンの形状を良化できるという観点から、オキシム化合物（特にオキシムエステル化合物）がより好ましい。 (E) Specific examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples thereof include organic boric acid compounds, disulfonic acid compounds, oxime compounds (particularly oxime ester compounds), onium salt compounds, and acylphosphine (oxide) compounds. More specific examples include polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749. Among the above polymerization initiators, an oxime compound (particularly an oxime ester compound) is more preferable from the viewpoint that the shape of the pattern to be obtained can be improved.
　本発明の重合性組成物における（Ｅ）重合開始剤の含有量は、重合性組成物の全固形分中、０．１質量％～３０質量％であることが好ましく、１質量％～２５質量％がより好ましく、２質量％～２０質量％が更に好ましい。 The content of the (E) polymerization initiator in the polymerizable composition of the present invention is preferably 0.1% by mass to 30% by mass in the total solid content of the polymerizable composition, and 1% by mass to 25% by mass. % Is more preferable, and 2% by mass to 20% by mass is still more preferable.
〔（Ｆ）その他の添加剤〕
　本発明の重合性組成物には、本発明の分散組成物、（Ｄ）重合性化合物、及び（Ｅ）重合開始剤に加え、目的に応じて、種々の添加剤を使用することができる。 [(F) Other additives]
In addition to the dispersion composition of the present invention, (D) polymerizable compound, and (E) polymerization initiator, various additives can be used in the polymerizable composition of the present invention depending on the purpose.
（Ｆ－１）バインダーポリマー
　本発明の重合性組成物においては、皮膜特性向上などの目的で、必要に応じて、更に（Ｆ－１）バインダーポリマーを含むことができる。
　（Ｆ－１）バインダーポリマーとしては、線状有機ポリマーを用いることが好ましい。このような「線状有機ポリマー」としては、公知のものを任意に使用できる。好ましくは水現像或いは弱アルカリ水現像を可能とするために、水或いは弱アルカリ水に可溶性又は膨潤性である線状有機ポリマーが選択される。線状有機ポリマーは、皮膜形成剤としてだけでなく、水、弱アルカリ水、或いは有機溶剤からなる現像液（現像剤）に応じて選択使用される。 (F-1) Binder polymer The polymerizable composition of the present invention may further contain (F-1) a binder polymer, if necessary, for the purpose of improving film properties.
(F-1) A linear organic polymer is preferably used as the binder polymer. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent but also according to a developer (developer) composed of water, weak alkaline water, or an organic solvent.
　例えば、水可溶性有機ポリマーを用いると水現像が可能になる。このような線状有機ポリマーの例としては、側鎖にカルボン酸基を有するラジカル重合体、例えば特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５４－９２７２３号、特開昭５９－５３８３６号、特開昭５９－７１０４８号に記載されているもの、すなわち、カルボキシル基を有するモノマーを単独或いは共重合させた樹脂、酸無水物を有するモノマーを単独或いは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシル基を有するモノマーの例としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、４－カルボキシルスチレン等があげられ、酸無水物を有するモノマーの例としては、無水マレイン酸等が挙げられる。また、同様に側鎖にカルボン酸基を有する酸性セルロース誘導体も例として挙げられる。この他に水酸基を有する重合体に環状酸無水物を付加させたものなどが有用である。 For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. No. 25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. Is mentioned. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxyl styrene, and examples of the monomer having an acid anhydride include maleic anhydride. An acid etc. are mentioned. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
　また、特公平７－１２００４号、特公平７－１２００４１号、特公平７－１２００４２号、特公平８－１２４２４号、特開昭６３－２８７９４４号、特開昭６３－２８７９４７号、特開平１－２７１７４１号、特願平１０－１１６２３２号等に記載される酸基を含有するウレタン系バインダーポリマーは、非常に、強度に優れるので、低露光適性の点で有利である。 In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Application Laid-Open No. 63-287944, Japanese Patent Application Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. Urethane binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and advantageous in terms of suitability for low exposure.
　また、欧州特許第９９３９６６号、欧州特許第１２０４０００号、特開２００１－３１８４６３号等の各公報に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダーポリマーは、膜強度、現像性のバランスに優れており、好適である。
　更に、この他に水溶性線状有機ポリマーとして、ポリビニルピロリドンやポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるために、アルコール可溶性ナイロンや２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンのポリエーテル等も有用である。 Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent Nos. 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
　特に、これらの中でも、〔ベンジル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体、及び〔アリル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体は、膜強度、感度、現像性のバランスに優れており、好適である。 In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
　本発明の重合性組成物に使用される（Ｆ－１）バインダーポリマーの重量平均分子量は、現像時のパターン剥離抑制と現像性の観点から、１，０００～３００，０００であることが好ましく、１，５００～２５０，０００であることがより好ましく、２，０００～２００，０００であることが更に好ましく、２，５００～１００，０００であることが特に好ましい。（Ｆ－１）バインダーポリマーの数平均分子量については、好ましくは１０００以上であり、更に好ましくは１５００～２５万の範囲である。（Ｆ－１）バインダーポリマーの多分散度（重量平均分子量／数平均分子量）は、１以上が好ましく、更に好ましくは１．１～１０の範囲である。
　ここで、（Ｆ－１）バインダーポリマーの重量平均分子量は、例えば、ＧＰＣによって測定することができる。 The weight average molecular weight of the (F-1) binder polymer used in the polymerizable composition of the present invention is preferably 1,000 to 300,000 from the viewpoint of pattern peeling inhibition during development and developability. It is more preferably 1,500 to 250,000, further preferably 2,000 to 200,000, and particularly preferably 2,500 to 100,000. (F-1) The number average molecular weight of the binder polymer is preferably 1000 or more, and more preferably in the range of 1500 to 250,000. (F-1) The polydispersity (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 1 or more, more preferably in the range of 1.1 to 10.
Here, the weight average molecular weight of the (F-1) binder polymer can be measured, for example, by GPC.
　これらの（Ｆ－１）バインダーポリマーは、ランダムポリマー、ブロックポリマー、グラフトポリマー等いずれでもよい。 These (F-1) binder polymers may be random polymers, block polymers, graft polymers or the like.
　本発明で用いうる（Ｆ－１）バインダーポリマーは、従来公知の方法により合成できる。合成する際に用いられる溶媒としては、例えば、テトラヒドロフラン、エチレンジクロリド、シクロヘキサノン等が挙げられる。これらの溶媒は単独で又は２種以上混合して用いられる。
　また、（Ｆ－１）バインダーポリマーを合成する際に用いられるラジカル重合開始剤としては、アゾ系開始剤、過酸化物開始剤等公知の化合物が挙げられる。 The (F-1) binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer (F-1) include known compounds such as azo initiators and peroxide initiators.
　本発明において、（Ｆ－１）バインダーポリマーとして、側鎖に二重結合を有するアルカリ可溶性樹脂を用いることで、特に露光部の硬化性と未露光部のアルカリ現像性の双方を向上させることができる。側鎖に二重結合を有するアルカリ可溶性樹脂は、その構造その中に、樹脂がアルカリ可溶となるための酸基と、少なくとも１つの不飽和二重結合を有することで、非画像部除去性などの諸性能を向上させる。このような構造を有する樹脂は、特開２００３－２６２９５８号公報に詳細に記載され、ここに記載の樹脂を本発明におけるバインダーポリマーとして使用することができる。 In the present invention, by using an alkali-soluble resin having a double bond in the side chain as the (F-1) binder polymer, it is possible to improve both the curability of the exposed area and the alkali developability of the unexposed area. it can. The alkali-soluble resin having a double bond in the side chain has a non-image area removability by having an acid group for making the resin alkali-soluble in the structure and at least one unsaturated double bond. Improve various performances. The resin having such a structure is described in detail in JP-A No. 2003-262958, and the resin described therein can be used as the binder polymer in the present invention.
　本発明の重合性組成物におけるバインダーポリマーの含有量は、組成物の全固形分中に対して、０．１質量％～２５質量％であることが好ましく、遮光膜の剥がれ抑制と現像残渣抑制の両立の観点からは、０．３質量％～２０質量％であることがより好ましく、１．０～１５質量％であることが更に好ましい。 The content of the binder polymer in the polymerizable composition of the present invention is preferably 0.1% by mass to 25% by mass with respect to the total solid content of the composition. From the viewpoint of achieving both, it is more preferably 0.3% by mass to 20% by mass, and further preferably 1.0% by mass to 15% by mass.
（Ｆ－２）着色剤
　本発明の重合性組成物には、所望の遮光性を発現させるべく、公知の有機顔料や染料などの無機顔料以外の（Ｆ－２）着色剤を併用することが可能である。 (F-2) Colorant The polymerizable composition of the present invention may be used in combination with a colorant (F-2) other than known inorganic pigments such as organic pigments and dyes in order to develop desired light-shielding properties. Is possible.
　併用することができる（Ｆ－２）着色剤としては、有機顔料では、例えば、特開２００８－２２４９８２号公報段落番号〔００３０〕～〔００４４〕に記載の顔料や、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ５８、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ ７９のＣｌ置換基をＯＨに変更したものなどが挙げられ、これらの中でも、好ましく用いることができる顔料として、以下のものを挙げることができる。但し、本発明に適用しうる（Ｆ－２）着色剤は、これらに限定されるものではない。 (F-2) Colorants that can be used in combination include organic pigments such as pigments described in paragraphs [0030] to [0044] of JP-A-2008-224982, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the Cl substituent is changed to OH and the like. Among these, pigments that can be preferably used include the following. However, the colorant (F-2) applicable to the present invention is not limited to these.
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１１，２４，１０８，１０９，１１０，１３８，１３９，１５０，１５１，１５４，１６７，１８０，１８５、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ３６，３８，６２，６４、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２，１５０，１７１，１７５，１７７，２０９，２２４，２４２，２５４、２５５、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １９，２３，２９，３２、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：１，１５：３，１５：６，１６，２２，６０，６６、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７，３６，３７，５８、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌａｃｋ １ C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 38, 62, 64,
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255,
C. I. Pigment Violet 19, 23, 29, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58,
C. I. Pigment Black 1
　また、（Ｆ－２）着色剤として使用可能な染料の例としては、特に制限はなく、公知の染料を適宜選択して使用できる。例えば、特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号、米国特許第４，８０８，５０１号明細書、米国特許第５，６６７，９２０号明細書、米国特許第５，０５９，５００号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、特開平６－１９４８２８号公報、特開平８－２１１５９９号公報、特開平４－２４９５４９号公報、特開平１０－１２３３１６号公報、特開平１１－３０２２８３号公報、特開平７－２８６１０７号公報、特開２００１－４８２３号公報、特開平８－１５５２２号公報、特開平８－２９７７１号公報、特開平８－１４６２１５号公報、特開平１１－３４３４３７号公報、特開平８－６２４１６号公報、特開２００２－１４２２０号公報、特開２００２－１４２２１号公報、特開２００２－１４２２２号公報、特開２００２－１４２２３号公報、特開平８－３０２２２４号公報、特開平８－７３７５８号公報、特開平８－１７９１２０号公報、特開平８－１５１５３１号公報等に記載の色素が挙げられる。 Further, examples of the dye that can be used as the colorant (F-2) are not particularly limited, and known dyes can be appropriately selected and used. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808,501 Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 Examples thereof include dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
　染料が有する化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アンスラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の化学構造が挙げられる。 The chemical structure of the dye includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole Examples include chemical structures such as azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene.
　本発明の重合性組成物における（Ｆ－２）着色剤としては、該組成物が必須に含有するチタンブラック粒子と組み合わせた場合に、硬化性と遮光性を両立しうるという観点から、オレンジ顔料、赤色顔料、及び、バイオレット顔料からなる群より選択される１種以上の有機顔料が好ましく、最も好ましくは赤色顔料との組み合わせである。 The (F-2) colorant in the polymerizable composition of the present invention is an orange pigment from the viewpoint that when combined with titanium black particles that the composition essentially contains, both curability and light shielding properties can be achieved. One or more organic pigments selected from the group consisting of red pigments and violet pigments are preferred, and most preferred are combinations with red pigments.
　オレンジ顔料、赤色顔料、及びバイオレット顔料としては、例えば、前記で例示した「Ｃ．Ｉ．ＰｉｇｍｅｎｔＯｒａｎｇｅ」、「Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ」、「Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ」に属する各種顔料を、目的とする遮光性に応じて適宜選択すればよい。遮光性向上の観点からは、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２９、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ３６，３８，６２，６４、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １７７，２５４、２５５などが好ましい。 Examples of the orange pigment, red pigment, and violet pigment include various pigments belonging to “CI Pigment Orange”, “CI Pigment Red”, and “CI Pigment Violet” exemplified above. What is necessary is just to select suitably according to light-shielding property. From the viewpoint of improving the light shielding property, C.I. I. Pigment Violet 29, C.I. I. Pigment Orange 36, 38, 62, 64, C.I. I. Pigment Red 177, 254, 255 and the like are preferable.
（Ｆ－３）増感剤
　本発明の重合性組成物には、（Ｅ）重合開始剤のラジカル発生効率の向上、感光波長の長波長化の目的で、（Ｆ－３）増感剤を含有していてもよい。
　（Ｆ－３）増感剤としては、用いられる（Ｅ）重合開始剤を、電子移動機構又はエネルギー移動機構で増感させるものが好ましい。
　（Ｆ－３）増感剤の好ましい例としては、特開２００８－２１４３９５号公報の段落番号〔００８５〕～〔００９８〕に記載された化合物を挙げることができる。
　（Ｆ－３）増感剤の含有量は、感度と保存安定性の観点から、重合性組成物の全固形分に対し、０．１質量％～３０質量％の範囲内であることが好ましく、１～２０質量％の範囲内であることがより好ましく、２～１５質量％の範囲内であることが更に好ましい。 (F-3) Sensitizer The polymerizable composition of the present invention contains (F-3) a sensitizer for the purpose of (E) improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. You may contain.
As the (F-3) sensitizer, one that sensitizes the polymerization initiator (E) used by an electron transfer mechanism or an energy transfer mechanism is preferable.
Preferable examples of (F-3) sensitizers include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
The content of (F-3) sensitizer is preferably in the range of 0.1% by mass to 30% by mass with respect to the total solid content of the polymerizable composition from the viewpoint of sensitivity and storage stability. The content is more preferably in the range of 1 to 20% by mass, and still more preferably in the range of 2 to 15% by mass.
（Ｆ－４）重合禁止剤
　本発明の重合性組成物には、該組成物の製造中或いは保存中において、重合性化合物の不要な熱重合を阻止するために少量の（Ｆ－４）重合禁止剤を添加することが望ましい。
　（Ｆ－４）重合禁止剤としては、公知の熱重合防止剤を用いることができ、具体的には、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、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）、Ｎ－ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。
　（Ｆ－４）熱重合防止剤の含有量は、重合性組成物の全固形分に対し、約０．０１質量％～約５質量％が好ましい。 (F-4) Polymerization inhibitor The polymerizable composition of the present invention contains a small amount of (F-4) polymerization in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. It is desirable to add an inhibitor.
(F-4) As the polymerization inhibitor, a known thermal polymerization inhibitor can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl. Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt Etc.
The content of (F-4) thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total solid content of the polymerizable composition.
　また、必要に応じて、酸素による重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加して、塗布後の乾燥の過程で塗布膜の表面に高級脂肪酸誘導体等を偏在させてもよい。高級脂肪酸誘導体の添加量は、全組成物の約０．５質量％～約１０質量％が好ましい。 In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and a higher fatty acid derivative is applied to the surface of the coating film during the drying process after coating. Etc. may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% by weight of the total composition.
（Ｆ－５）密着向上剤
　本発明の重合性組成物には、支持体などの硬質表面との密着性を向上させるために、（Ｆ－５）密着向上剤を添加することができる。
　（Ｆ－５）密着向上剤としては、シラン系カップリング剤、チタンカップリング剤等が挙げられる。 (F-5) Adhesion improver In order to improve the adhesion to a hard surface such as a support, (F-5) an adhesion improver can be added to the polymerizable composition of the present invention.
Examples of (F-5) adhesion improvers include silane coupling agents and titanium coupling agents.
　シラン系カップリング剤としては、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－アクリロキシプロピルトリメトキシシラン、γ－アクリロキシプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、フェニルトリメトキシシラン、が好ましく、γ－メタクリロキシプロピルトリメトキシシランが好ましく挙げられる。 Silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is preferable.
　（Ｆ－５）密着向上剤の含有量は、重合性組成物の全固形分中０．５質量％３０質量％であることが好ましく、０．７質量％～２０質量％であることがより好ましい。 The content of (F-5) adhesion improver is preferably 0.5% by mass to 30% by mass and more preferably 0.7% by mass to 20% by mass in the total solid content of the polymerizable composition. preferable.
　なお、本発明の重合性組成物を適用して遮光膜を有するウエハレベルレンズに、ガラス基板を適用する場合には、感度向上の観点から、（Ｆ－５）密着向上剤を添加することが好ましい。 In addition, when a glass substrate is applied to a wafer level lens having a light-shielding film by applying the polymerizable composition of the present invention, (F-5) an adhesion improver may be added from the viewpoint of improving sensitivity. preferable.
（Ｆ－６）界面活性剤
　本発明の重合性組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 (F-6) Surfactant Various surfactants may be added to the polymerizable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
　特に、本発明の重合性組成物は、フッ素系界面活性剤を含有することで、塗布液として調製したときの液特性（特に、流動性）がより向上することから、塗布厚の均一性や省液性をより改善することができる。即ち、フッ素系界面活性剤を含有する重合性組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。 In particular, since the polymerizable composition of the present invention contains a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. The liquid-saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a polymerizable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、３質量％～４０質量％が好適であり、より好ましくは５質量％～３０質量％であり、特に好ましくは７質量％～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、重合性組成物中における溶解性も良好である。 The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the polymerizable composition.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
　ノニオン系界面活性剤として具体的には、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセリンエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１、ソルスパース２００００（日本ルーブリゾール（株）製）等が挙げられる。 Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
　カチオン系界面活性剤として具体的には、フタロシアニン誘導体（商品名：ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株））、Ｗ００１（裕商（株）製）等が挙げられる。 Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング（株「トーレシリコーンＤＣ３ＰＡ」、「トーレシリコーンＳＨ７ＰＡ」、「トーレシリコーンＤＣ１１ＰＡ」，「トーレシリコーンＳＨ２１ＰＡ」，「トーレシリコーンＳＨ２８ＰＡ」、「トーレシリコーンＳＨ２９ＰＡ」、「トーレシリコーンＳＨ３０ＰＡ」、「トーレシリコーンＳＨ８４００」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越シリコーン株式会社製「ＫＰ３４１」、「ＫＦ６００１」、「ＫＦ６００２」、ビックケミー社製「ＢＹＫ３０７」、「ＢＹＫ３２３」、「ＢＹＫ３３０」等が挙げられる。 Examples of silicone-based surfactants include Toray Dow Corning (Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA. ”,“ Tole Silicone SH30PA ”,“ Tole Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF-4442 ”manufactured by Momentive Performance Materials, Inc. ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie.
　界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
　界面活性剤の添加量は、本発明の重合性組成物の全質量に対して、０．００１質量％～２．０質量％が好ましく、より好ましくは０．００５質量％～１．０質量％である。 Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the polymerizable composition of the present invention. It is.
（Ｆ－７）その他の添加剤
　更に、重合性組成物は、増感色素や開始剤の放射線に対する感度を一層向上させる、或いは酸素による光重合性化合物の重合阻害を抑制する等の目的で共増感剤を含有してもよい。また、硬化皮膜の物性を改良するために、希釈剤、可塑剤、感脂化剤等の公知の添加剤を必要に応じて加えてもよい。 (F-7) Other additives Further, the polymerizable composition is used for the purpose of further improving the sensitivity of the sensitizing dye or initiator to radiation, or suppressing the inhibition of polymerization of the photopolymerizable compound by oxygen. A sensitizer may be contained. Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as a diluent, a plasticizer, a fat-sensitizing agent, as needed.
＜分散組成物の調製＞
　本発明の分散組成物の調製態様は、特に制限されないが、例えば、（Ａ）チタンブラック、（Ｂ）高分子化合物、及び（Ｃ）溶媒を、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、湿式分散機、等を用いて分散処理を行なうことにより調製することができるが、その方法はこれらに限定されない。分散処理は、２回以上の分散処理（多段分散）により行ってもよい。 <Preparation of dispersion composition>
The preparation mode of the dispersion composition of the present invention is not particularly limited. For example, (A) titanium black, (B) polymer compound, and (C) solvent are mixed with a stirrer, homogenizer, high-pressure emulsifier, wet pulverizer, Although it can prepare by performing a dispersion process using a wet disperser etc., the method is not limited to these. The dispersion process may be performed by two or more dispersion processes (multistage dispersion).
＜重合性組成物の調製＞
　本発明の重合性組成物の調製態様についても特に制限されないが、例えば、本発明の分散組成物、（Ｄ）重合性化合物、（Ｅ）重合開始剤、及び、所望により併用される各種の添加剤を混合し、調製することができる。 <Preparation of polymerizable composition>
Although it does not restrict | limit especially about the preparation aspect of the polymeric composition of this invention, For example, the dispersion composition of this invention, (D) polymeric compound, (E) polymerization initiator, and various addition used together as needed Agents can be mixed and prepared.
＜遮光性カラーフィルタ＞
　本発明の着色パターンを有する遮光性カラーフィルタは、前述の本発明の重合性組成物を用いて形成されたものである。本発明の重合性組成物を用いて形成された着色パターン（例えばブラックマトリックス）は、残渣が抑制され、平坦性の良化ができる。 <Light-shielding color filter>
The light-shielding color filter having the colored pattern of the present invention is formed using the above-described polymerizable composition of the present invention. In the colored pattern (for example, black matrix) formed using the polymerizable composition of the present invention, the residue is suppressed and the flatness can be improved.
　着色パターン（例えばブラックマトリックス）の膜厚としては特に限定はないが、本発明による効果をより効果的に得る観点からは、乾燥後の膜厚で、０．２μｍ以上５０μｍ以下が好ましく、０．５μｍ以上３０μｍ以下がより好ましく、０．７μｍ以上２０μｍ以下が更に好ましい。着色パターン（例えばブラックマトリックス）のサイズ（一辺の長さ）としては、本発明による効果をより効果的に得る観点からは、０．００１ｍｍ以上５ｍｍ以下が好ましく、０．０５ｍｍ以上４ｍｍ以下がより好ましく、０．１ｍｍ以上３．５ｍｍ以下が更に好ましい。 The thickness of the colored pattern (for example, black matrix) is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the thickness after drying is preferably 0.2 μm or more and 50 μm or less. 5 to 30 μm is more preferable, and 0.7 to 20 μm is even more preferable. The size (length of one side) of the coloring pattern (for example, black matrix) is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less from the viewpoint of obtaining the effect of the present invention more effectively. More preferably, it is 0.1 mm or more and 3.5 mm or less.
＜遮光性カラーフィルタ及びその製造方法＞
　次に、本発明の遮光性カラーフィルタ及びその製造方法について説明する。本発明の遮光性カラーフィルタは、基板上に、本発明の重合性組成物を用いてなる着色パターン（例えばブラックマトリックス）を有することを特徴とする。
　以下、本発明の着色パターン（例えばブラックマトリックス）を有する遮光性カラーフィルタについて、その製造方法を通じて詳述する。 <Light-shielding color filter and manufacturing method thereof>
Next, the light-shielding color filter of the present invention and the manufacturing method thereof will be described. The light-shielding color filter of the present invention is characterized by having a colored pattern (for example, a black matrix) formed using the polymerizable composition of the present invention on a substrate.
Hereinafter, a light-shielding color filter having a colored pattern (for example, a black matrix) of the present invention will be described in detail through its manufacturing method.
　本発明の遮光性カラーフィルタの製造方法は、基板上に、本発明の重合性組成物を塗布して重合性組成物層を形成する工程（以下、適宜「重合性組成物層形成工程」と略称する。）と、前記重合性組成物層をマスクを介して露光する工程（以下、適宜「露光工程」と略称する。）と、露光後の前記重合性組成物層を現像して着色パターンを形成する工程（以下、適宜「現像工程」と略称する。）とを含むことを特徴とする。 The method for producing a light-shielding color filter of the present invention comprises a step of applying a polymerizable composition of the present invention on a substrate to form a polymerizable composition layer (hereinafter referred to as “polymerizable composition layer forming step” as appropriate). Abbreviated), a step of exposing the polymerizable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing the polymerizable composition layer after exposure to develop a colored pattern. (Hereinafter, abbreviated as “development step” as appropriate).
　具体的には、本発明の重合性組成物を、直接又は他の層を介して基板上に塗布して、重合性組成物層を形成し（重合性組成物層形成工程）、所定のマスクパターンを介して露光し、光照射された塗布膜部分だけを硬化させ（露光工程）、現像液で現像することによって（現像工程）、画素からなるパターン状皮膜を形成し、本発明の遮光性カラーフィルタを製造することができる。
　以下、本発明の遮光性カラーフィルタの製造方法における各工程について説明する。 Specifically, the polymerizable composition of the present invention is applied on a substrate directly or via another layer to form a polymerizable composition layer (polymerizable composition layer forming step), and a predetermined mask. By exposing only the coating film portion exposed through the pattern and curing the light (exposure process) and developing with a developer (development process), a pattern-like film composed of pixels is formed, and the light-shielding property of the present invention A color filter can be manufactured.
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.
［重合性組成物層形成工程］
　重合性組成物層形成工程では、基板上に、本発明の重合性組成物を塗布して重合性組成物層を形成する。 [Polymerizable composition layer forming step]
In the polymerizable composition layer forming step, the polymerizable composition layer of the present invention is coated on the substrate to form a polymerizable composition layer.
　前記基板としては、例えば、液晶表示装置等に用いられる無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラス、及びこれらに透明導電膜を付着させたものや、固体撮像素子等に用いられる光電変換素子基板、例えばシリコン基板等や、相補性金属酸化膜半導体（ＣＭＯＳ）等が挙げられる。
　また、これらの基板上には、必要により、上部の層との密着改良、物質の拡散防止あるいは基板表面の平坦化のために下塗り層を設けてもよい。 Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, solid-state imaging devices, and the like. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS).
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
　基板上への本発明の重合性組成物の塗布方法としては、スリット塗布、インクジェット法、回転塗布、流延塗布、ロール塗布、スプレー塗布、スクリーン印刷法等の各種の塗布方法を適用することができる。 As a coating method of the polymerizable composition of the present invention on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, spray coating, screen printing method, etc. can be applied. it can.
　固体撮像素子用のブラックマトリックスを有するカラーフィルタを製造する際には、重合性組成物の塗布膜厚としては、解像度と現像性の観点から、０．３５μｍ以上１．５μｍ以下が好ましく、０．４０μｍ以上１．０μｍ以下がより好ましい。 When producing a color filter having a black matrix for a solid-state imaging device, the coating thickness of the polymerizable composition is preferably from 0.35 μm to 1.5 μm from the viewpoint of resolution and developability. More preferably, it is 40 μm or more and 1.0 μm or less.
　基板上に塗布された重合性組成物は、通常、７０℃以上１１０℃以下で２分以上４分以下程度の条件下で乾燥され、重合性組成物層が形成される。 The polymerizable composition applied on the substrate is usually dried at 70 ° C. or more and 110 ° C. or less for about 2 minutes or more and 4 minutes or less to form a polymerizable composition layer.
〔露光工程〕
　露光工程では、前記重合性組成物層形成工程において形成された重合性組成物層をマスクを介して露光し、光照射された塗布膜部分だけを硬化させる。
　露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、ｇ線、ｈ線、ｉ線等の紫外線が好ましく用いられ、高圧水銀灯がより好まれる。照射強度は５ｍＪ／ｃｍ２以上１５００ｍＪ／ｃｍ２以下が好ましく１０ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下がより好ましく、１０ｍＪ／ｃｍ２以上８００ｍＪ／ｃｍ２以下が最も好ましい。 [Exposure process]
In the exposure step, the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. Irradiation intensity 5 mJ / cm 2 or more 1500 mJ / cm 2 or less is preferably 10 mJ / cm 2 or more 1000 mJ / cm 2 and more preferably less, 10 mJ / cm 2 or more 800 mJ / cm 2 or less is most preferable.
〔現像工程〕
　露光工程に次いで、アルカリ現像処理（現像工程）を行い、露光工程における光未照射部分をアルカリ水溶液に溶出させる。これにより、光硬化した部分だけが残る。現像液としては、固体撮像素子用のブラックマトリクスを有する遮光性カラーフィルタを作製する場合には、下地の回路などにダメージを起さない、有機アルカリ現像液が望ましい。現像温度としては通常２０℃以上３０℃以下であり、現像時間は２０秒以上９０秒以下である。 [Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains. As the developer, when producing a light-shielding color filter having a black matrix for a solid-state imaging device, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable. The development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.
　前記アルカリ性の水溶液としては、例えば、無機系現像液としては水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウム、有機アルカリ現像液としては、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、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５，４，０］－７－ウンデセン等のアルカリ性化合物を、濃度が０．００１～１０質量％、好ましくは０．０１～１質量％となるように溶解したアルカリ性水溶液が挙げられる。アルカリ性水溶液には、例えばメタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄（リンス）する。 Examples of the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as an inorganic developer, ammonia water, ethylamine as an organic alkali developer. Alkaline compounds such as diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, with a concentration of 0 An alkaline aqueous solution dissolved in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
　なお、本発明の遮光性カラーフィルタの製造方法においては、上述した、重合性組成物層形成工程、露光工程、及び現像工程を行った後に、必要により、形成された着色パターン（例えばブラックマトリックス）を加熱及び／又は露光により硬化する硬化工程を含んでいてもよい。 In the method for producing a light-shielding color filter of the present invention, a colored pattern (for example, a black matrix) formed as necessary after the above-described polymerizable composition layer forming step, exposure step, and development step is performed. A curing step of curing by heating and / or exposure may be included.
　本発明の遮光性カラーフィルタは、本発明の重合性組成物を用いているため、形成された着色パターン（例えばブラックマトリックス）が支持体基板との高い密着性を示し、硬化した組成物は耐現像性に優れるため、露光感度に優れ、露光部の基板との密着性が良好であり、かつ、所望の断面形状を与える高解像度のパターンを形成することができる。従って、液晶表示装置やＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）等の固体撮像素子に好適に用いることができ、特に１００万画素を超えるような高解像度のＣＣＤ素子やＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ　Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）等に好適である。すなわち、本発明のブラックマトリクスを備えた遮光性カラーフィルタは、固体撮像素子に適用されることが好ましい。
　本発明の遮光性カラーフィルタは、例えば、ＣＣＤを構成する各画素の受光部と集光するためのマイクロレンズとの間に配置されるブラックマトリックスとして用いることができる。 Since the light-shielding color filter of the present invention uses the polymerizable composition of the present invention, the formed colored pattern (for example, a black matrix) exhibits high adhesion to the support substrate, and the cured composition is resistant to Since the developability is excellent, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD (Charge Coupled Device), and particularly suitable for a high-resolution CCD device exceeding 1 million pixels, a CMOS (Complementary Metal Oxide Semiconductor), or the like. is there. That is, the light-shielding color filter provided with the black matrix of the present invention is preferably applied to a solid-state image sensor.
The light-shielding color filter of the present invention can be used, for example, as a black matrix disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.
＜固体撮像素子＞
　本発明の固体撮像素子は、既述の本発明の遮光性カラーフィルタ（例えばブラックマトリックス）と必要により他の色（３色あるいは４色）の画素からなるパターン状皮膜とを有するカラーフィルタを備えて構成される。
　本発明の固体撮像素子は、周辺部における遮光能の低下が抑制された本発明の遮光性カラーフィルタ（例えばブラックマトリックス）が備えられているため、ノイズを低減でき、色再現性を向上させることができる。
　本発明の固体撮像素子は、本発明の遮光性カラーフィルタ（例えばブラックマトリックス）を備えた構成であり、固体撮像素子として機能する構成であれば特に限定はなく、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、基板の受光素子形成面の反対側の面に本発明の遮光性カラーフィルタ（例えばブラックマトリックス）が備えられた構成等が挙げられる。 <Solid-state imaging device>
The solid-state imaging device of the present invention includes a color filter having the light-shielding color filter (for example, a black matrix) of the present invention described above and a patterned film composed of pixels of other colors (three colors or four colors) as necessary. Configured.
Since the solid-state imaging device of the present invention includes the light-shielding color filter of the present invention (for example, a black matrix) in which a decrease in light-shielding ability at the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved. Can do.
The solid-state imaging device of the present invention has a configuration including the light-shielding color filter (for example, a black matrix) of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. It has a light receiving element composed of a plurality of photodiodes and polysilicon forming a light receiving area of an element (CCD image sensor, CMOS image sensor, etc.), and the light shielding property of the present invention is provided on the surface opposite to the light receiving element forming surface of the substrate. Examples include a configuration provided with a color filter (for example, a black matrix).
＜液晶表示装置＞
　本発明の液晶表示装置の１つは、少なくとも１つが光透過性の１対の基板の間にカラーフィルタ、液晶層及び液晶駆動手段（単純マトリックス駆動方式、及びアクティブマトリックス駆動方式を含む）を少なくとも備えたもので、カラーフィルタとして、前記のごとき複数の画素群を有し、前記画素群を構成する各画素が、互いに本発明の重合性組成物により作成された遮光性カラーフィルタ（例えばブラックマトリックス；以下同様）により離画されているカラーフィルタを用いるものである。前記遮光性カラーフィルタは、平坦性が高いため、この遮光性カラーフィルタを備える液晶表示装置は、カラーフィルタと基板との間にセルギャップムラが発生せず、色ムラ等の表示不良が発生することがない。 <Liquid crystal display device>
One of the liquid crystal display devices of the present invention includes at least a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of substrates that are light transmissive. As a color filter, a light-shielding color filter (for example, a black matrix) having a plurality of pixel groups as described above, wherein each pixel constituting the pixel group is made of the polymerizable composition of the present invention. ; The same applies to the following) is used. Since the light-shielding color filter has high flatness, a liquid crystal display device including the light-shielding color filter does not cause cell gap unevenness between the color filter and the substrate, and causes display defects such as color unevenness. There is nothing.
　また、本発明の液晶表示装置の別の態様のものは、少なくとも１つが光透過性の１対の基板の間に、カラーフィルタ、液晶層及び液晶駆動手段を少なくとも備え、前記液晶駆動手段がアクティブ素子（例えばＴＦＴ）を有し、かつ各アクティブ素子の間に本発明の重合性組成物により作成された遮光性カラーフィルタ（例えばブラックマトリックス）を有する。 According to another aspect of the liquid crystal display device of the present invention, at least one includes a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is active. A light-shielding color filter (for example, a black matrix) made of the polymerizable composition of the present invention is included between the active elements and the elements (for example, TFTs).
＜ウエハレベルレンズ＞
　本発明のウエハレベルレンズは、既述の本発明の遮光性カラーフィルタ（例えばブラックマトリックス）を有するカラーフィルタを設けて構成されている。図１は、ウエハレベルレンズの構成の一例を示す平面図であり、図２は図１のＡ－Ａ線断面図である。 <Wafer level lens>
The wafer level lens of the present invention is configured by providing a color filter having the light-shielding color filter (for example, black matrix) of the present invention described above. FIG. 1 is a plan view showing an example of the configuration of a wafer level lens, and FIG. 2 is a cross-sectional view taken along line AA of FIG.
　ウエハレベルレンズは、基板１と、該基板１に配列された複数のレンズ１０とを備えている。複数のレンズ１０は、基板１に対して１次元又は２次元に配列されている。この構成例では、図１のように、複数のレンズ１０が、基板１に対して２次元配列されている構成を例に説明する。レンズ１０は、基板１と同じ材料から構成され、該基板１に成形されたものである。 The wafer level lens includes a substrate 1 and a plurality of lenses 10 arranged on the substrate 1. The plurality of lenses 10 are arranged one-dimensionally or two-dimensionally with respect to the substrate 1. In this configuration example, as shown in FIG. 1, a configuration in which a plurality of lenses 10 are two-dimensionally arranged on the substrate 1 will be described as an example. The lens 10 is made of the same material as the substrate 1 and is formed on the substrate 1.
　図２に示すように、レンズ１０は、凹状のレンズ面１０ａと、該レンズ面１０ａの周囲にレンズ縁部１０ｂとを有する。ここで、レンズ面１０ａは、レンズ１０に入射した光を所望の方向に集光又は発散させる光学的特性を有し、この光学的特性を考慮して曲率や表面形状が設計されている部位の面をいうものとする。この例では、レンズ縁部１０ｂの基板１に対する高さがレンズ面１０ａの中央よりも高くなるように構成されている。なお、レンズ１０の形状は、特に限定されず、例えば、レンズ面１０ａが凸状に突出した、所謂、凸状レンズとしてもよく、又は非球面のレンズとしてもよい。 As shown in FIG. 2, the lens 10 has a concave lens surface 10a and a lens edge 10b around the lens surface 10a. Here, the lens surface 10a has an optical characteristic that condenses or diverges light incident on the lens 10 in a desired direction, and is a part of a portion where the curvature and the surface shape are designed in consideration of this optical characteristic. It shall mean a surface. In this example, the height of the lens edge 10b relative to the substrate 1 is configured to be higher than the center of the lens surface 10a. The shape of the lens 10 is not particularly limited. For example, the lens 10 may be a so-called convex lens in which the lens surface 10a protrudes in a convex shape, or may be an aspherical lens.
　ここでは、基板１の一方の面に複数のレンズ１０が設けられた構成を例示しているが、基板１の両方の面に複数のレンズ１０が設けられた構成としてもよい。基板１の両方の面に複数のレンズ１０が設ける場合には、一方の面の各レンズの光軸が、他方の面の各レンズの光軸と一致するように成形される。 Here, a configuration in which a plurality of lenses 10 are provided on one surface of the substrate 1 is illustrated, but a configuration in which a plurality of lenses 10 are provided on both surfaces of the substrate 1 may be employed. When a plurality of lenses 10 are provided on both surfaces of the substrate 1, the lens is molded so that the optical axis of each lens on one surface coincides with the optical axis of each lens on the other surface.
　図２では、ウエハレベルレンズは、複数のレンズ１０が成形された基板１を１層有する構成としたが、２層以上の基板を積層させた構成としてもよい。 In FIG. 2, the wafer level lens is configured to have one layer of the substrate 1 on which a plurality of lenses 10 are molded, but may be configured to stack two or more layers.
　ウエハレベルレンズは、レンズ１０のレンズ縁部１０ｂの表面と、レンズ１０同士の間の基板１の表面とを覆うように遮光層１４が設けられている。遮光層１４は、基板１において、前記レンズのレンズ面１０ａを除く領域にパターニングされたものである。ウエハレベルレンズが基板を１層以上有する構成では、少なくとも１層の基板の表面に遮光層１４が備えられる。遮光層１４は黒色レジスト層で構成されている。黒色レジスト層は、光反射率が金属層などに比べて低いため、光反射に伴うゴーストやフレア等の不都合を低減できる。黒色レジスト層は、黒色レジスト組成物を含んでいる。 The wafer level lens is provided with a light shielding layer 14 so as to cover the surface of the lens edge 10b of the lens 10 and the surface of the substrate 1 between the lenses 10. The light shielding layer 14 is patterned in a region of the substrate 1 excluding the lens surface 10a of the lens. In the configuration in which the wafer level lens has one or more substrates, the light shielding layer 14 is provided on the surface of at least one substrate. The light shielding layer 14 is composed of a black resist layer. Since the black resist layer has a lower light reflectance than a metal layer or the like, it is possible to reduce inconveniences such as ghost and flare caused by light reflection. The black resist layer contains a black resist composition.
　図３は、ウエハレベルレンズの他の構成例を示す断面図である。
　この例では、基板１の一方の面に図２と同様の形状のレンズ１０が成形され、他方の面に凸状のレンズ２０が成形されている。また、他方の面には、他のウェハレンズアレイに重ね合わせる際に距離を確保するためのスペーサが形成されている。スペーサ１２は、平面視において格子状の部材であって、基板１の他方の面に接合される。この例では、ウエハレベルレンズにスペーサを接合した後、ダイシングによって、基板１にレンズ１０及びレンズ２０が１個ずつ備えられた構成となるように分離したものである。スペーサ１２は、基板１の一部として該基板１に一体に成形されたものとしてもよい。 FIG. 3 is a cross-sectional view showing another configuration example of the wafer level lens.
In this example, a lens 10 having the same shape as that shown in FIG. 2 is molded on one surface of the substrate 1, and a convex lens 20 is molded on the other surface. On the other surface, a spacer is formed for securing a distance when overlapping with another wafer lens array. The spacer 12 is a lattice-like member in plan view, and is joined to the other surface of the substrate 1. In this example, after a spacer is bonded to a wafer level lens, the substrate 1 is separated by dicing so that a lens 10 and a lens 20 are provided. The spacer 12 may be formed integrally with the substrate 1 as a part of the substrate 1.
　図４は、撮像ユニットの構成の一例を示す断面図である。
　撮像ユニットは、ウエハレベルレンズをダイシングしてレンズごとに分離したレンズモジュールと、撮像素子（ここでは、固体撮像素子）Ｄと、固体撮像素子Ｄが設けられたセンサ基板Ｗとを備える。この例では、３つのレンズモジュールＬＭ１，ＬＭ２，ＬＭ３を光の入射側（図４の上側）からのこの順に積層した構成としている。 FIG. 4 is a cross-sectional view illustrating an example of the configuration of the imaging unit.
The imaging unit includes a lens module obtained by dicing a wafer level lens and separating each lens, an imaging element (here, a solid-state imaging element) D, and a sensor substrate W provided with the solid-state imaging element D. In this example, three lens modules LM1, LM2, and LM3 are stacked in this order from the light incident side (upper side in FIG. 4).
　レンズモジュールＬＭ１は、基板１Ａの上側の面に凸状のレンズ１０Ａが成形され、下側の面に凹状のレンズ面を有するレンズ２０Ａが成形されている。基板１Ａの上側の面には、レンズ１０Ａのレンズ面を除く領域にパターニングされた遮光層１４が設けられている。レンズ２０Ａには、レンズ面を除く領域にパターニングされた遮光層１４が設けられている。 In the lens module LM1, a convex lens 10A is molded on the upper surface of the substrate 1A, and a lens 20A having a concave lens surface is molded on the lower surface. On the upper surface of the substrate 1A, a light shielding layer 14 patterned in a region excluding the lens surface of the lens 10A is provided. The lens 20A is provided with a light shielding layer 14 patterned in a region excluding the lens surface.
　レンズモジュールＬＭ２は、基板１Ｂの上側の面に凹状のレンズ１０Ｂが成形され、下側の面に凸状のレンズ面を有するレンズ２０Ｂが成形されている。このレンズモジュールＬＭ２は図３に示す構成と基本的に同じである。基板１Ａの上側の面には、レンズ１０Ａのレンズ面を除く領域、つまり、レンズ縁部及び基板表面の領域にパターニングされた遮光層１４が設けられている。この例では基板１Ｂの下側の面に遮光層１４を設けていないが、レンズ２０Ｂのレンズ面を除く領域にパターニングされた遮光層１４を設けてもよい。 In the lens module LM2, a concave lens 10B is molded on the upper surface of the substrate 1B, and a lens 20B having a convex lens surface is molded on the lower surface. This lens module LM2 is basically the same as the configuration shown in FIG. On the upper surface of the substrate 1A, a light shielding layer 14 patterned in a region excluding the lens surface of the lens 10A, that is, a lens edge and a region of the substrate surface is provided. In this example, the light shielding layer 14 is not provided on the lower surface of the substrate 1B, but the patterned light shielding layer 14 may be provided in a region other than the lens surface of the lens 20B.
　レンズモジュールＬＭ３は、基板１Ｃの上側の面に非球面形状のレンズ１０Ｃが成形され、下側の面に非球面形状のレンズ面を有するレンズ２０Ｃが成形されている。レンズ１０Ｃ及びレンズ２０Ｃには、レンズ面を除く領域にパターニングされた遮光層１４が設けられている。 In the lens module LM3, an aspherical lens 10C is molded on the upper surface of the substrate 1C, and a lens 20C having an aspherical lens surface is molded on the lower surface. The lens 10C and the lens 20C are provided with a light shielding layer 14 patterned in a region excluding the lens surface.
　前記レンズモジュールにおいて、遮光層１４は、本発明の分散組成物又は重合性組成物を用いて形成されたものである。
　なお、レンズ１０Ａ，１０Ｂ，１０Ｃ，２０Ａ，２０Ｂ，２０Ｃは、いずれも光軸に対して回転対称となる形状で設けられている。レンズモジュールＬＭ１，ＬＭ２，ＬＭ３は、全てのレンズ１０Ａ，１０Ｂ，１０Ｃ，２０Ａ，２０Ｂ，２０Ｃの光軸が一致するように、スペーサ１２を介して接合されている。 In the lens module, the light shielding layer 14 is formed using the dispersion composition or the polymerizable composition of the present invention.
The lenses 10A, 10B, 10C, 20A, 20B, and 20C are all provided in a shape that is rotationally symmetric with respect to the optical axis. The lens modules LM1, LM2, and LM3 are joined via the spacer 12 so that the optical axes of all the lenses 10A, 10B, 10C, 20A, 20B, and 20C coincide.
　レンズモジュールＬＭ１，ＬＭ２，ＬＭ３は、スペーサ１２を介してセンサ基板Ｗに接合される。レンズモジュールＬＭ１，ＬＭ２，ＬＭ３のレンズ１０Ａ，１０Ｂ，１０Ｃ，２０Ａ，２０Ｂ，２０Ｃは、センサ基板Ｗに設けられた固体撮像素子Ｄに被写体像を結像させる。 The lens modules LM1, LM2, and LM3 are bonded to the sensor substrate W through the spacer 12. The lenses 10A, 10B, 10C, 20A, 20B, and 20C of the lens modules LM1, LM2, and LM3 form a subject image on the solid-state imaging device D provided on the sensor substrate W.
　センサ基板Ｗは、例えばシリコンなどの半導体材料で形成されたウェハを平面視略矩形状に切り出して成形されている。固体撮像素子Ｄは、センサ基板Ｗの略中央部に設けられている。固体撮像素子Ｄは、例えばＣＣＤイメージセンサやＣＭＯＳイメージセンサである。固体撮像素子Ｄは、チップ化された後で、配線等が形成された半導体基板上にボンディングした構成とすることができる。又は、固体撮像素子Ｄは、センサ基板Ｗに対して周知の成膜工程、フォトリソグラフィ工程、エッチング工程、不純物添加工程等を行い、該センサ基板Ｗに電極、絶縁膜、配線等を形成して構成されてもよい。 The sensor substrate W is formed by cutting a wafer formed of a semiconductor material such as silicon into a substantially rectangular shape in plan view. The solid-state imaging device D is provided at a substantially central portion of the sensor substrate W. The solid-state image sensor D is, for example, a CCD image sensor or a CMOS image sensor. The solid-state imaging device D can be configured to be bonded on a semiconductor substrate on which wirings and the like are formed after being formed into a chip. Alternatively, the solid-state imaging device D performs a well-known film formation process, photolithography process, etching process, impurity addition process, etc. on the sensor substrate W, and forms electrodes, insulating films, wirings, etc. on the sensor substrate W. It may be configured.
　レンズモジュールＬＭ３のスペーサ１２とセンサ基板Ｗとは、例えば接着剤などを用いて接合される。各スペーサ１２は、レンズモジュールＬＭ１，ＬＭ２，ＬＭ３のレンズ１０Ａ，１０Ｂ，１０Ｃ，２０Ａ，２０Ｂ，２０Ｃが固体撮像素子Ｄ上で被写体像を結像させるように設計されている。また、各スペーサ１２は、レンズ１０Ａ，１０Ｂ，１０Ｃ，２０Ａ，２０Ｂ，２０Ｃが、重なり合うレンズモジュールＬＭ１，ＬＭ２，ＬＭ３同士、又は、レンズモジュールＬＭ３とセンサ基板Ｗとが互いに接触しないように、それぞれの間に所定の距離を隔てる厚みで形成されている。 The spacer 12 of the lens module LM3 and the sensor substrate W are bonded using, for example, an adhesive. Each spacer 12 is designed such that the lenses 10A, 10B, 10C, 20A, 20B, and 20C of the lens modules LM1, LM2, and LM3 form a subject image on the solid-state imaging device D. Further, each spacer 12 is arranged so that the lenses 10A, 10B, 10C, 20A, 20B, and 20C are not in contact with each other, or the lens modules LM3 and LM3 are not in contact with each other. It is formed with a thickness separating a predetermined distance therebetween.
　スペーサ１２は、レンズモジュールＬＭ１，ＬＭ２，ＬＭ３同士を、又は、レンズモジュールＬＭ３とセンサ基板Ｗとの間隔を所定の距離を隔てた位置関係で保持できる範囲で、その形状は特に限定されず適宜変形することができる。例えば、スペーサ１２は、基板１Ａ，１Ｂ，１Ｃの４隅にそれぞれ設けられる柱状の部材であってもよい。また、スペーサ１２は、固体撮像素子Ｄの周囲を取り囲むような枠状の部材であってもよい。固体撮像素子Ｄを枠状のスペーサ１２によって取り囲むことで外部から隔絶すれば、固体撮像素子Ｄにレンズを透過する光以外の光が入射しないように遮光することができる。また、固体撮像素子Ｄを外部から密封することで、固体撮像素子Ｄに塵埃が付着することを防止できる。 The spacer 12 is a range in which the lens modules LM1, LM2, and LM3 can be held between each other, or the distance between the lens module LM3 and the sensor substrate W can be held in a positional relationship with a predetermined distance therebetween. can do. For example, the spacer 12 may be a columnar member provided at each of the four corners of the substrates 1A, 1B, and 1C. The spacer 12 may be a frame-shaped member that surrounds the solid-state imaging device D. If the solid-state image pickup device D is isolated from the outside by being surrounded by the frame-shaped spacer 12, the solid-state image pickup device D can be shielded from light other than the light passing through the lens. Moreover, it can prevent that dust adheres to the solid-state image sensor D by sealing the solid-state image sensor D from the outside.
　図４に示すように、基板１Ａ，１Ｂ，１Ｃを複数重ね合わせた構成とする場合には、光入射側に最も近い最上部の基板における表面には、遮光層１４のかわりに反射層を設けてもよい。反射層は、光に対して透過率が０．０１％以下と小さく、かつ、反射率が（４％）以上と高い反射材料を含む。反射材料としては、クロム（Ｃｒ）などの金属又は金属材料を用いることが好ましい。 As shown in FIG. 4, when a plurality of substrates 1A, 1B, and 1C are stacked, a reflective layer is provided on the surface of the uppermost substrate closest to the light incident side instead of the light shielding layer 14. May be. The reflective layer includes a reflective material having a small transmittance of 0.01% or less with respect to light and a high reflectance of (4%) or more. As the reflective material, it is preferable to use a metal such as chromium (Cr) or a metal material.
　以上のように構成された撮像ユニットは、携帯端末等に内蔵される図示しない回路基板にリフロー実装される。回路基板には、撮像ユニットが実装される位置に予めペースト状の半田が適宜印刷されており、そこに撮像ユニットが載せられ、この撮像ユニットを含む回路基板に赤外線の照射や熱風の吹付けといった加熱処理が施され、撮像ユニットが回路基板に溶着される。 The imaging unit configured as described above is reflow-mounted on a circuit board (not shown) built in a portable terminal or the like. The circuit board is preliminarily printed with paste-like solder at a position where the imaging unit is mounted, and the imaging unit is mounted on the circuit board. The circuit board including the imaging unit is irradiated with infrared rays or hot air is blown. Heat treatment is performed, and the imaging unit is welded to the circuit board.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」「％」は質量基準である。また、室温は２５℃を指す。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass. Room temperature refers to 25 ° C.
＜特定樹脂１の合成＞
　１０００ｍＬの三口フラスコに、ε－カプロラクトン　６００ｇ、２－エチルー１－ヘキサノール　２２．８ｇを導入し、窒素を吹き込みながら撹拌した。モノブチルすずオキシド　０．１ｇ加え１００℃に加熱した。８時間後、ガスクロマトグラフィーにて原料が消失したのを確認後、８０℃まで冷却した。２，６－ジｔブチルー４－メチルフェノール　０．１ｇ添加した後、２－メタクリロイルオキシエチルイソシアネート　２７．２ｇを添加した。５時間撹拌した後、１Ｈ－ＮＭＲにて原料が消失したのを確認後、室温まで冷却し、固体状の前駆体Ｍ１（下記構造）を６５０ｇ得た。Ｍ１であることは１Ｈ－ＮＭＲ、ＩＲ、質量分析により確認した。 <Synthesis of specific resin 1>
Into a 1000 mL three-necked flask, 600 g of ε-caprolactone and 22.8 g of 2-ethyl-1-hexanol were introduced and stirred while blowing nitrogen. 0.1 g of monobutyltin oxide was added and heated to 100 ° C. After 8 hours, after confirming disappearance of the raw material by gas chromatography, the mixture was cooled to 80 ° C. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 27.2 g of 2-methacryloyloxyethyl isocyanate was added. After stirring for 5 hours, the disappearance of the raw material was confirmed by 1 H-NMR, and then cooled to room temperature to obtain 650 g of a solid precursor M1 (the following structure). M1 was confirmed by 1 H-NMR, IR, and mass spectrometry.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　前駆体Ｍ１　８０．０ｇ、メタクリル酸イソブチル　２０．０ｇ、ドデシルメルカプタン　２．３ｇ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　２３３．３ｇを、窒素置換した三口フラスコに導入し、攪拌機（新東科学（株）：スリーワンモーター）にて撹拌し、窒素をフラスコ内に流しながら加熱して７５℃まで昇温した。これに２，２－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業（株）製のＶ－６５）を０．２ｇ加え、７５℃にて２時間加熱撹拌を行った。２時間後、更にＶ－６５を０．２ｇ加え、３時間加熱撹拌した後、以下に示す特定樹脂１の３０％溶液を得た。
　なお、特定樹脂１の左側の構造単位に付記したＣｌｏｇＰ値は、当該構造単位に対応する化合物（モノマー）におけるＣｌｏｇＰ値を表す。 Precursor M1 80.0 g, isobutyl methacrylate 20.0 g, dodecyl mercaptan 2.3 g and propylene glycol monomethyl ether acetate 233.3 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). ) And heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.2 g of V-65 was further added and the mixture was heated and stirred for 3 hours, and then a 30% solution of the specific resin 1 shown below was obtained.
The ClogP value added to the left structural unit of the specific resin 1 represents the ClogP value in the compound (monomer) corresponding to the structural unit.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
＜特定樹脂２～９及び比較樹脂１の合成＞
　特定樹脂１を構成する構造単位に対応するモノマーを変更して、特定樹脂１の合成方法と同様にして、下記に記載の特定樹脂２～９及び比較樹脂１を合成した。下記表１にこれら樹脂の組成比、水素原子を除いたグラフト鎖の原子数、酸価、重量平均分子量を示す。また、以下の特定樹脂及び比較樹脂に記載のＣｌｏｇＰ値は、このＣｌｏｇＰ値が付記された構造単位に対応する化合物（モノマー）におけるＣｌｏｇＰ値を表す。 <Synthesis of Specific Resins 2-9 and Comparative Resin 1>
The specific resins 2 to 9 and the comparative resin 1 described below were synthesized in the same manner as the synthesis method of the specific resin 1 by changing the monomer corresponding to the structural unit constituting the specific resin 1. Table 1 below shows the composition ratio of these resins, the number of graft chain atoms excluding hydrogen atoms, the acid value, and the weight average molecular weight. Moreover, the ClogP value described in the following specific resin and comparative resin represents the ClogP value in the compound (monomer) corresponding to the structural unit to which this ClogP value is added.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
（実施例１）
＜チタンブラック分散物の調製＞
－チタンブラックＡ－１の作製－
　平均粒径１５ｎｍの酸化チタンＭＴ－１５０Ａ（商品名：テイカ（株）製）を１００ｇ、ＢＥＴ表面積３００ｍ２／ｇのシリカ粒子ＡＥＲＯＰＥＲＬ（登録商標）３００／３０（エボニック製）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（株式会社モトヤマ製）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原子を含み、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原子を含む被分散体〕を得た。 Example 1
<Preparation of titanium black dispersion>
-Production of Titanium Black A-1-
100 g of titanium oxide MT-150A (trade name: manufactured by Teika Co., Ltd.) having an average particle size of 15 nm, 25 g of silica particles AROPERL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m 2 / g, and dispersion 100 g of the agent Disperbyk 190 (trade name: manufactured by Big Chemie), add 71 g of ion-exchange water, and use MURASTAR KK-400W manufactured by KURABO for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm. Gave a homogeneous aqueous mixture. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was carried out by flowing. After the completion, the collected powder was pulverized in a mortar to obtain titanium black A-1 [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
＜実施例１のチタンブラック分散物の調製＞
　下記組成１に示す成分を、攪拌機（ＩＫＡ社製ＥＵＲＯＳＴＡＲ）を使用して、１５分間混合し、分散物ａを得た。 <Preparation of titanium black dispersion of Example 1>
The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.
（組成１）
・上記のようにして得られたチタンブラック（Ａ－１）　　　・・・２５部
・特定樹脂１のプロピレングリコールモノメチルエーテルアセテート３０質量％溶液
　　　　　　　　　　　　　　　　　　　　　　　　　　　　・・・２５部
・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）（溶剤）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　・・・５０部 (Composition 1)
-Titanium black (A-1) obtained as described above-25 parts-30% by weight propylene glycol monomethyl ether acetate solution of specific resin 1-25 parts-Propylene glycol monomethyl ether acetate (PGMEA) ( solvent)
... 50 copies
　得られた分散物ａに対し、寿工業（株）製のウルトラアペックスミルＵＡＭ０１５を使用して下記条件にて分散処理を行い、実施例１のチタンブラック分散物を得た。 The obtained dispersion a was subjected to a dispersion treatment using the Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a titanium black dispersion of Example 1.
（分散条件）
・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 (Distribution condition)
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Mill peripheral speed: 8m / sec
・ Amount of liquid mixture to be dispersed: 500 g
・ Circulation flow rate (pump supply amount): 13 kg / hour
・ Processing liquid temperature: 25-30 ℃
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Number of passes: 90 passes
＜実施例１の重合性組成物の調製＞
　下記組成Ａ中の成分を攪拌機で混合して、実施例１の重合性組成物を調製した。
（組成Ａ）
・ベンジルメタクリレート／アクリル酸共重合体　　　　　　　　５．０部
　（組成比：ベンジルメタクリレート／アクリル酸共重合体＝８０／２０（質量％）、重量平均分子量：２５０００；バインダーポリマー）
・ジペンタエリスリトールヘキサアクリレート（重合性化合物）　５．０部
・エトキシ化ペンタエリスリトールテトラアクリレート（重合性化合物）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　２．０部
・実施例１のチタンブラック分散物　　　　　　　　　　　　　７０．０部
・プロピレングリコールモノメチルエーテルアセテート（溶剤）８．９４部
・エチル－３－エトキシプロピオネート（溶剤）　　　　　　　　７．０部
・重合開始剤：下記表２に記載の化合物　　　　　　　　　　　　１．０部
・４－メトキシフェノール（重合禁止剤）　　　　　　　　　　０．０１部
・３－メタクリロキシプロピルトリメトキシシラン　　　　　　　１．０部
（シランカップリング剤）
・メガファックＦ７８１（ＤＩＣ（株）製）（界面活性剤）　　０．０５部 <Preparation of polymerizable composition of Example 1>
Components in the following composition A were mixed with a stirrer to prepare a polymerizable composition of Example 1.
(Composition A)
Benzyl methacrylate / acrylic acid copolymer 5.0 parts (composition ratio: benzyl methacrylate / acrylic acid copolymer = 80/20 (mass%), weight average molecular weight: 25000; binder polymer)
・ Dipentaerythritol hexaacrylate (polymerizable compound) 5.0 parts ・ Ethoxylated pentaerythritol tetraacrylate (polymerizable compound)
2.0 parts Titanium black dispersion of Example 1 70.0 parts Propylene glycol monomethyl ether acetate (solvent) 8.94 parts Ethyl-3-ethoxypropionate (solvent) 7.0 parts Polymerization initiator : Compounds shown in Table 2 below 1.0 part 4-methoxyphenol (polymerization inhibitor) 0.01 part 3-methacryloxypropyltrimethoxysilane 1.0 part (silane coupling agent)
・ Megafac F781 (manufactured by DIC Corporation) (surfactant) 0.05 parts
（実施例２～１４，比較例１）
　実施例１のチタンブラック分散物の調製において、特定樹脂１を、それぞれ、表２に示す特定樹脂及び比較樹脂に代えることにより、実施例２～１４，比較例１のチタンブラック分散物を調製した。
　また、実施例１の重合性組成物の調製において、実施例１のチタンブラック分散物を、それぞれ、表２に示す特定樹脂を有する上記のチタンブラック分散物に代えるとともに、重合開始剤を表２に示す重合開始剤とした以外は、実施例１と同様にして、実施例２～１４，比較例１の重合性組成物を調製した。 (Examples 2 to 14, Comparative Example 1)
In the preparation of the titanium black dispersion of Example 1, the specific resin 1 was replaced with the specific resin and the comparative resin shown in Table 2, respectively, to prepare the titanium black dispersions of Examples 2 to 14 and Comparative Example 1. .
In the preparation of the polymerizable composition of Example 1, the titanium black dispersion of Example 1 was replaced with the above titanium black dispersion having the specific resin shown in Table 2, and the polymerization initiator was changed to Table 2. The polymerizable compositions of Examples 2 to 14 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the polymerization initiators shown in Table 1 were used.
＜固体撮像素子用ブラックマトリックスを有するカラーフィルタの作製＞
　上記のようにして調製した各重合性組成物により、下塗り層付シリコンウエハの下塗り層上にスピーンコーター塗布した後、１０分間そのままの状態で待機させ、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行うことにより、乾燥膜厚が０．７μｍの塗布膜を形成した。
　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して３６５ｎｍの波長でパターンが２μｍ四方のＩｓｌａｎｄパターンマスクを通して１０００ｍＪ／ｃｍ２の露光量で露光した。 <Preparation of color filter having black matrix for solid-state image sensor>
Using each polymerizable composition prepared as described above, a spine coater was applied onto the undercoat layer of the silicon wafer with the undercoat layer, and then allowed to stand for 10 minutes and heated for 120 seconds using a hot plate at 100 ° C. By performing the treatment (pre-baking), a coating film having a dry film thickness of 0.7 μm was formed.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 1000 mJ / cm 2 through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
　その後、照射された塗布膜が形成されているシリコンウエハ基板をスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で９０秒間パドル現像を行った。
　次いで塗布膜が形成されているシリコンウエハを真空チャック方式で前記水平回転テーブルに固定し、回転装置によって該シリコンウエハ基板を回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スプレー乾燥し、ブラックマトリックスを有するウエハを形成した。 Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film). Paddle development was performed for 90 seconds at 23 ° C. using Electronics Materials Co., Ltd.
Next, the silicon wafer on which the coating film is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center. Then, the wafer was supplied in a shower form and rinsed, and then spray-dried to form a wafer having a black matrix.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　前記表２に記載の重合開始剤は、以下の通りである。 The polymerization initiators listed in Table 2 are as follows.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
〔評価〕
　上記のようにして得られた分散組成物及び重合性組成物を用いて、以下の評価を行った。その結果をまとめて表２に示した。 [Evaluation]
The following evaluation was performed using the dispersion composition and polymerizable composition obtained as described above. The results are summarized in Table 2.
（１）分散組成物の粘度
　また、分散組成物の２５℃における粘度をＥ型回転粘度計（東機産業社製）を用いて測定した。分散組成物の粘度が小さいほど分散性が高いことを示している。 (1) Viscosity of dispersion composition The viscosity of the dispersion composition at 25 ° C was measured using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). The smaller the viscosity of the dispersion composition, the higher the dispersibility.
（２）保存安定性（経時安定性）評価
　各重合性組成物を室温で１ケ月保存した後、チタンブラックの沈降の度合いを下記判定基準に従って評価した。保存安定性を示す数値は、可視光吸光度計（ｖａｒｉａｎ製ｃａｒｙ－５）により、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１０００倍に希釈した重合性組成物の吸光度変化率から算出したものである。 (2) Evaluation of Storage Stability (Stability with Time) After each polymerizable composition was stored at room temperature for 1 month, the degree of sedimentation of titanium black was evaluated according to the following criteria. The numerical value indicating storage stability was calculated from the absorbance change rate of the polymerizable composition diluted 1000-fold with propylene glycol monomethyl ether acetate (PGMEA) using a visible light absorptiometer (cary-5, varian).
－判定基準－
　許容値は３以上である。
５：０％以上２％未満のチタンブラックの沈降が観測された。
４：２％以上３％未満のチタンブラックの沈降が観測された。
３：３％以上４％未満のチタンブラックの沈降が観測された。
２：４％以上５％未満のチタンブラックの沈降が観測された。
１：５％以上のチタンブラックの沈降が観測された。 -Criteria-
The allowable value is 3 or more.
Sedimentation of 5: 0% or more and less than 2% of titanium black was observed.
4: Sedimentation of titanium black of 2% or more and less than 3% was observed.
3: Titanium black sedimentation of 3% or more and less than 4% was observed.
2: Sedimentation of 4% or more and less than 5% of titanium black was observed.
Sedimentation of titanium black of 1: 5% or more was observed.
（３）残渣の評価
　上記した露光工程で光が照射されなかった領域（未露光部）の残渣の有無を走査型電子顕微鏡（ＳＥＭ）で観察し、残渣を評価した。評価基準は以下の通りである。 (3) Evaluation of residue The presence or absence of the residue of the area | region (unexposed part) where light was not irradiated by the above-mentioned exposure process was observed with the scanning electron microscope (SEM), and the residue was evaluated. The evaluation criteria are as follows.
－評価基準－
　許容値は３以上である。
５：未露光部には、残渣がまったく確認されなかった。
４：未露光部には、残渣がごくわずかに確認された。
３：未露光部に、残渣がわずかに確認されたが、実用上問題のない程度であった。
２：未露光部に、多くの残渣が確認され、実用上問題のある程度であった。
１：未露光部に、残渣が著しく確認された。 -Evaluation criteria-
The allowable value is 3 or more.
5: No residue was observed at all in the unexposed area.
4: Very little residue was observed in the unexposed area.
3: Residues were slightly confirmed in the unexposed areas, but there was no practical problem.
2: Many residues were confirmed in the unexposed area, which was a practically problematic level.
1: The residue was remarkably confirmed in the unexposed part.
（４）塗布時の均一塗布性の評価
　各重合性組成物の塗布時の均一塗布性について、下記の方法で評価した。即ち、各重合性組成物をスピンコータ－で、８インチのシリコンウエハーの上に、乾燥後の膜厚が１μｍになるように塗布し、光学顕微鏡で観察し、均一塗布性を評価した。評価基準は以下の通りである。 (4) Evaluation of uniform applicability during application The following method evaluated the uniform applicability during application of each polymerizable composition. That is, each polymerizable composition was applied on an 8-inch silicon wafer with a spin coater so that the film thickness after drying was 1 μm, and observed with an optical microscope to evaluate the uniform coating property. The evaluation criteria are as follows.
－評価基準－
　許容値は３以上である。
５：全く塗布ムラが確認されなかった。
４：ごくわずかに塗布ムラが確認された。
３：わずかに塗布ムラが確認されたが、実用上問題のない程度であった。
２：多くの塗布ムラが確認され、実用上問題のある程度であった。
１：塗布ムラが著しく確認された。 -Evaluation criteria-
The allowable value is 3 or more.
5: Application unevenness was not confirmed at all.
4: Very slight coating unevenness was confirmed.
3: Slight coating unevenness was confirmed, but there was no practical problem.
2: A lot of coating unevenness was confirmed, which was a practically problematic level.
1: Coating unevenness was remarkably confirmed.
（５）現像マージンの評価
　基板（素ガラス）上に、各重合性組成物をスピンコーター（回転数：７５０ｒｐｍ，塗布膜厚：１．５μｍ）にて塗布した後、１００℃，１２０秒間のプリベークを行った。
　次いで、塗布膜に対して、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して３６５ｎｍの波長で、２０μｍ，５０μｍ，１００μｍ及び２００μｍの各線幅を有するラインアンドスペースパターンのマスクを通して、４００ｍＪ／ｃｍ２の露光量で露光した。
　その後、照射された塗布膜が形成されている基板をスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、Ｄ１０３０（テトラメチルアンモニウムヒドロキシドの０．３１質量％水溶液）（富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で１２０秒間、パドル現像を行った。
　以上のようにして形成した、２０μｍ，５０μｍ，１００μｍ及び２００μｍの各線幅を有するラインアンドスペースのパターンを光学顕微鏡で観察し、各線幅のライン部が残っているかどうかを確認した。 (5) Evaluation of development margin Each polymerizable composition was applied on a substrate (raw glass) with a spin coater (rotation speed: 750 rpm, coating film thickness: 1.5 μm), and then pre-baked at 100 ° C. for 120 seconds. Went.
Next, a line-and-space pattern mask having a line width of 20 μm, 50 μm, 100 μm, and 200 μm at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) on the coating film. Through exposure, the exposure amount was 400 mJ / cm 2 .
Then, the substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and D1030 (tetramethylammonium hydroxide) is placed. Paddle development was performed at 23 ° C. for 120 seconds using a 0.31 mass% aqueous solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.).
The line-and-space pattern having the line widths of 20 μm, 50 μm, 100 μm, and 200 μm formed as described above was observed with an optical microscope, and it was confirmed whether or not the line portion of each line width remained.
－評価基準－
　許容値は３以上である。
５：　線幅２０μｍのライン部が残存している。
４：　線幅２０μｍのライン部は剥がれているが、線幅５０μｍのライン部が残存している。
３：　線幅５０μｍのライン部は剥がれているが、線幅１００μｍのライン部が残存している。
２：　線幅１００μｍのライン部は剥がれているが、線幅２００μｍのライン部が残存している。
１：　線幅２００μｍのライン部が剥がれている。 -Evaluation criteria-
The allowable value is 3 or more.
5: A line portion having a line width of 20 μm remains.
4: The line part with a line width of 20 μm is peeled off, but the line part with a line width of 50 μm remains.
3: The line portion having a line width of 50 μm is peeled off, but the line portion having a line width of 100 μm remains.
2: The line portion with a line width of 100 μm is peeled off, but the line portion with a line width of 200 μm remains.
1: A line part having a line width of 200 μm is peeled off.
（６）現像ラチチュードの評価
　上記「（５）現像マージンの評価」と同様の方法で、各重合性組成物から形成した塗布膜を露光した。
　その後、照射された塗布膜が形成されている基板をスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ１０３０（テトラメチルアンモニウムヒドロキシドの０．３１質量％水溶液）（富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で現像を行った。
　この際、パターンの生成（解像）を目視して判断し、現像開始から、線幅２０μｍのライン部が生成（解像）するまでの時間、すなわち、「パターンが生じる（解像する時間）」を測定した。
　また、現像開始から３０秒後、６０秒後、１２０秒後、１５０秒後、１８０秒後、２１０秒後、２４０秒後のそれぞれの時点において、光学顕微鏡観察にて２０μｍのライン部が残っているかどうかを確認し、線幅２０μｍのライン部が最後に確認された時点を、「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」と定義した（すなわち、例えば、線幅２０μｍのライン部が、現像開始から１２０秒後の時点では確認されたものの、現像開始から１５０秒後の時点では確認されなかった場合は、「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」を１２０秒とした）。
　以上のようにして測定した「パターンが生じる（解像する時間）」及び「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」に基づき、現像ラチチュードを以下の評価基準にて評価した。 (6) Evaluation of development latitude The coating film formed from each polymeric composition was exposed by the method similar to said "(5) Evaluation of development margin".
Thereafter, the substrate on which the irradiated coating film is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD1030 (tetramethylammonium hydroxide) is placed. Development was performed at 23 ° C. using 0.31 mass% aqueous solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.).
At this time, the generation (resolution) of the pattern is determined by visual observation, and the time from the start of development to the generation (resolution) of the line portion having a line width of 20 μm, that is, “pattern occurs (time for resolution)”. Was measured.
Further, at the time points of 30 seconds, 60 seconds, 120 seconds, 150 seconds, 180 seconds, 210 seconds, and 240 seconds after the start of development, a 20 μm line portion remains by observation with an optical microscope. The time when the line part having a line width of 20 μm was finally confirmed was defined as “the time from the start of development until the last line part having a line width of 20 μm remained” (ie, for example, the line width If the 20 μm line portion was confirmed 120 seconds after the start of development but not 150 seconds after the start of development, the line portion with a line width of 20 μm from the start of development remained. "Time to do" was 120 seconds).
Based on the “pattern generation (resolution time)” and “time from the start of development to the last remaining line portion having a line width of 20 μm” measured as described above, the development latitude was evaluated according to the following evaluation criteria. evaluated.
－評価基準－
　許容値は３以上である。
５：「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」－「パターンが生じる（解像する）時間」＝１２０秒以上
４：「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」－「パターンが生じる（解像する）時間」＝９０秒以上１２０秒未満
３：「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」－「パターンが生じる（解像する）時間」＝６０秒以上９０秒未満
２：「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」－「パターンが生じる（解像する）時間」＝３０秒以上６０秒未満
１：「現像開始から線幅２０μｍのライン部が最後に残存するまでの時間」－「パターンが生じる（解像する）時間」＝３０秒未満 -Evaluation criteria-
The allowable value is 3 or more.
5: “Time from the start of development until a line part having a line width of 20 μm finally remains” − “Time when a pattern is generated (resolved)” = 120 seconds or more “Time until the last remaining”-“Time when pattern is generated (resolved)” = 90 seconds or more and less than 120 seconds 3: “Time from the start of development until the last line portion having a line width of 20 μm”-“ Time when pattern is generated (resolved) = 60 seconds or more and less than 90 seconds 2: “Time from the start of development until the end of the line portion having a line width of 20 μm” − “Time when pattern is generated (resolved)” = 30 seconds or more and less than 60 seconds 1: “Time from the start of development until a line part having a line width of 20 μm finally remains” — “Pattern generation (resolution) time” = less than 30 seconds
　表２から明らかなように、本発明の分散組成物を固体撮像素子用ブラックマトリックスに用いた実施例１～１４は、分散組成物の粘度が小さく、チタンブラックの分散性が良好であることがわかる。本発明の分散組成物を用いた重合性組成物は、良好な保存安定性を示し、また基板に塗布した際の均一塗布性が良好で、未露光部における残渣が抑制されることがわかった。これに加え、本発明の分散組成物を用いた重合性組成物は、本発明における疎水性構造単位を有さない高分子化合物を用いた比較例１と比較して、現像マージンが広く、また露光ラチチュードにも優れ、製造プロセス適性に優れることが分かった。 As is apparent from Table 2, Examples 1 to 14 in which the dispersion composition of the present invention was used for the black matrix for a solid-state imaging device had a low viscosity of the dispersion composition and good dispersibility of titanium black. Recognize. It was found that the polymerizable composition using the dispersion composition of the present invention exhibits good storage stability, has good uniform coating properties when coated on a substrate, and suppresses residues in unexposed areas. . In addition, the polymerizable composition using the dispersion composition of the present invention has a wide development margin as compared with Comparative Example 1 using the polymer compound having no hydrophobic structural unit in the present invention. It was found that the exposure latitude was excellent and the manufacturing process suitability was excellent.
（実施例１５～２３，比較例２）
＜液晶表示装置用ブラックマトリックスの作製＞
　次に、固体撮像素子用で用いた重合性組成物をそのまま用いて、液晶表示装置用ブラックマトリックスを有するカラーフィルタを作製し、評価を行った。
　即ち、固体撮像素子用カラーフィルタの作製で用いたものと同一の重合性組成物を用いて、２５０ｍｍ×３５０ｍｍのガラス基板に下記条件でスリット塗布した後、１０分間そのままの状態で待機させ、真空乾燥とプリベーク（１００℃、８０秒）を施して重合性組成物塗膜を形成した。ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して３６５ｎｍの波長で、２００μｍの直径を有するホールパターンのマスクを通して、１０００ｍＪ／ｃｍ２の露光量で露光した。
　その後、アルカリ現像液（商品名：ＣＤＫ－１、富士フイルムエレクトロニクスマテリアルズ（株）製）の１％水溶液にて露光済みの塗布膜を覆い、６０秒間静止した。その後、純水をシャワー状に散布して現像液を洗い流した。以上のように、露光処理及び現像処理を施した塗布膜を２２０℃のオーブンで１時間加熱処理（ポストベーク）を施し、ガラス基板上にブラックマトリックスを形成した。 (Examples 15 to 23, Comparative Example 2)
<Preparation of black matrix for liquid crystal display device>
Next, using the polymerizable composition used for the solid-state imaging device as it was, a color filter having a black matrix for a liquid crystal display device was produced and evaluated.
That is, using the same polymerizable composition as that used in the production of the color filter for the solid-state image sensor, slitting was applied to a 250 mm × 350 mm glass substrate under the following conditions, and then waiting for 10 minutes as it was. Drying and pre-baking (100 ° C., 80 seconds) were carried out to form a polymerizable composition coating film. Using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at a wavelength of 365 nm through a hole pattern mask having a diameter of 200 μm at an exposure amount of 1000 mJ / cm 2 .
Thereafter, the exposed coating film was covered with a 1% aqueous solution of an alkaline developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds. Thereafter, pure water was sprayed in a shower to wash away the developer. As described above, the coating film subjected to the exposure process and the development process was heat-treated (post-baked) in an oven at 220 ° C. for 1 hour to form a black matrix on the glass substrate.
（スリット塗布条件）
　・塗布ヘッド先端の開口部の間隙：　　　　　　５０μｍ
　・塗布速度：　　　　　　　　　　　　　１００ｍｍ／秒
　・基板と塗布ヘッドとのクリヤランス：　　　１５０μｍ
　・乾燥膜厚　　　　　　　　　　　　　　　１．７５μｍ
　・塗布温度：　　　　　　　　　　　　　　　　　２３℃ (Slit application conditions)
・ Gap at the opening of the coating head tip: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
・ Dry film thickness 1.75μm
・ Application temperature: 23 ℃
〔評価〕
　上記のようにして得られた塗布基板、及び重合性組成物を用いて、以下の評価を行った。その結果を表３に示す。 [Evaluation]
The following evaluation was performed using the coated substrate and the polymerizable composition obtained as described above. The results are shown in Table 3.
（１）塗布時の均一塗布性の評価
　上記のように、重合性組成物をスリット塗布した後、１０分間そのままの状態で待機させた後、ホットプレートで、９０℃、６０秒間プリベークした後、塗布面のスジ状のムラをナトリウム光源を用いて目視にてカウントし、以下の基準で評価した。 (1) Evaluation of uniform coating property at the time of coating After slit coating the polymerizable composition as described above, after waiting for 10 minutes as it is, after prebaking on a hot plate at 90 ° C. for 60 seconds, Striped unevenness on the coated surface was visually counted using a sodium light source and evaluated according to the following criteria.
（塗布基板の面状評価の基準）
３：塗布面にスジ状のムラが確認されなかった。
２：スジ状のムラが１～６本確認された。実用上問題のない程度であった。
１：スジ状のムラが７本以上、あるいは異物のいずれかが観察され、実用上問題のある程度であった。 (Standard for surface evaluation of coated substrate)
3: No streak-like unevenness was observed on the coated surface.
2: 1 to 6 streaky irregularities were confirmed. There was no problem in practical use.
1: Seven or more streaky irregularities or foreign matters were observed, which was a practically problematic level.
（２）残渣の評価
　上記した露光工程で光が照射されなかった領域（未露光部）の残渣の有無を走査型電子顕微鏡（ＳＥＭ）で観察し、残渣を評価した。評価基準は以下の通りである。
－評価基準－
許容値は３以上である。
５：未露光部には、残渣がまったく確認されなかった。
４：未露光部には、残渣がごくわずかに確認された。
３：未露光部に、残渣がわずかに確認されたが、実用上問題のない程度であった。
２：未露光部に、多くの残渣が確認され、実用上問題のある程度であった。
１：未露光部に、残渣が著しく確認された。 (2) Evaluation of residue The presence or absence of the residue of the area | region (unexposed part) where light was not irradiated by the above-mentioned exposure process was observed with the scanning electron microscope (SEM), and the residue was evaluated. The evaluation criteria are as follows.
-Evaluation criteria-
The allowable value is 3 or more.
5: No residue was observed at all in the unexposed area.
4: Very little residue was observed in the unexposed area.
3: Residues were slightly confirmed in the unexposed areas, but there was no practical problem.
2: Many residues were confirmed in the unexposed area, which was a practically problematic level.
1: The residue was remarkably confirmed in the unexposed part.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　上記表３から明らかなように、液晶表示装置用のブラックマトリックスを有するカラーフィルタとして、本発明の重合性組成物は、基板に塗布した際の均一塗布性が良好で、未露光部における残渣が抑制されることがわかった。 As apparent from Table 3 above, as a color filter having a black matrix for a liquid crystal display device, the polymerizable composition of the present invention has a good uniform coating property when applied to a substrate, and a residue in an unexposed part is present. It was found to be suppressed.
＜固体撮像素子の作製＞
（有彩色着色重合性組成物の調製）
　～ＲＧＢ各色着色画素形成用の有彩色顔料～
・赤色（Ｒ）用顔料
　Ｃ．Ｉ．ピグメント・レッド２５４
・緑色（Ｇ）用顔料
　Ｃ．Ｉ．ピグメント・グリーン３６とＣ．Ｉ．ピグメント・イエロー２１９との３０／７０〔質量比〕混合物
・青色（Ｂ）用顔料
　Ｃ．Ｉ．ピグメント・ブルー１５：６とＣ．Ｉ．ピグメント・バイオレット２３との３０／７０〔質量比〕混合物 <Production of solid-state image sensor>
(Preparation of chromatic coloring polymerizable composition)
-Chromatic pigments for forming colored pixels for each color of RGB-
-Red (R) pigment C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture Blue (B) pigment C.I. I. Pigment blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23
　上記顔料（すなわち、赤色（Ｒ）用顔料、緑色（Ｇ）用顔料、及び、青色（Ｂ）用顔料の各顔料）４０部、分散剤としてＤｉｓｐｅｒｂｙｋ－１６１（ビックケミー（ＢＹＫ）社製、３０％溶液）５０部、及び溶剤としてプロピレングリコールモノメチルエーテル１１０部からなる混合液を、ビーズミルにより１５時間混合・分散して、顔料分散液（Ｐ１）を調製した。
　前記分散処理した顔料分散液（Ｐ１）を用いて下記組成比となるよう撹拌混合し、それぞれ、赤色（Ｒ）用着色重合性組成物Ｒ－１、緑色（Ｇ）用着色重合性組成物Ｇ－１、及び青色（Ｂ）用着色重合性組成物Ｂ－１を調製した。
　<組成>
・着色剤（顔料分散液（Ｐ１））　　　　　　　　　　　　　　３５０部
・重合開始剤（オキシム系光重合開始剤）（ＣＧＩ－１２４、ＢＡＳＦ社製）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　３０部
・ＴＯ－１３８２　　　　　　　　　　　　　　　　　　　　　２５部
（重合性化合物　東亜合成化学（株）製　カルボキシル基含有５官能アクリレート）
・ジペンタエリスリトールヘキサアクリレート　　　　　　　　３０部
・溶剤（ＰＧＭＥＡ）　　　　　　　　　　　　　　　　　　２００部
・基板密着剤（３－メタクリロキシプロピルトリメトキシシラン）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１部 40 parts of the above-mentioned pigment (that is, each pigment of red (R) pigment, green (G) pigment, and blue (B) pigment), Dispersbyk-161 (BYK) (manufactured by BYK) as a dispersant, 30% Solution) A mixed liquid consisting of 50 parts and 110 parts of propylene glycol monomethyl ether as a solvent was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
The pigment dispersion (P1) that has been subjected to the dispersion treatment is stirred and mixed so that the following composition ratios are obtained, and the colored polymerizable composition R-1 for red (R) and the colored polymerizable composition G for green (G), respectively. -1 and a colored polymerizable composition B-1 for blue (B) were prepared.
<Composition>
-Colorant (pigment dispersion (P1)) 350 parts-Polymerization initiator (oxime photopolymerization initiator) (CGI-124, manufactured by BASF) 30 parts-TO-1382 25 parts (polymerizable compound Toa Gosei Chemical ( Co., Ltd. Carboxyl group-containing pentafunctional acrylate)
・ Dipentaerythritol hexaacrylate 30 parts ・ Solvent (PGMEA) 200 parts ・ Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane)
1 copy
（固体撮像素子用カラーフィルタの作製）
　前記実施例１で作製したブラックマトリックスを有する遮光性フィルタのウエハ上に、前記赤色（Ｒ）用着色重合性組成物Ｒ－１を用いて、１．６μｍ×１．６μｍの赤色（Ｒ）の着色パターンを形成した。更に、同様にして緑色（Ｇ）用着色重合性組成物Ｇ－１を用いて１．６μｍ×１．６μｍの緑色（Ｇ）の着色パターンを、及び青色（Ｂ）用着色重合性組成物Ｂ－１を用いて青色（Ｂ）の着色パターンを、順次形成して固体撮像素子用のカラーフィルタを作製した。 (Preparation of color filter for solid-state image sensor)
On the wafer of the light-shielding filter having the black matrix prepared in Example 1, the red (R) colored polymerizable composition R-1 was used, and a red (R) of 1.6 μm × 1.6 μm was formed. A colored pattern was formed. Further, in the same manner, a green (G) coloring pattern of 1.6 μm × 1.6 μm and a blue (B) colored polymerizable composition B using the green (G) colored polymerizable composition G-1. A blue (B) coloring pattern was sequentially formed using -1 to produce a color filter for a solid-state imaging device.
（評価）
　フルカラーのカラーフィルタを固体撮像素子に組み込んだところ、該固体撮像素子は、ブラックマトリックスの遮光性が高く、高解像度で色分離性に優れることが確認された。 (Evaluation)
When a full-color color filter was incorporated in the solid-state imaging device, it was confirmed that the solid-state imaging device has a high black matrix light-shielding property, high resolution, and excellent color separation.
＜液晶表示装置の作製＞
（有彩色着色重合性組成物の調製）
　前記分散処理した顔料分散液（Ｐ１）を用いて下記組成比となるよう撹拌混合し、重合性組成物の塗布液Ｒ－２を調製した。
・着色剤（顔料分散液（Ｐ１））　　　　　　　　　　　　　　　２００部
・プロピレングリコールモノメチルエーテルアセテート　　　１９．２０部
　（ＰＧＭＥＡ：溶剤）
・乳酸エチル　　　　　　　　　　　　　　　　　　　　　　３６．６７部
・樹脂　　　　　　　　　　　　　　　　　　　　　　　　　３３．５１部
　（メタクリル酸ベンジル／メタクリル酸／メタクリル酸－２－ヒドロキシエチル共重合体（＝６０／２２／１８［モル比］）の４０％ＰＧＭＥＡ溶液）
・エチレン性不飽和二重結合含有化合物　　　　　　　　　　１２．２０部
　（ジペンタエリスリトールヘキサアクリレート）
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　０．００６１部
・フッ素系界面活性剤　　　　　　　　　　　　　　　　　　　０．８３部
　（Ｆ－４７５、ＤＩＣ（株）製）
・光重合開始剤（トリハロメチルトリアジン系の光重合開始剤）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．５８６部 <Production of liquid crystal display device>
(Preparation of chromatic coloring polymerizable composition)
Using the pigment dispersion (P1) subjected to the dispersion treatment, the mixture was stirred and mixed so as to have the following composition ratio to prepare a coating liquid R-2 for a polymerizable composition.
Colorant (Pigment dispersion (P1)) 200 parts Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
-36.67 parts of ethyl lactate-33.51 parts of resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (= 60/22/18 [molar ratio]))
-Compound containing ethylenically unsaturated double bond 12.20 parts (dipentaerythritol hexaacrylate)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by DIC Corporation)
-Photopolymerization initiator (trihalomethyltriazine photopolymerization initiator)
0.586 parts
　また、緑色（Ｇ）用着色重合性組成物、及び青色（Ｂ）用着色重合性組成物としては、それぞれ、前記した固体撮像素子用カラーフィルタの作製のために調製した緑色（Ｇ）用着色重合性組成物Ｇ－１、及び青色（Ｂ）用着色重合性組成物Ｂ－１を用いた。 Moreover, as the coloring polymerizable composition for green (G) and the coloring polymerizable composition for blue (B), the coloring for green (G) prepared for the production of the color filter for the solid-state imaging device described above, respectively. The polymerizable composition G-1 and the colored polymerizable composition B-1 for blue (B) were used.
（液晶表示装置用カラーフィルタの作製）
　実施例１で作製した遮光性フィルタをブラックマトリックスとし、該ブラックマトリックス上に、前記赤色（Ｒ）用着色重合性組成物Ｒ－２を用いて、上記（固体撮像素子用カラーフィルタの作製）に記載の方法と同じ要領で８０×８０μｍの赤色（Ｒ）の着色パターンを形成した。更に、同様にして緑色（Ｇ）用着色重合性組成物Ｇ－１を用いて緑色（Ｇ）の有彩色着色パターンを、及び青色（Ｂ）用着色重合性組成物Ｂ－１を用いて青色（Ｂ）の有彩色着色パターンを順次形成して液晶表示装置用のブラックマトリクスを有するカラーフィルタを作製した。 (Production of color filters for liquid crystal display devices)
The light-shielding filter prepared in Example 1 was used as a black matrix, and the above-described (Preparation of color filter for solid-state imaging device) was performed on the black matrix using the colored polymerizable composition R-2 for red (R). A red (R) colored pattern of 80 × 80 μm was formed in the same manner as described. Further, in the same manner, a green (G) chromatic coloring pattern is obtained using the green (G) colored polymerizable composition G-1, and a blue color using the blue (B) colored polymerizable composition B-1. A chromatic color pattern of (B) was sequentially formed to produce a color filter having a black matrix for a liquid crystal display device.
－評価－
　上記のようにして作成したフルカラーの液晶表示装置カラーフィルタにＩＴＯ透明電極、配向膜等の加工を施し、液晶表示装置を設けた。本発明の重合性組成物は塗布面が均一性が良好で、液晶表示装置は表示ムラもなく、画質は良好であった。 -Evaluation-
The full color liquid crystal display device color filter prepared as described above was processed with an ITO transparent electrode, an alignment film and the like to provide a liquid crystal display device. The polymerizable composition of the present invention had good uniformity on the coated surface, the liquid crystal display device had no display unevenness, and the image quality was good.
＜ウエハレベルレンズの作製＞
　実施例１で作製した重合性組成物を用い、これを、レンズを設けたシリコンウエハ上に塗布することにより、遮光層が設けられたウエハレベルレンズを作製した。 <Production of wafer level lens>
A wafer level lens provided with a light shielding layer was prepared by applying the polymerizable composition prepared in Example 1 onto a silicon wafer provided with a lens.
　作製されたウエハレベルレンズを切断し、これにレンズモジュールを作製した後に撮像素子及びセンサ基板を取り付け、撮像ユニットを作製した。
　本発明のウエハレベルレンズは、遮光層の部分の塗布面の均一性が高く、遮光性が高く、この撮像ユニットを際の画質は良好であった。 The produced wafer level lens was cut, and a lens module was produced thereon, and then an imaging device and a sensor substrate were attached to produce an imaging unit.
The wafer level lens of the present invention has high uniformity of the coating surface of the light shielding layer portion and high light shielding properties, and the image quality when using this imaging unit was good.
　本発明によれば、分散性、保存安定性及び塗布性が高く、重合性化合物と組み合わせて重合性組成物とし、この重合性組成物を用いてパターン形成を行った場合に、未露光部における残渣が抑制されたパターンを形成可能であり、また、パターン形成における現像マージン及び現像ラチチュードを向上できる分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニットを提供することができる。 According to the present invention, the dispersibility, the storage stability and the coating property are high. When a polymerizable composition is combined with a polymerizable compound and pattern formation is performed using this polymerizable composition, in the unexposed area. A dispersion composition capable of forming a pattern in which a residue is suppressed and improving a development margin and development latitude in pattern formation, and a polymerizable composition, a light-shielding color filter, a solid-state imaging device, A liquid crystal display device, a wafer level lens, and an imaging unit can be provided.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１２年６月１日出願の日本特許出願（特願２０１２－１２６４７１）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on June 1, 2012 (Japanese Patent Application No. 2012-126471), the contents of which are incorporated herein by reference.
１　　　基板
１０　　レンズ
１４　　遮光層 1 substrate 10 lens 14 light shielding layer

Claims (18)

  1. 　（Ａ）チタンブラック、（Ｂ）グラフト鎖を有する構造単位と、前記グラフト鎖を有する構造単位とは異なる疎水性構造単位とを有する高分子化合物、及び、（Ｃ）溶媒を含有する分散組成物。 (A) titanium black, (B) a polymer compound having a structural unit having a graft chain and a hydrophobic structural unit different from the structural unit having the graft chain, and (C) a dispersion composition containing a solvent .
  2. 　前記疎水性構造単位は、ＣｌｏｇＰ値が１．２以上の化合物に由来する構造単位である、請求項１に記載の分散組成物。 The dispersion composition according to claim 1, wherein the hydrophobic structural unit is a structural unit derived from a compound having a ClogP value of 1.2 or more.
  3. 　前記疎水性構造単位が、下記一般式（ｉ）～（ｉｉｉ）で表される単量体に由来する構造単位から選択される１種以上の構造単位である、請求項１又は２に記載の分散組成物。
    Figure JPOXMLDOC01-appb-C000001
    　上記一般式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に、水素原子、ハロゲン原子、又はアルキル基を表す。
    　Ｘは、酸素原子又はイミノ基を表す。
    　Ｌは、単結合又は２価の連結基である。
    　Ｚは、脂肪族基、芳香族基、複素環基、又はそれらと酸素原子、硫黄原子、イミノ基、置換イミノ基若しくはカルボニル基との組合せを表す。
    　Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子、又はアルキル基、Ｚ、又は－Ｌ－Ｚを表す。     3. The hydrophobic structural unit according to claim 1, wherein the hydrophobic structural unit is one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii): Dispersion composition.
    Figure JPOXMLDOC01-appb-C000001
    In the general formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
    X represents an oxygen atom or an imino group.
    L is a single bond or a divalent linking group.
    Z represents an aliphatic group, an aromatic group, a heterocyclic group, or a combination thereof with an oxygen atom, a sulfur atom, an imino group, a substituted imino group or a carbonyl group.
    R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, Z, or —LZ.
  4. 　前記高分子化合物（Ｂ）の重量平均分子量が、６，０００～１００，０００である、請求項１～３のいずれか１項に記載の分散組成物。 The dispersion composition according to any one of claims 1 to 3, wherein the polymer compound (B) has a weight average molecular weight of 6,000 to 100,000.
  5. 　前記グラフト鎖を構成する原子の内、水素原子を除いた原子の数が４０～１００００の範囲である、請求項１～４のいずれか１項に記載の分散組成物。 The dispersion composition according to any one of claims 1 to 4, wherein the number of atoms excluding hydrogen atoms among the atoms constituting the graft chain is in the range of 40 to 10,000.
  6. 　前記グラフト鎖が、ポリエステル構造、ポリエーテル構造、及びポリ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種を有するグラフト鎖である、請求項１～５のいずれか１項に記載の分散組成物。 The dispersion composition according to any one of claims 1 to 5, wherein the graft chain is a graft chain having at least one selected from the group consisting of a polyester structure, a polyether structure, and a polyacrylate structure.
  7. 　前記高分子化合物（Ｂ）が、前記グラフト鎖を有する構造単位として、下記式（１）～式（４）で表される構造単位から選択された１種以上の構造単位を有する高分子化合物である、請求項１～６のいずれか１項に記載の分散組成物。
    Figure JPOXMLDOC01-appb-C000002
    〔式（１）～式（４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４はそれぞれ独立に酸素原子或いはＮＨを表し、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５はそれぞれ独立に水素原子又は１価の有機基を表し、Ｙ１、Ｙ２、Ｙ３、及びＹ４はそれぞれ独立に２価の連結基を表し、Ｚ１、Ｚ２、Ｚ３、及びＺ４はそれぞれ独立に１価の有機基を表す。Ｒ３は分岐又は直鎖のアルキレン基を表し、Ｒ４は水素原子又は１価の有機基を表す。ｎ、ｍ、ｐ、及びｑはそれぞれ独立に１から５００の整数を表す。ｊ及びｋはそれぞれ独立に２～８の整数を表す。式（３）において、ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。式（４）において、ｑが２～５００のとき、複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。〕     The polymer compound (B) is a polymer compound having one or more structural units selected from the structural units represented by the following formulas (1) to (4) as the structural unit having the graft chain. The dispersion composition according to any one of claims 1 to 6, wherein
    Figure JPOXMLDOC01-appb-C000002
    [In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, and X 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a monovalent organic group, Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group. R 3 represents a branched or straight chain alkylene group, and R 4 represents a hydrogen atom or a monovalent organic group. n, m, p, and q each independently represents an integer of 1 to 500. j and k each independently represents an integer of 2 to 8. In the formula (3), when p is 2 to 500, a plurality of R 3 may be the same or different from each other. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 may be the same or different from each other. ]
  8. 　前記高分子化合物（Ｂ）が、前記式（１）～式（４）で表される構造単位から選択された１種以上の構造単位を、前記高分子化合物（Ｂ）の総質量に対し質量換算で、１０％～９０％の範囲で含む高分子化合物である、請求項７に記載の分散組成物。 The polymer compound (B) has one or more structural units selected from the structural units represented by the formulas (1) to (4) in a mass relative to the total mass of the polymer compound (B). The dispersion composition according to claim 7, wherein the dispersion composition is a polymer compound contained in a range of 10% to 90% in terms of conversion.
  9. 　前記高分子化合物（Ｂ）が、前記チタンブラックと相互作用を形成しうる官能基を有する構造単位を更に有する高分子化合物である、請求項１～８のいずれか１項に記載の分散組成物。 The dispersion composition according to any one of claims 1 to 8, wherein the polymer compound (B) is a polymer compound further having a structural unit having a functional group capable of interacting with the titanium black. .
  10. 　前記高分子化合物（Ｂ）が、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種を有する構造単位を更に有する高分子化合物である、請求項１～９のいずれか１項に記載の分散組成物。 10. The polymer compound according to claim 1, wherein the polymer compound (B) is a polymer compound further having a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The dispersion composition described in 1.
  11. 　前記高分子化合物（Ｂ）の酸価が、１０～１４０ｍｇＫＯＨ／ｇである、請求項１～１０のいずれか１項に記載の分散組成物。 The dispersion composition according to any one of claims 1 to 10, wherein the polymer compound (B) has an acid value of 10 to 140 mgKOH / g.
  12. 　請求項１～１１のいずれか１項に記載の分散組成物、（Ｄ）重合性化合物、及び（Ｅ）重合開始剤を含む、重合性組成物。 A polymerizable composition comprising the dispersion composition according to any one of claims 1 to 11, (D) a polymerizable compound, and (E) a polymerization initiator.
  13. 　前記（Ｅ）重合開始剤が、オキシム化合物である、請求項１２に記載の重合性組成物。 The polymerizable composition according to claim 12, wherein the (E) polymerization initiator is an oxime compound.
  14. 　基板上に、請求項１２又は１３に記載の重合性組成物を用いて形成された着色パターンを有する遮光性カラーフィルタ。 A light-shielding color filter having a colored pattern formed on the substrate using the polymerizable composition according to claim 12 or 13.
  15. 　請求項１４に記載の遮光性カラーフィルタを備えた固体撮像素子。 A solid-state imaging device comprising the light-shielding color filter according to claim 14.
  16. 　請求項１４に記載の遮光性カラーフィルタを備えた液晶表示装置。 A liquid crystal display device comprising the light-shielding color filter according to claim 14.
  17. 　複数のレンズが一体に成形された基板と、該基板の前記レンズのレンズ面を除く領域に設けられた請求項１４に記載の遮光性カラーフィルタと、を備えたウエハレベルレンズ。 A wafer level lens comprising: a substrate on which a plurality of lenses are integrally formed; and the light-shielding color filter according to claim 14 provided in a region excluding the lens surface of the lens.
  18. 　請求項１７に記載のウエハレベルレンズを備えた撮像ユニット。 An image pickup unit comprising the wafer level lens according to claim 17.
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