WO2022024969A1 - 光学フィルタの製造方法および固体撮像素子の製造方法 - Google Patents
光学フィルタの製造方法および固体撮像素子の製造方法 Download PDFInfo
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
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- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—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 side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- 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
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/18—Solid spheres inorganic
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
Definitions
- the present invention relates to a method for manufacturing an optical filter having a partition wall and a solid-state image pickup device.
- CCD charge-coupled device
- the color filter is manufactured, for example, by using a coloring composition containing a coloring material and forming a pattern by a photolithography method.
- Patent Document 1 describes a coating film forming step of applying a colored photosensitive resin composition on a support to form a coating film, and a region having a colored pattern of the coating film of 300 nm or less using a mask.
- an object of the present invention is to provide a method for manufacturing an optical filter and a method for manufacturing a solid-state image sensor in which the occurrence of variation in the line width of pixels is suppressed even when heated to a high temperature.
- the present invention provides the following. ⁇ 1> An ethylenically unsaturated bond with a coloring material is provided on a support having a partition having a refractive index of 1.10 to 1.30 for light having a wavelength of 300 nm and having a plurality of regions partitioned by the partition. A step of applying a pixel-forming composition containing a compound having a containing group and containing 50% by mass or more of a coloring material in the total solid content to form a composition layer.
- the compound having an ethylenically unsaturated bond-containing group includes a polymerizable monomer having an ethylenically unsaturated bond-containing group and a resin having an ethylenically unsaturated bond-containing group, ⁇ 1> or ⁇ 2>.
- the method for manufacturing an optical filter ⁇ 4> The method for producing an optical filter according to ⁇ 3>, which contains 100 to 1000 parts by mass of a resin having an ethylenically unsaturated bond-containing group with respect to 100 parts by mass of the polymerizable monomer.
- ⁇ 5> The method for producing an optical filter according to any one of ⁇ 1> to ⁇ 4>, wherein the pixel-forming composition contains a photopolymerization initiator.
- ⁇ 6> The method for producing an optical filter according to ⁇ 5>, wherein the photopolymerization initiator contains an oxime compound.
- ⁇ 7> The method for manufacturing an optical filter according to any one of ⁇ 1> to ⁇ 6>, wherein the color material contains a chromatic color material.
- ⁇ 8> The method for manufacturing an optical filter according to any one of ⁇ 1> to ⁇ 7>, wherein the light having a wavelength of 300 nm or less irradiating the composition layer is light having a wavelength of 248 nm.
- a method for manufacturing a solid-state image sensor which comprises the method for manufacturing an optical filter according to any one of ⁇ 1> to ⁇ 8>.
- the present invention it is possible to provide a method for manufacturing an optical filter and a method for manufacturing a solid-state image sensor in which variation in the line width of pixels is suppressed even when heated to a high temperature.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent.
- alkyl group when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). It means.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or.
- Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic", or either.
- concentration of solids in a composition is expressed as a percentage of the total mass of the composition by the mass of the other components excluding the solvent.
- Mw weight average molecular weight
- Mn number average molecular weight
- the near infrared ray means light having a wavelength of 700 to 2500 nm.
- the direction in which the layers are stacked with respect to the support is referred to as "upper”, and the opposite direction is referred to as “lower”.
- the "upward” direction in the present specification may be different from the vertical upward direction.
- the term "process” is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
- the method for manufacturing an optical filter of the present invention is as follows.
- a colorant and an ethylenically unsaturated bond-containing group are placed on a support having a partition having a refractive index of 1.10 to 1.30 for light having a wavelength of 300 nm and having a plurality of regions partitioned by the partition.
- the reaction efficiency of the compound having an ethylenically unsaturated bond-containing group contained in the composition layer can be enhanced.
- the refractive index of the partition wall with respect to light having a wavelength of 300 nm is 1.10 to 1.30, the exposure light can be reflected or scattered by the partition wall to improve the utilization efficiency of the exposure light, and the composition at the time of exposure can be improved. It is presumed that the layer can be sufficiently cured. Therefore, it is presumed that even when heated to a high temperature, it was possible to form pixels in which the occurrence of line width variation was suppressed.
- composition layer forming step First, a color material and an ethylenically unsaturated bond are contained on a support having a partition having a refractive index of 1.10 to 1.30 for light having a wavelength of 300 nm and having a plurality of regions partitioned by the partition. A composition for forming a pixel containing a compound having a group and containing 50% by mass or more of a coloring material in the total solid content is applied to form a composition layer (composition layer forming step).
- the support having a partition wall will be explained.
- FIG. 1 is a side sectional view showing an embodiment of a support having a partition wall
- FIG. 2 is a plan view seen from directly above the support.
- a partition wall 11 is formed on the surface of the support 10.
- a plurality of regions partitioned by the partition wall 11 are provided on the surface of the support 10.
- FIG. 2 is a plan view seen from directly above the support.
- the partition wall 11 is formed in a grid pattern on the surface of the support 10, and the shape of the region partitioned by the partition wall 11 on the support 10 (hereinafter, also referred to as the shape of the opening of the partition wall) is Although it has a square shape, the shape of the opening of the partition wall 11 is not particularly limited, and may be, for example, a rectangular shape, a circular shape, an elliptical shape, a polygonal shape, or the like. Further, in FIG. 1, the partition wall 11 has a columnar shape, but the shape of the partition wall is not limited to the columnar shape, and may be a forward taper shape or a reverse taper shape. Further, the width of the partition wall may be gradually increased or reduced in diameter from the support side toward the tip.
- the forward taper shape is a shape in which the width of the partition wall is continuously reduced from the support side toward the tip
- the reverse taper shape is a shape in which the width of the partition wall is continuous from the support side to the tip.
- the columnar shape means that the width of the partition wall is almost the same on the support side and the tip side.
- the material of the support 10 is not particularly limited.
- a silicon substrate, an InGaAs substrate, and the like can be mentioned.
- a base layer may be formed on the surface of the support 10 in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.
- the support 10 may be provided with a photoelectric conversion unit. Examples of the photoelectric conversion unit include a silicon photodiode, an InGaAs photodiode, an organic photoelectric conversion film, and quantum dots. Further, a gap may be formed between adjacent photoelectric conversion units.
- a partition wall 11 is arranged on the surface of the support 10.
- the refractive index of the partition wall 11 with respect to light having a wavelength of 300 nm is 1.10 to 1.30.
- the lower limit of the refractive index is preferably 1.12 or more, and more preferably 1.15 or more, from the viewpoint of the strength of the partition wall.
- the upper limit of the refractive index is preferably 1.29 or less, and more preferably 1.28 or less, from the viewpoint of light condensing property.
- the value of the refractive index is a value at 25 ° C.
- the refractive index of the partition wall 11 with respect to light having a wavelength of 300 nm is preferably smaller than the refractive index of the pixels (for example, pixels 31 to 33 in FIG. 5) formed by the pixel forming composition. According to this aspect, at the time of pixel formation, the exposure light can be more effectively reflected or scattered by the partition wall, and the utilization efficiency of the exposure light can be further improved.
- the difference between the refractive index of the partition wall 11 with respect to light having a wavelength of 533 nm and the refractive index of the pixel formed by the pixel forming composition with respect to light having a wavelength of 1000 nm is preferably 0.30 to 0.80. According to this aspect, even if light is incident on the pixels of the optical filter from an oblique direction, it is possible to suppress light leakage to adjacent pixels. Therefore, the light transmitted through the pixels can be efficiently incident on the photoelectric conversion unit or the like, and the difference between the sensitivity to the vertically incident light and the sensitivity to the oblique incident light in the photoelectric conversion unit can be reduced.
- the lower limit of the difference in refractive index is preferably 0.40 or more, and more preferably 0.50 or more, for the reason of suppressing crosstalk.
- the upper limit of the difference in refractive index is preferably 0.75 or less, and more preferably 0.70 or less.
- the width W1 of the partition wall 11 is preferably 80 to 150 nm.
- the lower limit of the width W1 of the partition wall 11 is preferably 90 nm or more, more preferably 100 nm or more, and further preferably 110 nm or more from the viewpoint of the strength of the partition wall.
- the upper limit of the width W1 of the partition wall 11 is preferably 140 nm or less, and more preferably 130 nm or less from the viewpoint of ensuring an effective pixel size.
- the thickness (height) H1 of the partition wall 11 is preferably 300 to 650 nm.
- the lower limit of the thickness H1 of the partition wall 11 is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more.
- the upper limit of the thickness H1 of the partition wall 11 is preferably 600 nm or less, more preferably 550 nm or less, and further preferably 500 nm or less.
- the thickness of the partition wall means the length of the partition wall in the vertical direction
- the width of the partition wall means the length of the partition wall in the horizontal direction
- the porosity of the partition wall 11 is preferably 20 to 80%.
- the lower limit of the porosity is preferably 30% or more, more preferably 40% or more.
- the upper limit of the porosity is preferably 70% or less, more preferably 60% or less.
- the porosity of the partition wall is a value measured by the X-ray reflectivity method. Further, since the partition wall has a void, the thermal conductivity of the partition wall is lowered, and heat transfer from the partition wall to the pixel portion can be suppressed.
- the pitch W3 of the partition wall 11 arranged on the support 10 is preferably 400 to 1200 nm.
- the lower limit of the pitch W3 is preferably 450 nm or more, and more preferably 500 nm or more.
- the upper limit of the pitch W3 is preferably 1000 nm or less, more preferably 900 nm or less, and further preferably 800 nm or less.
- the bulkhead pitch is the total value of the bulkhead width W1 and the bulkhead opening 12 width W2 (distance between facing surfaces of the facing bulkheads).
- the width W2 of the partition wall opening 12 is preferably 300 to 1100 nm.
- the lower limit is preferably 400 nm or more, and more preferably 450 nm or more.
- the upper limit is preferably 1000 nm or less, more preferably 900 nm or less.
- the width W2 of the partition wall opening 12 corresponds to the width of the pixels formed between the partition walls. If the width W2 of the partition wall opening 12 is within the above-mentioned range, the solid-state image sensor can be miniaturized and have high resolution.
- the material of the partition wall 11 is not particularly limited. Examples thereof include organic materials such as siloxane resin and fluororesin, and inorganic particles such as silica particles and magnesium fluoride.
- the partition wall 11 preferably contains silica particles because the strength of the partition wall can be increased.
- the silica particles are silica particles having a shape in which a plurality of spherical silicas are connected in a bead shape because the transfer of heat from the partition wall to the pixel portion can be suppressed when the optical filter is exposed to a high temperature. It is preferably silica particles having a hollow structure (hereinafter, also referred to as hollow silica), and more preferably beaded silica. Further, it is also preferable that at least a part of the hydroxy groups on the surface of the silica particles of the silica particles is treated with a hydrophobic treatment agent that reacts with the hydroxy groups.
- a hydrophobic treatment agent that reacts with the hydroxy groups.
- the hydrophobizing agent a compound having a structure that reacts with the hydroxy group on the surface of the silica particles (preferably a structure that couples with the hydroxy group on the surface of the silica particles) and improves the hydrophobicity of the silica particles is used. ..
- the hydrophobizing agent is preferably an organic compound.
- Specific examples of the hydrophobizing agent include an organic silane compound, an organic titanium compound, an organic zirconium compound and an organic aluminum compound, and an organic silane compound is more preferable because an increase in the refractive index can be suppressed.
- "spherical" means that it may be substantially spherical and may be deformed as long as the effect of the present invention is exhibited.
- a plurality of spherical silica particles connected in a bead shape means a structure in which a plurality of spherical silica particles are connected in a linear and / or branched form.
- a plurality of spherical silica particles are connected by a joint having a smaller outer diameter.
- the structure in which "a plurality of spherical silica particles are connected in a bead shape" is not only a structure in which the particles are connected in a ring shape but also a chain shape having an end. Structure is also included.
- the beaded silica preferably has a ratio D 1 / D 2 of the average particle diameter D 1 measured by a dynamic light scattering method and the average particle diameter D 2 obtained by the following formula (1) of 3 or more.
- the upper limit of D 1 / D 2 is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. By setting D 1 / D 2 in such a range, good optical characteristics can be exhibited.
- D 2 is the average particle size of the beaded silica
- the unit is nm
- S is the specific surface area of the beaded silica measured by the nitrogen adsorption method, and the unit is m 2 / g. be.
- the average particle diameter D 2 of the beaded silica can be regarded as an average particle diameter close to the diameter of the primary particles of spherical silica.
- the average particle diameter D 2 is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 7 nm or more.
- the upper limit is preferably 100 nm or less, more preferably 80 nm or less, further preferably 70 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less.
- the average particle diameter D 2 can be replaced by the equivalent circle diameter (D0) in the projected image of the spherical portion measured by a transmission electron microscope (TEM). Unless otherwise specified, the average particle diameter based on the diameter equivalent to a circle is evaluated by the average number of 50 or more particles.
- D0 equivalent circle diameter
- TEM transmission electron microscope
- the average particle size D 1 of the beaded silica can be regarded as the number average particle size of the secondary particles in which a plurality of spherical silicas are collected. Therefore, the relationship D 1 > D 2 usually holds.
- the average particle size D 1 is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 10 nm or more.
- the upper limit is preferably 100 nm or less, more preferably 70 nm or less, further preferably 50 nm or less, and particularly preferably 45 nm or less.
- the measurement of the average particle size D 1 of the beaded silica is performed using a dynamic light scattering type particle size distribution measuring device (Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd.).
- the procedure is as follows. The dispersion of beaded silica is divided into 20 ml sample bottles and diluted with propylene glycol monomethyl ether so that the solid content concentration becomes 0.2% by mass. The diluted sample solution is irradiated with 40 kHz ultrasonic waves for 1 minute, and immediately after that, it is used for the test. Data is captured 10 times using a 2 ml quartz cell for measurement at a temperature of 25 ° C., and the obtained "number average” is taken as the average particle size.
- JISZ8828 2013 "Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
- the beaded silica it is preferable that a plurality of spherical silicas having an average particle diameter of 1 to 80 nm are connected via a connecting material.
- the upper limit of the average particle size of the spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and further preferably 50 nm or less.
- the lower limit of the average particle size of the spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more.
- the value of the average particle diameter of the spherical silica the value of the average particle diameter obtained from the equivalent circle diameter in the projected image of the spherical portion measured by the transmission electron microscope (TEM) is used.
- TEM transmission electron microscope
- Examples of the connecting material for connecting spherical silica to each other in prayer-shaped silica include metal oxide-containing silica.
- Examples of the metal oxide include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti.
- Examples of the metal oxide-containing silica include a reaction product and a mixture of these metal oxides and silica (SiO 2 ).
- the connecting material the description of International Publication No. 2000/015552 can be taken into consideration, and this content is incorporated in the present specification.
- the number of connected spherical silicas in the beaded silica is preferably 3 or more, and more preferably 5 or more.
- the upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.
- the number of connected spherical silicas can be measured by TEM.
- particle liquids containing beaded silica include Snowtex series and organosilica sol series (methanol dispersion, isopropyl alcohol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, etc.) manufactured by Nissan Chemical Industry Co., Ltd., product number IPA. -ST-UP, MEK-ST-UP, etc.). Further, as the particle liquid containing beaded silica, for example, the silica sol described in Japanese Patent No. 4328935 can be used.
- the average particle size of hollow silica is preferably 10 to 500 nm.
- the lower limit is preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more.
- the upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
- the average particle size of hollow silica is a value measured by a dynamic light scattering method. Examples of commercially available particle liquids containing hollow silica include "Thruria 4110" manufactured by JGC Catalysts and Chemicals Co., Ltd.
- the partition wall 11 can be formed by using a conventionally known method.
- the partition wall can be formed as follows.
- a partition wall material layer is formed on the support.
- the partition wall material layer can be formed, for example, by applying a composition containing inorganic particles such as silica particles (partition wall forming composition) onto a support and then curing the partition wall material layer.
- the composition for forming a partition wall further contains a surfactant.
- the surfactant include materials exemplified as those used in the pixel forming composition described later.
- the composition for forming a partition wall may further contain a polymerizable compound or a resin. Examples of such a material include materials exemplified as those used for the pixel forming composition described later.
- a 1 to 6-functional (meth) acrylate compound may be contained as the polymerizable compound.
- a monofunctional or bifunctional (meth) acrylate compound more preferably a bifunctional (meth) acrylate compound containing an alkylene group having 6 or more carbon atoms, and 9 or more carbon atoms. It is more preferable to contain a bifunctional (meth) acrylate compound containing the alkylene group of.
- the monofunctional (meth) acrylate compound include isodecyl (meth) acrylate.
- the bifunctional (meth) acrylate compound examples include 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate.
- Examples of such a composition include the compositions described in paragraphs 0012 to 0077 and 093 to 0105 of International Publication No. 2019/017280, and the compositions described in paragraph numbers 0081 to 0091 of International Publication No. 2019/11748. Items and the like are mentioned, and these contents are incorporated in the present specification.
- the solid content concentration of the partition wall forming composition is preferably 3 to 20% by mass, more preferably 5 to 18% by mass, and even more preferably 7 to 16% by mass.
- the partition wall material layer can be formed by forming an inorganic material such as silicon dioxide on a support by a vapor deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering.
- a vapor deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering.
- a resist pattern is formed on the partition wall material layer using a mask having a pattern along the shape of the partition wall.
- the partition wall material layer is etched to form a pattern.
- the etching method include a dry etching method and a wet etching method. Etching by the dry etching method can be performed under the conditions described in paragraphs 0128 to 0133 of JP-A-2016-014856.
- the resist pattern is then stripped off from the bulkhead material layer. In this way, the partition wall can be formed.
- a base layer may be provided on the surfaces of the partition wall 11 and the support 10. By providing the base layer, the adhesion between the pixel and the partition wall can be improved. Further, it is possible to suppress the diffusion of the components in the pixel into the partition wall and increase the strength of the partition wall.
- the material of the base layer various inorganic materials and organic materials can be used.
- the organic material include acrylic resin, polystyrene resin, polyimide resin, and organic SOG (Spin On Glass) resin.
- a composition containing a compound having an ethylenically unsaturated bond-containing group can also be used to form an underlayer.
- an organic silane compound such as 1,1,1,3,3,3-hexamethyldisilazane can be used to form an underlayer.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group and the like, and a (meth) allyl group and a (meth) acryloyl group are preferable.
- the compound having an ethylenically unsaturated bond-containing group may be a monomer or a resin such as a polymer.
- the inorganic material include silicon dioxide and aluminum oxide.
- the base layer can be formed by using a conventionally known method.
- a composition containing an organic material can be applied and dried on a partition wall to form the base layer.
- the inorganic material constituting the underlayer is formed on the surface of a partition wall by a vapor deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering. Can be formed.
- the contact angle of the base layer with water at 25 ° C. is preferably 10 to 60 °, preferably 15 to 50 °, and even more preferably 20 to 45 °. When the contact angle of the base layer is within the above range, it is possible to achieve both suppression of residue generation and high-level pixel adhesion.
- the contact angle of the base layer is a value obtained by measuring the static contact angle by the sessile drop method.
- FIG. 3 is a diagram showing a state in which the pixel-forming composition is applied onto the support shown in FIG. 1 to form the composition layer 30.
- the composition for forming pixels will be described later.
- a known method can be used as a method for applying the composition for forming pixels.
- a drop method drop cast
- a slit coat method for example, a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
- Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
- Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned.
- the method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
- the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.
- the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
- the prebake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 2200 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.
- the composition layer on the support formed as described above is exposed by irradiating the composition layer having a wavelength of 300 nm or less in a pattern (exposure step). This makes it possible to cure the exposed portion of the composition layer.
- the light used for exposure may be light having a wavelength of 300 nm or less, preferably light having a wavelength of 180 to 300 nm.
- Specific examples thereof include KrF line (wavelength 248 nm) and ArF (wavelength 193 nm), and KrF line (light having a wavelength of 248 nm) is preferable because the effect of the present invention can be remarkably obtained.
- pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).
- the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 .
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the oxygen concentration performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume.
- the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2 ). Can be done.
- the oxygen concentration and the exposure illuminance may be appropriately combined with each other, and for example, the illuminance may be 10,000 W / m 2 when the oxygen concentration is 10% by volume, the illuminance may be 20000 W / m 2 when the oxygen concentration is 35% by volume, and the like.
- composition layer in the unexposed portion of the composition layer after the exposure step is developed and removed (development step).
- development step the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains, and as shown in FIG. 4, the pixels are contained in the region partitioned by the partition wall 11 on the support 10. 31 is formed.
- the temperature of the developer is preferably, for example, 20 to 30 ° C.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
- Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
- the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
- the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc.
- examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
- the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
- the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
- the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed.
- the nozzle for discharging the rinse liquid from the central portion of the support it is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support.
- the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.
- Additional exposure processing and post-baking are post-development curing treatments to complete the curing.
- the heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
- Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. ..
- the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
- an optical filter having a plurality of pixels can be manufactured by repeating each of the above-mentioned steps (composition layer forming step, exposure step, developing step) for each pixel. ..
- FIG. 5 is a schematic diagram of an optical filter in which pixels 31 to 33 are formed by repeating each of the above steps.
- a composition containing a coloring material and a compound having an ethylenically unsaturated bond-containing group and containing 50% by mass or more of the coloring material in the total solid content is used.
- the types of pixels formed by the pixel forming composition include colored pixels such as red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, and magenta pixels; white pixels; black pixels; near-infrared cut filters. Pixels; and pixels of near-infrared transmission filters.
- Examples of the pixels of the near-infrared cut filter include pixels having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm.
- the pixels of the near-infrared cut filter are preferably pixels having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and more preferably pixels having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
- the light transmittance of the pixels of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. preferable.
- the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
- the absorbance Amax / absorbance A550 which is the ratio of the absorbance Amax at the maximum absorption wavelength of the pixel of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, preferably 50 to 500. More preferably, it is more preferably 70 to 450, and particularly preferably 100 to 400.
- the pixel of the near-infrared ray transmission filter is a pixel that transmits at least a part of the near-infrared ray.
- the pixel of the near-infrared transmission filter may be a pixel that transmits both visible light and near-infrared light, or may be a pixel that shields at least a part of visible light and transmits at least a part of near-infrared light. ..
- the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance is in the wavelength range of 1100 to 1300 nm.
- a pixel satisfying the spectral characteristics in which the minimum value of the rate is 70% or more (preferably 75% or more, more preferably 80% or more) is mentioned.
- the pixels of the near-infrared transmission filter are preferably pixels that satisfy any of the following spectral characteristics (IR1) to (IR5).
- IR1 The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 800 to 1300 nm is. Pixels that are 70% or more (preferably 75% or more, more preferably 80% or more).
- IR2 The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1300 nm is. Pixels that are 70% or more (preferably 75% or more, more preferably 80% or more).
- IR3 The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is. Pixels that are 70% or more (preferably 75% or more, more preferably 80% or more).
- IR4 The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300 nm is. Pixels that are 70% or more (preferably 75% or more, more preferably 80% or more).
- IR5 The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1200 to 1500 nm is. Pixels that are 70% or more (preferably 75% or more, more preferably 80% or more).
- Examples of the pixel forming composition preferably used for forming colored pixels include a composition containing a chromatic color material as a color material. Further, examples of the pixel forming composition preferably used for forming the pixels of the near-infrared cut filter include a composition containing a near-infrared absorbing color material as the coloring material. Further, as a pixel forming composition preferably used for forming pixels of a near-infrared transmission filter, two or more kinds of chromatic color materials are contained as color materials, and black color is obtained by combining two or more kinds of chromatic color materials. Examples thereof include a composition using the presenting material. Further, a black color material or a near-infrared absorbing color material may be contained.
- a pixel forming composition preferably used for forming black pixels a composition containing a black coloring material as a coloring material and the like can be mentioned. Further, it is also possible to use a composition containing two or more kinds of chromatic color materials as the color material and using a combination of two or more kinds of chromatic color materials which exhibits black color. Further, as a pixel forming composition preferably used for forming white pixels, a composition containing a white coloring material as a coloring material and the like can be mentioned. Hereinafter, each component used in the pixel forming composition will be described in more detail.
- the pixel forming composition contains a coloring material.
- the coloring material may be a pigment or a dye. Pigments and dyes may be used in combination.
- the pigment may be either an inorganic pigment or an organic pigment.
- an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated.
- the average primary particle size of the pigment is preferably 1 to 200 nm.
- the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
- the upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less.
- the primary particle size of the pigment can be obtained from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
- the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments.
- the primary particles of the pigment refer to independent particles without aggregation.
- the content of the pigment in the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 90% by mass or more. Especially preferable.
- the color material used in the pixel forming composition examples include a chromatic color material, a black color material, a white color material, and a near-infrared absorbing color material.
- a pigment derivative can also be used as the coloring material.
- the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one kind of pigment derivative may be used, or two or more kinds may be used in combination. When two or more types are used in combination, the total amount thereof is preferably in the above range.
- a chromatic color material is preferably a pigment (chromatic color pigment).
- the content of the chromatic color material in the color material is preferably 80% by mass or more, and more preferably 90% by mass or more.
- a pixel-forming composition can be preferably used as a composition for forming colored pixels.
- chromatic color material examples include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.
- C. I. Pigment Green 7,10,36,37,58,59,62,63,64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type) and other green pigments.
- halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphate ester as a ligand according to International Publication No. 2012/102395, and Japanese Patent Application Laid-Open No. 2019-008014.
- an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue color material. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
- a nickel azobarbiturate complex having the following structure can also be used.
- a red color material As a red color material, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838.
- Naftor azo compound described in JP-A-2012-229344 red color material described in Japanese Patent No.
- red pigment a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. can.
- diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used as the coloring material.
- a dye can be used as a chromatic color material.
- the dye is not particularly limited, and known dyes can be used.
- pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound, xanthene compound examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds.
- a dye multimer can also be used.
- the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures.
- the upper limit is not particularly limited, but may be 100 or less.
- the plurality of dye structures contained in one molecule may have the same dye structure or may have different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- the compounds described in 031442 and the like can also be used.
- the chromatic color material may be used in combination of two or more.
- a green color may be formed in combination with Pigment Yellow 185
- a green color may be formed in combination with Pigment Yellow 185.
- black may be formed by a combination of two or more kinds of chromatic color materials.
- a combination include the following aspects (1) to (7).
- a pixel forming composition should be used.
- An embodiment containing a red color material and a blue color material An embodiment containing a red color material, a blue color material, and a yellow color material.
- An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material (5) An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material. (6) An embodiment containing a red color material, a blue color material, and a green color material. (7) An embodiment containing a yellow color material and a purple color material.
- pigment derivative examples include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
- the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, inimium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrolop pigment.
- Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group and salts thereof.
- alkali metal ions Li + , Na + , K + , etc.
- alkaline earth metal ions Ca 2+ , Mg 2+ , etc.
- ammonium ions imidazolium ions, pyridinium ions, etc.
- Examples include phosphonium ion.
- Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
- the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
- a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be contained.
- the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L ⁇ mol -1 ⁇ cm -1 or less, and 1000 L ⁇ mol -1 ⁇ cm -1 or less. Is more preferable, and 100 L ⁇ mol -1 ⁇ cm -1 or less is further preferable.
- the lower limit of ⁇ max is, for example, 1 L ⁇ mol -1 ⁇ cm -1 or more, and may be 10 L ⁇ mol -1 ⁇ cm -1 or more.
- pigment derivative examples include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961.
- Japanese Patent Laid-Open No. 03-026767 Japanese Patent Application Laid-Open No. 03-153780
- Japanese Patent Application Laid-Open No. 03-045662 Japanese Patent Application Laid-Open No. 04-285669
- Japanese Patent Application Laid-Open No. 06-145546 Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158
- Japanese Patent Laid-Open No. 10-030063 Japanese Patent Application Laid-Open No.
- White coloring materials include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples thereof include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
- the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide.
- the white pigment is preferably particles having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.
- titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, by Manabu Kiyono, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.
- the white pigment is not limited to a single inorganic substance, but particles compounded with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of core particles composed of polymer particles, and core and shell composite particles composed of a shell layer composed of inorganic nanoparticles are used. Is preferable.
- the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles for example, the description in paragraphs 0012 to 0042 of JP2015-047520 can be referred to. This content is incorporated herein.
- Hollow inorganic particles can also be used as the white pigment.
- Hollow inorganic particles are inorganic particles having a structure having cavities inside, and refer to inorganic particles having cavities surrounded by an outer shell.
- Examples of the hollow inorganic particles include the hollow inorganic particles described in JP-A-2011-075786, International Publication No. 2013/06621, JP-A-2015-164881, and the like, and the contents thereof are incorporated in the present specification. Is done.
- Black color material The black color material is not particularly limited, and known materials can be used.
- examples of the inorganic black coloring material include carbon black, titanium black, graphite and the like, with carbon black and titanium black being preferable, and titanium black being more preferable.
- Titanium black is black particles containing a titanium atom, and low-order titanium oxide or titanium oxynitride is preferable. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesion. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, it is also possible to treat with a water-repellent substance as shown in Japanese Patent Application Laid-Open No.
- Titanium black preferably has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle size is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles and having a content ratio of Si atoms and Ti atoms in the dispersion adjusted to be in the range of 0.20 to 0.50 can be mentioned. Regarding the above dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilak D (Tilak) D (trade name: manufactured by Mitsubishi Materials Corporation).
- Examples of the organic black coloring material include a bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound and the like, and a bisbenzofuranone compound and a perylene compound are preferable. Examples of the bisbenzofuranone compound are described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No.
- the near-infrared absorbing color material is preferably a pigment, more preferably an organic pigment. Further, the near-infrared absorbing color material is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. Further, the maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less.
- the near-infrared absorbing color material preferably has A 550 / A max , which is the ratio of the absorbance A 550 at a wavelength of 550 nm and the absorbance A max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less. It is more preferably 0.03 or less, and particularly preferably 0.02 or less.
- the lower limit is not particularly limited, but may be, for example, 0.0001 or more, or 0.0005 or more.
- the maximum absorption wavelength of the near-infrared absorbing color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the photosensitive composition containing the near-infrared absorbing color material.
- the near-infrared absorbing color material is not particularly limited, but is limited to pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, iminium compound, dithiol compound, and tria.
- Examples thereof include a reelmethane compound, a pyrromethene compound, an azomethin compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex.
- Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037-0052 of JP2011-066731A, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033.
- Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph No. 0072 of International Publication No.
- JP2012-077153 the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480.
- Examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP2012-07715A.
- Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
- Examples of the near-infrared absorbing color material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953.
- Squarylium compound described in Japanese Patent Publication No. 6036689 Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, Squarylium compound described in paragraphs 0090 to 0107 of International Publication No.
- Concatenated squalylium compound compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-type squarylium compound described in JP-A-2017-082029, JP-A-2017-066120
- the asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-067963, the pyrrol ring-containing compound (carbazole type) described in Japanese Patent Application Laid-Open No. 2017-067963, the phthalocyanine compound described in Japanese Patent No. 6251530, and the like are used. You can also do it.
- the content of the coloring material in the total solid content of the pixel forming composition is 50% by mass or more, preferably 54% by mass or more, more preferably 58% by mass or more, and 60% by mass or more. Is more preferable.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.
- the composition for forming a pixel contains a compound having an ethylenically unsaturated bond-containing group (hereinafter, also referred to as a polymerizable compound).
- a compound having an ethylenically unsaturated bond-containing group hereinafter, also referred to as a polymerizable compound.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styrene group and the like.
- the polymerizable compound may be a polymerizable monomer having an ethylenically unsaturated bond-containing group (hereinafter, also referred to as a polymerizable monomer), or a resin having an ethylenically unsaturated bond-containing group (hereinafter, also referred to as a polymerizable resin). ) May be.
- the molecular weight of the polymerizable monomer is preferably less than 2000, more preferably 1500 or less, and even more preferably 1000 or less.
- the lower limit is preferably 100 or more, and more preferably 150 or more.
- the weight average molecular weight (Mw) of the polymerizable resin is preferably 2000 to 2000000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3000 or more, and more preferably 5000 or more.
- the content of the polymerizable resin is preferably 100 to 1000 parts by mass, more preferably 200 to 900 parts by mass, and 300 to 800 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is more preferably by mass.
- the ratio of both is in the above range, various bonds other than the bonds between the polymerizable resins and the polymerizable monomers occur, so that a stronger film can be easily obtained.
- the polymerizable monomer is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 2 to 6 containing groups. Further, the polymerizable monomer is preferably a 2 to 15 functional (meth) acrylate compound, and more preferably a 2 to 6 functional (meth) acrylate compound.
- polymerizable compound examples include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A.
- the compounds described in paragraph numbers 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048637, Japanese Patent No. 6057891 and Japanese Patent Application Laid-Open No. 6031807 are These contents are incorporated herein by reference.
- the lower limit is preferably 3 mmol / g or more.
- the upper limit is preferably 11.8 mmol / g or less, more preferably 11.6 mmol / g or less, and even more preferably 11.4 mmol / g or less.
- the polymerizable monomer it is also preferable to use a polymerizable monomer having a fluorene skeleton.
- a polymerizable monomer having a fluorene skeleton By using a polymerizable monomer having a fluorene skeleton, a stronger film can be formed.
- the polymerizable monomer having a fluorene skeleton is preferably a bifunctional polymerizable monomer.
- Examples of the polymerizable monomer having a fluorene skeleton include a compound having a partial structure represented by the following formula (Fr). (Fr)
- R f1 and R f2 each independently represent a substituent
- m and n each independently represent an integer of 0 to 5.
- m R f1s may be the same or different from each other, and two R f1s out of m R f1s are bonded to each other to form a ring. May be good.
- n R f2s may be the same or different from each other, and two R f2s out of the n R f2s are bonded to each other to form a ring. May be good.
- R f1 and R f2 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , and -NR f15 .
- R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO 2 R f24 , -SO 2 OR f25 , -NHSO 2 R f26 or -SO 2 NR f27 R f28 can be mentioned.
- R f11 to R f28 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
- polymerizable monomer having a fluorene skeleton examples include compounds having the following structures.
- examples of commercially available products of the polymerizable monomer having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).
- n 0 to 14 and m is 1 to 8.
- a plurality of Rs and Ts existing in one molecule may be the same or different from each other.
- Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779.
- the compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).
- R 1 indicates a hydrogen atom or a methyl group
- m indicates a number of 1 or 2
- "*" indicates a bond.
- R 1 indicates a hydrogen atom or a methyl group, and "*" indicates a bond.
- a compound represented by the formula (Z-4) or (Z-5) can also be used.
- E is independently ⁇ ((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-.
- Y each independently represents an integer of 0 to 10
- X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
- the total number of (meth) acryloyl groups is 3 or 4
- each of m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40.
- the total number of (meth) acryloyl groups is 5 or 6, where n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
- -((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-in the formula (Z-4) or the formula (Z-5) is on the oxygen atom side. The form in which the end of is bound to X is preferable.
- the upper limit is preferably 2.5 mmol / g or less, and more preferably 2.0 mmol / g or less.
- the lower limit is preferably 0.2 mmol / g or more, and more preferably 0.25 mmol / g or more.
- HPLC high performance liquid chromatography
- the polymerizable resin is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain, and may be a resin containing a repeating unit represented by the following formula (A-1-1). More preferred. Further, in the polymerizable resin, the content of the repeating unit having an ethylenically unsaturated bond-containing group is preferably 10 mol% or more, and preferably 10 to 80 mol% in all the repeating units of the polymerizable resin. More preferably, it is more preferably 20 to 70 mol%.
- X 1 represents a trivalent linking group
- L 1 represents a single bond or a divalent linking group
- Y 1 represents an ethylenically unsaturated bond-containing group.
- Examples of the trivalent linking group X 1 in the formula (A-1-1) include a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, and a polyurea-based linking group.
- Polyester-based linking group, polyether-based linking group, polystyrene-based linking group and the like, and poly (meth) acrylic-based linking group, polyalkyleneimine-based linking group and polyester-based linking group are preferable, and poly (meth) acrylic-based linking group is preferable.
- Linking groups are more preferred.
- the divalent linking group represented by L 1 in the formula (A-1-1) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms).
- Group oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- , Examples thereof include -CO-, -O-, -COO-, -OCO-, -S-, and groups composed of a combination of two or more of these.
- the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, and a hydroxy group is preferable from the viewpoint of production suitability.
- Examples of the ethylenically unsaturated bond-containing group represented by Y 1 of the formula (A-1-1) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a styrene group, and the (meth) acryloyl group, A styrene group is preferable, a (meth) acryloyl group is more preferable, and an acryloyl group is particularly preferable.
- repeating unit represented by the formula (A-1-1) include a repeating unit represented by the following formula (A-1-1a) and a repeating unit represented by the following formula (A-1-1b). Units and the like can be mentioned.
- R a1 to R a3 independently represent a hydrogen atom or an alkyl group
- Q 1a is -CO-, -COO-, -OCO-, -CONH- or phenylene.
- a group is represented
- L 1 represents a single bond or a divalent linking group
- Y 1 represents an ethylenically unsaturated bond-containing group.
- the number of carbon atoms of the alkyl group represented by R a1 to Ra3 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.
- Q 1a is preferably -COO- or -CONH-, and more preferably -COO-.
- R a10 and R a11 each independently represent a hydrogen atom or an alkyl group
- m1 represents an integer of 1 to 5
- L1 is a single bond or a divalent linkage.
- Y 1 represents an ethylenically unsaturated bond-containing group.
- the number of carbon atoms of the alkyl group represented by R a10 and R a11 is preferably 1 to 10, and more preferably 1 to 3.
- the polymerizable resin is also preferably a resin having a graft chain.
- the resin having a graft chain include a resin containing a repeating unit having a graft chain.
- a polymerizable resin having a graft chain can be preferably used as a dispersant.
- the polymerizable resin can be polymerized in the vicinity of the coloring material at the time of exposure to firmly hold the coloring material in the film, and the heat diffusion of these compounds by heating can be performed. Can be effectively suppressed.
- the graft chain means a molecular chain branched from the main chain. Further, the main chain means a molecular chain having the most branch points.
- the weight average molecular weight of the graft chain is preferably 500 to 30,000, more preferably 1,000 to 20,000, and even more preferably 2,000 to 10,000.
- the graft chain preferably contains a repeating unit of at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure, and preferably contains a polyester structure and a poly structure. It is more preferable to include repeating units of at least one structure selected from an ether structure and a poly (meth) acrylic structure, and even more preferably to include repeating units of a polyester structure. Examples of the repeating unit of the polyester structure include the repeating unit of the structure represented by the following formula (G-1), formula (G-4) or formula (G-5).
- repeating unit of the polyether structure a repeating unit of the structure represented by the following formula (G-2) can be mentioned.
- the repeating unit of the poly (meth) acrylic structure a repeating unit of the structure represented by the following formula (G-3) can be mentioned.
- RG1 and RG2 each represent an alkylene group.
- the alkylene group represented by RG1 and RG2 a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable. , A linear or branched alkylene group having 3 to 12 carbon atoms is more preferable.
- RG3 represents a hydrogen atom or a methyl group.
- LG1 represents a single bond or a divalent linking group.
- the divalent linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylenecarbonyl group (preferably 1 to 12 carbon atoms).
- alkylene group preferably an alkylene group having 1 to 12 carbon atoms
- alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
- an oxyalkylenecarbonyl group preferably 1 to 12 carbon atoms.
- arylene group preferably arylene group having 6 to 20 carbon atoms
- RG4 represents a hydrogen atom or a substituent.
- the substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, and a cyclic ether.
- Examples include groups and blocked isocyanate groups.
- Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
- a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable, from the viewpoint of improving the dispersibility of the pigment.
- the alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.
- the polymerizable resin is preferably a resin containing a repeating unit represented by the following formula (A-1-2).
- X 2 represents a trivalent linking group
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- Examples of the trivalent linking group represented by X 2 in the formula (A-1-2) include the linking group having the valence described in X 1 in the formula (A-1-1), and the preferred range is also the same.
- the divalent linking group represented by L 2 of the formula (A-1-2) an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms).
- -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned.
- the graft chain represented by W 1 in the formula (A-1-2) include the above-mentioned graft chain.
- repeating unit represented by the formula (A-1-2) include the repeating unit represented by the following formula (A-1-2a) and the repeating unit represented by the following formula (A-1-2b). Units and the like can be mentioned.
- R b1 to R b3 independently represent a hydrogen atom or an alkyl group
- Q b1 is -CO-, -COO-, -OCO-, -CONH- or phenylene.
- Group represents a group
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- the number of carbon atoms of the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.
- Q b1 is preferably -COO- or -CONH-, and more preferably -COO-.
- R b10 and R b11 independently represent a hydrogen atom or an alkyl group
- m2 represents an integer of 1 to 5
- L 2 is a single bond or a divalent link.
- W 1 represents a graft chain.
- the number of carbon atoms of the alkyl group represented by R b10 and R b11 is preferably 1 to 10, and more preferably 1 to 3.
- the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and 1000 to 7500. Is more preferable.
- the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit.
- repeating units with graft chains can be formed by polymerizing macromonomers.
- the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer.
- the content of the repeating unit represented by the formula (A-1-2) is 1 in all the repeating units of the polymerizable resin. It is preferably 0.0 to 60 mol%, more preferably 1.5 to 50 mol%.
- the polymerizable resin further contains a repeating unit having an acid group.
- the dispersibility of the pigment or the like can be further improved.
- the developability can be improved.
- the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.
- the content of the repeating unit having an acid group is preferably 80 mol% or less in all the repeating units of the polymerizable resin, preferably 10 to 80 mol%. More preferred.
- the acid value of the polymerizable resin is preferably 20 to 150 mgKOH / g.
- the upper limit is more preferably 100 mgKOH / g or less.
- the lower limit is preferably 30 mgKOH / g or more, and more preferably 35 mgKOH / g or more.
- the polymerizable resin is also preferably a resin containing a repeating unit represented by the formula (Ac-1).
- Ar 10 represents a group containing an aromatic carboxyl group
- L 11 represents -COO- or -CONH-
- L 12 represents a trivalent linking group
- P 10 represents ethylene. Represents a polymer chain having a sex unsaturated bond-containing group.
- Examples of the group containing an aromatic carboxyl group represented by Ar 10 in the formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
- Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.
- Q 1 is represented by a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).
- n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
- n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
- n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
- Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , the above formula (Q-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
- * 1 represents the bonding position with L 11 .
- L 11 of the formula (Ac-1) represents -COO- or -CONH-, and preferably -COO-.
- the trivalent linking group represented by L 12 in the formula (Ac-1) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these.
- a group that combines species or more can be mentioned.
- the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
- the hydrocarbon group may have a substituent.
- substituent include a hydroxy group and the like.
- the trivalent linking group represented by L 12 is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).
- L 12b represents a trivalent linking group
- X 1 represents S
- * 1 represents the bonding position with L 11 in the formula (Ac-1)
- * 2 represents the bonding position of the formula (Ac-1). It represents the bonding position of Ac- 1 ) with P10.
- the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined with, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined is preferable.
- L 12c represents a trivalent linking group
- X 1 represents S
- * 1 represents the bonding position with L 11 in the formula (Ac-1)
- * 2 represents the bonding position with L 11 in the formula (Ac-1). It represents the bonding position of Ac- 1 ) with P10.
- the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.
- P10 of the formula (Ac- 1 ) represents a polymer chain having an ethylenically unsaturated bond-containing group.
- the polymer chain represented by P 10 preferably contains a repeating unit of at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure. It is more preferable to include repeating units of at least one structure selected from a polyester structure, a polyether structure and a poly (meth) acrylic structure, and further preferably to include repeating units of a polyester structure.
- repeating unit of the polyester structure examples include the repeating unit of the structure represented by the above-mentioned formula (G-1), formula (G-4) or formula (G-5). Further, as the repeating unit of the polyether structure, the repeating unit of the structure represented by the above-mentioned formula (G-2) can be mentioned. Further, as the repeating unit of the poly (meth) acrylic structure, the repeating unit of the structure represented by the above-mentioned formula (G-3) can be mentioned.
- the ratio of the repeating unit containing an ethylenically unsaturated bond-containing group in the side chain in all the repeating units constituting P 10 is preferably 5% by mass or more, and 10 mass by mass. % Or more, more preferably 20% by mass or more.
- the upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.
- the polymer chain represented by P 10 has a repeating unit containing an acid group.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
- the dispersibility of the pigment in the composition can be further improved.
- the developability can be further improved.
- the proportion of the repeating unit containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass.
- the weight average molecular weight of the polymer chain represented by P 10 is preferably 500 to 20000.
- the lower limit is preferably 600 or more, more preferably 1000 or more.
- the upper limit is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
- This resin is preferably used as a dispersant.
- the weight average molecular weight of the resin containing the repeating unit represented by the formula (Ac-1) is preferably 2000 to 35000.
- the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
- the lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
- the acid value of the resin containing the repeating unit represented by the formula (Ac-1) is preferably 5 to 200 mgKOH / g.
- the upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.
- the lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.
- the content of the polymerizable compound in the total solid content of the pixel-forming composition is preferably 20 to 50% by mass.
- the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
- the lower limit is preferably 22% by mass or more, and more preferably 24% by mass or more.
- the content of the polymerizable monomer in the total solid content of the pixel forming composition is preferably 2 to 15% by mass.
- the upper limit is preferably 14% by mass or less, and more preferably 13% by mass or less.
- the lower limit is preferably 3% by mass or more, and more preferably 4% by mass or more.
- the content of the polymerizable resin in the total solid content of the pixel forming composition is preferably 10 to 45% by mass.
- the upper limit is preferably 40% by mass or less, and more preferably 35% by mass or less.
- the lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the pixel-forming composition can contain a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
- It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an ⁇ -hydroxyketone compound.
- ⁇ -Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable.
- the photopolymerization initiator the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like.
- Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on.
- acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
- Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385.
- oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
- an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471.
- Compound (C-3) and the like can be mentioned.
- an oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
- an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
- the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
- the benzoyl group may have a substituent.
- the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
- an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
- the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
- RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
- RX3 to RX14 independently represent hydrogen atoms or substituents; However, at least one of RX10 to RX14 is an electron-withdrawing group.
- RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 and RX14 are hydrogen atoms.
- oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
- the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
- the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photopolymerization initiator.
- two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the colored composition with time can be improved.
- Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- the content of the photopolymerization initiator in the total solid content of the pixel forming composition is preferably 0.1 to 30% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
- the content of the photopolymerization initiator is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the lower limit is preferably 7 parts by mass or more, and more preferably 10 parts by mass or more.
- the upper limit is preferably 25 parts by mass or less, more preferably 22.5 parts by mass or less.
- the content of the photopolymerization initiator is preferably 30 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- the lower limit is preferably 40 parts by mass or more, and more preferably 50 parts by mass or more.
- the upper limit is preferably 180 parts by mass or less, more preferably 160 parts by mass or less.
- the content of the photopolymerization initiator is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polymerizable resin.
- the lower limit is preferably 11 parts by mass or more, more preferably 12 parts by mass or more.
- the upper limit is preferably 27.5 parts by mass or less, more preferably 25 parts by mass or less. Only one kind of photopolymerization initiator may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
- the pixel-forming composition can contain a resin other than the above-mentioned polymerizable resin (hereinafter, also referred to as another resin).
- Other resins are blended, for example, for the purpose of dispersing particles such as pigments in a pixel-forming composition or for a binder.
- a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant.
- such use of the resin is an example, and it can be used for purposes other than such use.
- the weight average molecular weight (Mw) of the other resin is preferably 3000 to 2000000.
- the upper limit is more preferably 1,000,000 or less, still more preferably 500,000 or less.
- the lower limit is more preferably 4000 or more, further preferably 5000 or more.
- resins include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamide.
- examples thereof include imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like.
- One of these resins may be used alone, or two or more thereof may be mixed and used.
- the resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, and the resin described in JP-A-2017-066240 can also be used.
- the other resin it is preferable to use a resin having an acid group.
- the developability of the pixel forming composition can be improved.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable.
- the resin having an acid group can be used, for example, as an alkali-soluble resin.
- the resin having an acid group is preferably a resin containing a repeating unit having an acid group in the side chain, and is a resin containing 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin. Is more preferable.
- the upper limit of the content of the repeating unit having an acid group in the side chain is more preferably 50 mol% or less, and particularly preferably 30 mol% or less.
- the lower limit of the content of the repeating unit having an acid group in the side chain is more preferably 10 mol% or more, and particularly preferably 20 mol% or more.
- a resin as a dispersant can also be used.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
- the basic dispersant represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
- the basic group of the basic dispersant is preferably an amino group.
- the resin used as the dispersant is preferably a graft resin.
- the graft resin examples include the resins described in paragraphs 0025 to 0094 of JP2012-255128, the contents of which are incorporated in the present specification.
- the resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
- the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
- the resin to have is preferable.
- the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
- the polyimine-based dispersant examples include the resins described in paragraphs 0102 to 0166 of JP2012-255128A, the contents of which are incorporated in the present specification.
- the resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
- examples of such a resin include dendrimers (including star-shaped polymers).
- Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
- Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.
- the content of the other resin in the total solid content of the pixel forming composition is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less.
- the total content of the above-mentioned polymerizable resin and other resins in the total solid content of the pixel-forming composition is preferably 10 to 45% by mass.
- the lower limit is more preferably 15% by mass or more, further preferably 20% by mass or more.
- the upper limit is more preferably 40% by mass or less, further preferably 35% by mass or less.
- the total content of the above-mentioned polymerizable compound and other resins in the total solid content of the pixel-forming composition is preferably 20 to 50% by mass.
- the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
- the lower limit is preferably 22% by mass or more, and more preferably 24% by mass or more.
- the other resin may be only one kind or two or more kinds. When two or more kinds are contained, the total amount thereof is preferably in the above range.
- the composition for forming a pixel may contain a compound having three or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more (hereinafter, also referred to as a specific amine compound).
- the specific amine compound is used, for example, as a dispersion aid.
- the molecular weight of the specific amine compound is preferably 200 or more, more preferably 250 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2000 or less.
- the molecular weight of the specific amine compound is the value calculated from the structural formula.
- the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used.
- the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.
- the amine value of the specific amine compound is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.
- the number of basic groups contained in the specific amine compound is preferably 4 or more, more preferably 6 or more, and further preferably 10 or more.
- the basic group of the specific amine compound is preferably an amino group.
- the specific amine compound is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino. It is more preferable that the compound contains a group and a tertiary amino group, respectively.
- the amino group contained in the specific amine compound may be a cyclic amino group.
- the cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group.
- the cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group.
- the cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure.
- the hindered amine structure it is preferable that the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group.
- the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl.
- 2,6-dimethylpiperidyl group 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group.
- 1,2,2,6,6-pentamethylpiperidyl group or 2,2,6,6-tetramethylpiperidyl group is preferable, and 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.
- the specific amine compound is preferably polyalkyleneimine because it can further improve the storage stability of the pixel-forming composition.
- the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively.
- the number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
- alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. preferable.
- the polyalkyleneimine is particularly preferably polyethyleneimine.
- polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable.
- Examples of commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
- the content of the specific amine compound in the total solid content of the pixel forming composition is preferably 0.1 to 5% by mass.
- the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
- the content of the specific amine compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more.
- the upper limit is preferably 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.
- the specific amine compound may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the pixel-forming composition preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like.
- paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
- an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
- organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, cyclohexyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).
- an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
- the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
- the content of the solvent in the pixel forming composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
- the solvent may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the composition for forming pixels does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
- substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the composition for forming a pixel is 50 mass ppm or less, and is 30 mass ppm or less. Is preferable, and it is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
- the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
- REACH Registration Evolution Analysis and Restriction of Chemicals
- PRTR Policy Release and Transfer Register
- VOC Volatile and Transfer Registor
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- a method for reducing the environmentally regulated substance there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to improve efficiency.
- a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be.
- distillation methods are performed at the stage of the raw material, the stage of the product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a composition for forming a pixel prepared by mixing these compounds. It is possible at any stage such as a stage.
- the composition for forming pixels can contain a compound having a cyclic ether group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
- the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable.
- the epoxy compound preferably has 1 to 100 epoxy groups in one molecule.
- the upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less.
- the lower limit of the number of epoxy groups is preferably two or more.
- Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-0435556, and paragraph numbers 0083 to 0092 of JP2014-089408.
- Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated in the present specification.
- Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G.
- the pixel-forming composition contains a compound having a cyclic ether group
- the content of the compound having a cyclic ether group in the total solid content of the pixel-forming composition is preferably 0.1 to 20% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
- the compound having a cyclic ether group may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the pixel-forming composition can contain a silane coupling agent.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group.
- a phenyl group and the like preferably an amino group, a (meth) acryloyl group and an epoxy group.
- Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A.
- the contents of are incorporated herein by reference.
- the content of the silane coupling agent in the total solid content of the pixel forming composition is preferably 0.1 to 5% by mass.
- the upper limit is preferably 3% by mass or less, more preferably 2% by mass or less.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the silane coupling agent may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the pixel-forming composition can contain a surfactant.
- a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
- the surfactant is preferably a fluorine-based surfactant or a silicon-based surfactant.
- fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
- the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
- fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
- a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
- the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
- a fluorine-based surfactant the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.
- the fluorine-based surfactant a block polymer can also be used.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000.
- % indicating the ratio of the repeating unit is mol%.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
- nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like.
- silicon-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.).
- TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 all manufactured by Momentive Performance Materials
- KP-341, KF-6001, KF-6002, KF- Examples include 6003 (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.
- the content of the surfactant in the total solid content of the pixel forming composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass.
- the surfactant may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the composition for forming pixels can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-066814.
- the compounds described in paragraphs 0061 to 0080 of JP 2016-162946 are mentioned, the contents of which are incorporated herein by reference.
- Examples of commercially available products of the ultraviolet absorber include UV-503 (manufactured by Daito Kagaku Co., Ltd.), Tinuvin series manufactured by BASF, and Uvinul series.
- Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
- the ultraviolet absorber is a compound described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and International Publication No. 2020/137819.
- the thioaryl group-substituted benzotriazole type ultraviolet absorber described in 1 can also be used.
- the content of the ultraviolet absorber in the total solid content of the pixel forming composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
- the ultraviolet absorber may be only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount thereof is in the above range.
- the pixel-forming composition can contain a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like.
- examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable.
- the content of the polymerization inhibitor in the total solid content of the pixel forming composition is preferably 0.0001 to 5% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount thereof is within the above range.
- the pixel-forming composition includes sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (eg, conductive particles, defoaming agents, flame retardants, leveling). Agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc.
- the pixel-forming composition may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- the method for manufacturing a solid-state image sensor of the present invention includes the above-mentioned method for manufacturing an optical filter.
- the configuration of the solid-state image sensor is not particularly limited as long as it includes an optical filter and functions as a solid-state image sensor.
- composition 1 for base layer 0.33 parts by mass of the resin solution 1, 0.002 parts by mass of the surfactant 1 and 99.67 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) are mixed to obtain the composition 1 for the underlayer. Manufactured.
- composition 2 for the underlayer is obtained by mixing 0.33 parts by mass of the resin solution 2, 0.002 parts by mass of the surfactant 1 and 99.67 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Manufactured.
- PGMEA propylene glycol monomethyl ether acetate
- Resin solution 1 PGMEA 30% by mass solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 22000)
- Resin solution 2 PGMEA 30% by mass solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 13000)
- Surfactant 1 A compound having the following structure (weight average molecular weight 14000,% indicating the ratio of repeating units is mol%).
- composition 1 for partition wall 44.8 parts by mass of silica particle liquid 1, 0.2 parts by mass of surfactant 1, 8 parts by mass of 1,4-butanediol diacetate, and 43 parts by mass of propylene glycol monomethyl ether acetate (PGMEA).
- PMEA propylene glycol monomethyl ether acetate
- 2 parts by mass of methanol, 1 part by mass of ethanol, and 1 part by mass of water were mixed and filtered using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole to obtain the composition 1 for partition walls.
- composition for partition wall 2 26.1 parts by mass of silica particle liquid 2, 0.01 parts by mass of surfactant 2, 0.6 parts by mass of silane coupling agent 1, and 14 parts by mass of 1,4-butanediol diacetate.
- PGMEA 55 parts by mass, methanol 2.3 parts by mass, ethanol 1 part by mass and water 1 part by mass, and filter using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole.
- DFA4201NIEY 0.45 ⁇ m nylon filter
- composition for partition wall 3 Silica particle solution 3 is mixed with 54 parts by mass, ethylene glycol mono-t-butyl ether with 12 parts by mass, and diacetone alcohol with 35 parts by mass, and filtered using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole. The process was carried out to produce the composition 3 for partition walls.
- Composition for partition wall 4 35 parts by mass of silica particle liquid 1, 0.1 part by mass of surfactant 1, 6.2 parts by mass of 1,4-butanediol diacetate, 34 parts by mass of PGMEA, and propylene glycol monomethyl ether ( PGME) was mixed by 9.5 parts by mass, 1,6-hexanediol dimethacrylate by 11.2 parts by mass, methanol by 2 parts by mass, ethanol by 1 part by mass, and water by 1 part by mass.
- a partition composition 4 was produced by filtering using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole.
- Composition 5 for partition wall 35 parts by mass of silica particle liquid 1, 0.1 part by mass of surfactant 1, 6.2 parts by mass of 1,4-butanediol diacetate, 34 parts by mass of PGMEA, and propylene glycol monomethyl ether ( PGME) was mixed by 9.5 parts by mass, 1,9-nonanediol dimethacrylate by 11.2 parts by mass, methanol by 2 parts by mass, ethanol by 1 part by mass, and water by 1 part by mass.
- a partition composition 5 was produced by filtering using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole.
- Composition for partition wall 6 35 parts by mass of silica particle liquid 1, 0.1 part by mass of surfactant 1, 6.2 parts by mass of 1,4-butanediol diacetate, 34 parts by mass of PGMEA, and propylene glycol monomethyl ether ( PGME) was mixed by 9.5 parts by mass, 1,9-nonanediol diacrylate by 11.2 parts by mass, methanol by 2 parts by mass, ethanol by 1 part by mass, and water by 1 part by mass.
- a partition composition 6 was produced by filtering using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole.
- Composition for partition wall 7 35 parts by mass of silica particle liquid 1, 0.1 part by mass of surfactant 1, 6.2 parts by mass of 1,4-butanediol diacetate, 34 parts by mass of PGMEA, and propylene glycol monomethyl ether ( PGME) was mixed by 9.5 parts by mass, 1,10-decanediol diacrylate by 11.2 parts by mass, methanol by 2 parts by mass, ethanol by 1 part by mass, and water by 1 part by mass.
- a partition composition 7 was produced by filtering using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole.
- composition for partition wall 8 35 parts by mass of silica particle liquid 1, 0.1 part by mass of surfactant 1, 6.2 parts by mass of 1,4-butanediol diacetate, 34 parts by mass of PGMEA, and propylene glycol monomethyl ether ( 9.5 parts by mass of PGME), 11.2 parts by mass of isodecylmethacrylate, 2 parts by mass of methanol, 1 part by mass of ethanol, and 1 part by mass of water were mixed, and DFA4201NIEY manufactured by Nippon Paul Co., Ltd. ( The composition 8 for a partition wall was produced by filtering using a 0.45 ⁇ m nylon filter).
- Silica particle solution 1 PGME solution (silica particle concentration) of silica particles (beaded silica) in which a plurality of spherical silicas having an average particle diameter of 15 nm are connected in a bead shape by a metal oxide-containing silica (connecting material). It is a silica particle solution prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobic treatment agent to 100.0 g of (20% by mass) and reacting at 20 ° C. for 6 hours.
- PGME solution sica particle concentration of silica particles (beaded silica) in which a plurality of spherical silicas having an average particle diameter of 15 nm are connected in a bead shape by a metal oxide-containing silica (connecting material). It is a silica particle solution prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobic treatment agent to 100.0 g of (20% by mass) and reacting at 20
- the average particle diameter of the spherical silica was obtained by calculating the number average of the diameters corresponding to the circles in the projected images of the spherical portions of the 50 spherical silica measured by a transmission electron microscope (TEM). .. Further, in the silica particle liquid 1, it was examined by a TEM observation method whether or not a plurality of spherical silicas contained silica particles having a shape in which a plurality of spherical silicas were connected in a bead shape.
- TEM transmission electron microscope
- Silica particle solution 2 Silica particle solution prepared by the following method A reaction solution was prepared by mixing 100 g of silica sol having an average particle diameter of 5 nm and a SiO 2 concentration of 20% by mass and 1900 g of pure water, and heated to 80 ° C. .. The pH of this reaction solution was 10.5, and 9000 g of a 1.17% by mass sodium silicate aqueous solution as SiO 2 and 9000 g of a 0.83% by mass sodium aluminate aqueous solution as Al2O3 were simultaneously added to the mother liquor. During that time, the temperature of the reaction solution was maintained at 80 ° C.
- the pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and remained almost unchanged thereafter.
- the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO 2 ⁇ Al 2 O 3 primary particle dispersion having a solid content concentration of 20% by mass.
- 500 g of this SiO 2 ⁇ Al 2 O 3 primary particle dispersion was collected, 1700 g of pure water was added, and the mixture was heated to 98 ° C., and while maintaining this temperature, 50400 g of sodium sulfate having a concentration of 0.5% by mass was added.
- the aluminum salt dissolved in the ultrafiltration membrane was separated by adding 10 L of a hydrochloric acid aqueous solution having a pH of 3 and 5 L of pure water, and washed to obtain a dispersion liquid of silica-based fine particles (1) having a solid content concentration of 20% by mass.
- a dispersion liquid of silica-based fine particles (1) having a solid content concentration of 20% by mass.
- 500 g of pure water, 1750 g of ethanol, and 626 g of 28% ammonia water are added, and the obtained mixed solution is heated to 35 ° C. and then ethyl silicate (SiO). 228 mass%) 104 g was added.
- the mixture was washed with an ultrafiltration membrane to prepare a dispersion liquid of silica-based fine particles (2) having a solid content concentration of 20% by mass.
- the dispersion of the silica-based fine particles (2) was hydroheat-treated at 200 ° C. for 11 hours, and then washed with an ultrafiltration membrane while adding 5 L of pure water to adjust the solid content concentration to 20% by mass.
- the dispersion medium of this dispersion was replaced with propylene glycol monomethyl ether to prepare an organosol having a solid content concentration of 20% by mass.
- This organosol is an organosol in which hollow silica fine particles having an average particle diameter of 23 nm are dispersed (hereinafter, referred to as “hollow silica sol A”).
- hollow silica sol A silicon solid content concentration 20% by mass
- replace the solvent with methanol with an ultrafiltration membrane 100 g of organosol with 20% by mass of SiO 2 minutes (moisture content is SiO 2 minutes). 0.5% by mass) was prepared.
- a 28% aqueous ammonia solution was added to 100 g of the organosol so as to be 100 mass ppm as ammonia, and the mixture was sufficiently mixed.
- reaction solution moisture content was 0.6% by mass with respect to 2 parts of SiO. This was heated to 50 ° C. and heated at 50 ° C. for 15 hours with stirring. After the heating was completed, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a silica particle solution 3 composed of coated hollow fine particles having a SiO2 concentration of 20% by mass.
- -Silica particle solution 3 0.05 g (0.4 mmol) of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), trifluoro in a three-necked flask of 500 ml of silica particle solution prepared by the following method.
- KBM-13 methyltrimethoxysilane
- IPA-ST-UP (IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd.) was mixed in an amount of 224.37 g, and ethylene glycol mono-t-butyl ether (163.93 g) was added. While stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.088 g of phosphoric acid in 4.09 g of water was added over 3 minutes. Then, the flask was immersed in an oil bath at 40 ° C. and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes.
- silica particle solution 3 One hour after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a silica particle solution 3. During the temperature rise and heating and stirring, 0.05 liter (liter) / fraction of nitrogen was flowed. A total of 194.01 g of methanol and water, which are by-products, were distilled off during the reaction. The solid content concentration of the obtained silica particle liquid 3 was 24.3% by mass, and the contents of polysiloxane and silica particles in the solid content were 15% by mass and 85% by mass, respectively.
- Surfactant 1 A compound having the following structure (silicone-based nonionic surfactant, carbinol-modified silicone compound. Weight average molecular weight 3000, kinematic viscosity at 25 ° C. 45 mm 2 / s)
- -Surfactant 2 A compound having the following structure (fluorosurfactant, weight average molecular weight 14000,% value indicating the ratio of repeating units is mol%)
- a bead mill (zirconia beads) is a mixture of a pigment and a pigment derivative in a total of 14 parts by mass, a resin and a dispersion aid in a total of 4.9 parts by mass in terms of solid content, and a solvent in an amount of 81.1 parts by mass.
- a dispersion was prepared by mixing and dispersing for 3 hours using (0.1 mm diameter).
- a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm 3 and a flow rate of 500 g / min.
- This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid.
- the materials shown in the table below were used for the pigments, pigment derivatives, resins, dispersion aids and solvents.
- the mixing ratio of each material in the table below is a value in terms of solid content.
- Pigment Violet23 (purple pigment)
- P-9 A compound having the following structure (near-infrared absorbing pigment, in the following structural formula, Me represents a methyl group and Ph represents a phenyl group).
- P-10 Compound with the following structure (near infrared absorber pigment)
- P-11 Titanium black TB-1 (black pigment) manufactured by the following method 120 g of titanium oxide (TTO-51N, manufactured by Ishihara Sangyo) with a BET specific surface area of 110 m 2 / g, 25 g of silica particles (AEROSIL300, manufactured by Ebony) with a BET specific surface area of 300 m 2 / g, and a dispersant (Disperbyk190, manufactured by Big Chemie).
- TTO-51N titanium oxide
- AEROSIL300 silica particles
- Ebony silica particles
- Dispersant Dispersant
- Titanium Black TB-1 powdery titanium black TB-1 (dispersed body containing titanium black particles and Si atoms) having a specific surface area of 85 m 2 / g containing Si atoms.
- the titanium black particles in Titanium Black TB-1 correspond to titanium oxynitride.
- A-1 Polyethyleneimine (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd., molecular weight 300, amine value 21 mmol / g)
- A-2 Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd., molecular weight 600, amine value 21 mmol / g)
- A-3 Polyethyleneimine (Epomin SP-012, manufactured by Nippon Shokubai Co., Ltd., molecular weight 1200, amine value 19 mmol / g)
- [resin] B-1 30% by mass of resin synthesized by the following method 1-thioglycerol 108 parts by mass, 174 parts by mass of pyromellitic acid anhydride, 650 parts by mass of methoxypropyl acetate, 0.2 parts by mass of monobutyltin oxide as a catalyst The parts were charged in a reaction vessel, the atmosphere gas was replaced with nitrogen gas, and then the reaction was carried out at 120 ° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified.
- the compound obtained in the first step is 160 parts by mass in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, and 200 parts by mass of 2-methoxyethyl acrylate.
- 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are charged in a reaction vessel, and the inside of the reaction vessel is heated to 80 ° C. to 2,2'-azobis (2,4-dimethylvaleronitrile) 1 .2 parts by mass was added and reacted for 12 hours (second step).
- the reaction solution is cooled to obtain a resin having the following structure (acid group-containing resin) having an acid value of 68 mgKOH / g, an ethylenically unsaturated bond-containing base value of 0.62 mmol / g, and a weight average molecular weight of 13000. Obtained.
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 16000, acid value 67 mgKOH / g) 30% by mass PGMEA solution
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 24000, acid value 52. 5 mgKOH / g) 30 mass% PGMEA solution
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 18,000, acid value 82. 1 mgKOH / g) 30 mass% PGMEA solution
- Dispersions G-1 to G-13, R-1, Y-1, Y-2, B-1, IR-1, IR-2, Bk-1 Dispersions G-1, G-2, R- 1, Y-1, Y-2, B-1, IR-1, IR-2, Bk-1
- M-1 Compound with the following structure
- M-2 Compound with the following structure
- M-3 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- M-4 Compound with the following structure
- I-1 Irgure OXE02 (Oxime compound manufactured by BASF)
- I-2, I-3 Compounds with the following structure
- [Surfactant] F-1 A compound having the following structure (fluorine-based surfactant, weight average molecular weight 14000,% value indicating the ratio of repeating units is mol%)
- a silicon wafer having a diameter of 8 inches (20.32 cm) on which a silicon photodiode was formed was used.
- the composition for partition walls described in the table below is applied on the surface of the silicon wafer on the side where the silicon photodiode is formed by a spin coating method so that the film thickness after post-baking is 0.4 ⁇ m, and then a hot plate is applied. After heating at 100 ° C. for 120 seconds, the partition material layer was formed by heating at 200 ° C. for 300 seconds. A positive photoresist for KrF is applied onto this partition material layer with a spin coater, and heat treatment is performed at 100 ° C.
- the corresponding region was exposed in a pattern with an exposure amount of 30 mJ / cm 2 using a KrF scanner, and then heat-treated at 110 ° C. for 1 minute. Then, after a 1-minute development treatment with a developing solution, a 1-minute post-baking treatment was performed at 100 ° C. to remove the photoresist in the region where pixels should be formed.
- the partition wall material layer was treated under the following dry etching conditions, and partition walls having a width of 0.12 ⁇ m were formed in a grid pattern with a pitch width of 0.7 ⁇ m. The width of the partition wall opening was 0.58 ⁇ m.
- the pitch width of the partition wall is the sum of the width of the opening of the partition wall and the width of the partition wall.
- Upper bias / electrode bias 500 / 1000W Processing time: 220 sec
- the refractive index of the partition wall formed by using the partition wall composition 1 with respect to light having a wavelength of 300 nm is 1.26
- the refractive index of the partition wall formed by using the partition wall composition 2 with respect to light having a wavelength of 300 nm is 1. It is 1.30
- the refractive index of the partition wall formed by using the partition wall composition 3 with respect to light having a wavelength of 300 nm is 1.26
- the refractive index of the partition wall formed by using the partition wall composition 4 is 1.30 with respect to light having a wavelength of 300 nm.
- the refractive index is 1.20, and the refractive index of the partition wall formed by using the partition wall composition 5 with respect to light having a wavelength of 300 nm is 1.15, and the wavelength of the partition wall formed by using the partition wall composition 6 is 1.
- the refractive index for light at 300 nm is 1.19, and the refractive index for light having a wavelength of 300 nm of the partition wall formed by using the partition wall composition 7 is 1.17, which is formed by using the partition wall composition 8.
- the refractive index of the partition wall with respect to light having a wavelength of 300 nm was 1.20.
- the refractive index of the partition wall was measured by the following method.
- the composition for partition walls is applied onto a quartz glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film, and then heated at 100 ° C. for 120 seconds using a hot plate (pre-bake). ), And then heated (post-baked) at 200 ° C. for 300 seconds using a hot plate to form a film having a thickness of 0.3 ⁇ m.
- the refractive index of the obtained film was measured with respect to light having a wavelength of 300 nm using ellipsometry VUV-VASE (manufactured by JA Woolam Japan). The value of the refractive index is the value at 25 ° C.
- the composition for the underlayer layer of the types shown in the table below is applied to the surface of the silicon wafer and the partition wall on which these partition walls are formed by a spin coating method, and a hot plate is used at 100 ° C. for 2 minutes for another 230.
- a base layer having a film thickness of 10 nm was formed on the surfaces of the silicon wafer and the partition wall.
- a pixel-forming composition of the type shown in the table below is applied to the surface of the silicon wafer on which the base layer is formed by spin coating so that the film thickness is 0.5 ⁇ m after post-baking, and then hot. The plate was heated at 100 ° C. for 2 minutes to form a pixel-forming composition layer.
- the solid-state image sensor manufactured above was heat-treated at 260 ° C. for 5 minutes to perform a heat resistance test.
- 100 pixels embedded in the partition wall were observed using a scanning electron microscope (SEM), and the heat resistance was evaluated according to the following criteria. If it is A to C according to the following evaluation criteria, there is no problem in practical use.
- C There was a gap between the 3 to 5 pixels and the partition wall.
- D There was a gap between the six or more pixels and the partition wall.
- the evaluation result of heat resistance was "C" or higher, there was almost no gap between the pixel and the partition wall even after the heat resistance test, and the occurrence of variation in the line width of the pixel was sufficiently suppressed. ..
- the pixel-forming composition layer was exposed to light having a wavelength of 365 nm and developed by the same method as described above to form pixels to form a solid-state image sensor. It was possible to suppress the occurrence of variation in the line width of the pixels after the heat resistance test.
- the solid-state image sensor of each example had little variation in sensitivity characteristics between the central portion and the peripheral portion of the silicon photodiode even after the heat resistance test, and a clear image could be obtained.
- Support 11 Partition 30: Composition layer 31 to 33: Pixel
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Abstract
Description
<1> 波長300nmの光に対する屈折率が1.10~1.30の隔壁を有し、上記隔壁で区画された複数の領域が設けられた支持体上に、色材とエチレン性不飽和結合含有基を有する化合物とを含み、かつ、全固形分中に色材を50質量%以上含む画素形成用組成物を塗布して組成物層を形成する工程と、
上記組成物層に波長300nm以下の光をパターン状に照射して露光する工程と、
未露光部の上記組成物層を現像除去して上記隔壁で区画された領域内に画素を形成する工程と、
を含む光学フィルタの製造方法。
<2> 上記隔壁は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも1種を含む、<1>に記載の光学フィルタの製造方法。
<3> 上記エチレン性不飽和結合含有基を有する化合物は、エチレン性不飽和結合含有基を有する重合性モノマーと、エチレン性不飽和結合含有基を有する樹脂とを含む、<1>または<2>に記載の光学フィルタの製造方法。
<4> 上記重合性モノマーの100質量部に対して上記エチレン性不飽和結合含有基を有する樹脂を100~1000質量部含む、<3>に記載の光学フィルタの製造方法。
<5> 上記画素形成用組成物は、光重合開始剤を含む、<1>~<4>のいずれか1つに記載の光学フィルタの製造方法。
<6> 上記光重合開始剤は、オキシム化合物を含む、<5>に記載の光学フィルタの製造方法。
<7> 上記色材は、有彩色色材を含む、<1>~<6>のいずれか1つに記載の光学フィルタの製造方法。
<8> 上記組成物層に照射する波長300nm以下の光は、波長248nmの光である、<1>~<7>のいずれか1つに記載の光学フィルタの製造方法。
<9> <1>~<8>のいずれか1つに記載の光学フィルタの製造方法を含む固体撮像素子の製造方法。
本明細書における基(原子団)の表記について、置換およ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意味である。例えば、単に「アルキル基」と記載した場合には、これは、置換基を有さないアルキル基(無置換アルキル基)、および、置換基を有するアルキル基(置換アルキル基)の両方を包含する意味である。
本明細書において、「(メタ)アクリレート」は、「アクリレート」および「メタクリレート」の両方、または、いずれかを意味し、「(メタ)アクリル」は、「アクリル」および「メタクリル」の両方、または、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」および「メタクリロイル」の両方、または、いずれかを意味する。
本明細書において、組成物中の固形分の濃度は、その組成物の総質量に対する、溶剤を除く他の成分の質量百分率によって表される。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として示される。
本明細書において、近赤外線とは、波長700~2500nmの光をいう。
本明細書において、特に断らない限り、支持体に対し層が積み重なっていく方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における説明の便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本発明の光学フィルタの製造方法は、
波長300nmの光に対する屈折率が1.10~1.30の隔壁を有し、上記隔壁で区画された複数の領域が設けられた支持体上に、色材とエチレン性不飽和結合含有基を有する化合物とを含み、かつ、全固形分中に色材を50質量%以上含む画素形成用組成物を塗布して組成物層を形成する工程と、
上記組成物層に波長300nm以下の光をパターン状に照射して露光する工程と、
未露光部の上記組成物層を現像除去して上記隔壁で区画された領域内に画素を形成する工程と、
を含むことを特徴とする。
まず、波長300nmの光に対する屈折率が1.10~1.30の隔壁を有し、上記隔壁で区画された複数の領域が設けられた支持体上に、色材とエチレン性不飽和結合含有基を有する化合物とを含み、かつ、全固形分中に色材を50質量%以上含む画素形成用組成物を塗布して組成物層を形成する(組成物層形成工程)。
D2=2720/S ・・・(1)
式中、D2は数珠状シリカの平均粒子径であって、単位はnmであり、Sは、窒素吸着法により測定された数珠状シリカの比表面積であって、単位はm2/gである。
下地層の25℃の水に対する接触角は10~60°であることが好ましく、15~50°であることが好ましく、20~45°であることが更に好ましい。下地層の上記接触角が上記範囲であれば、残渣発生の抑制と、画素の密着性を高い水準で両立できる。下地層の上記接触角は静的接触角を液滴法で測定した値である。
次に、上述のようにして形成した支持体上の組成物層に、波長300nm以下の光をパターン状に照射して露光する(露光工程)。これにより、組成物層の露光部分を硬化することができる。
次に、露光工程後の組成物層における未露光部の組成物層を現像除去する(現像工程)。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが残り、図4に示すように、支持体10上の隔壁11で区画された領域内に画素31が形成される。
次に、光学フィルタの製造方法で使用する画素形成用組成物について説明する。
(IR2):波長400~750nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長900~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。
(IR3):波長400~830nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。
(IR4):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。
(IR5):波長400~1050nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1200~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。
画素形成用組成物は、色材を含有する。色材は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。また、顔料は、無機顔料、有機顔料のいずれでもよい。また、顔料には、無機顔料または有機-無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機-無機顔料を有機発色団で置換することで、色相設計をしやすくできる。
有彩色色材としては、波長400~700nmの範囲に極大吸収波長を有する色材が挙げられる。例えば、黄色色材、オレンジ色色材、赤色色材、緑色色材、紫色色材、青色色材などが挙げれる。有彩色色材の具体例としては、例えば、以下に示すものが挙げられる。
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等のオレンジ色顔料。
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294(キサンテン系、Organo Ultramarine、Bluish Red),295(モノアゾ系),296(ジアゾ系),297(アミノケトン系)等の赤色顔料。
C.I.Pigment Green 7,10,36,37,58,59,62,63,64(フタロシアニン系),65(フタロシアニン系),66(フタロシアニン系)等の緑色顔料。
C.I.Pigment Violet 1,19,23,27,32,37,42,60(トリアリールメタン系),61(キサンテン系)等の紫色顔料。
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87(モノアゾ系),88(メチン系)等の青色顔料。
(1)赤色色材と青色色材とを含有する態様。
(2)赤色色材と青色色材と黄色色材とを含有する態様。
(3)赤色色材と青色色材と黄色色材と紫色色材とを含有する態様。
(4)赤色色材と青色色材と黄色色材と紫色色材と緑色色材とを含有する態様。
(5)赤色色材と青色色材と黄色色材と緑色色材とを含有する態様。
(6)赤色色材と青色色材と緑色色材とを含有する態様。
(7)黄色色材と紫色色材とを含有する態様。
顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。顔料誘導体を構成する色素骨格としては、キノリン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾイソインドール色素骨格、ベンゾチアゾール色素骨格、イニミウム色素骨格、スクアリリウム色素骨格、クロコニウム色素骨格、オキソノール色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、アゾ色素骨格、アゾメチン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、アントラキノン色素骨格、キナクリドン色素骨格、ジオキサジン色素骨格、ペリノン色素骨格、ペリレン色素骨格、チオインジゴ色素骨格、イソインドリン色素骨格、イソインドリノン色素骨格、キノフタロン色素骨格、イミニウム色素骨格、ジチオール色素骨格、トリアリールメタン色素骨格、ピロメテン色素骨格等が挙げられる。酸基としては、スルホ基、カルボキシル基、リン酸基及びこれらの塩が挙げられる。塩を構成する原子または原子団としては、アルカリ金属イオン(Li+、Na+、K+など)、アルカリ土類金属イオン(Ca2+、Mg2+など)、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。
白色色材としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などの無機顔料(白色顔料)が挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。また、白色顔料は、波長589nmの光に対する屈折率が2.10以上の粒子であることが好ましい。前述の屈折率は、2.10~3.00であることが好ましく、2.50~2.75であることがより好ましい。
黒色色材としては特に限定されず、公知のものを用いることができる。例えば、無機黒色色材としては、カーボンブラック、チタンブラック、グラファイト等が挙げられ、カーボンブラック、チタンブラックが好ましく、チタンブラックがより好ましい。チタンブラックとは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンが好ましい。チタンブラックは、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。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。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。黒色色材として、カラーインデックス(C.I.)Pigment Black 1,7等が挙げられる。チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいことが好ましい。具体的には、平均一次粒子径が10~45nmであることが好ましい。チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のSi原子とTi原子との含有比が0.20~0.50の範囲に調整した分散物などが挙げられる。上記分散物については、特開2012-169556号公報の段落0020~0105の記載を参酌でき、この内容は本明細書に組み込まれる。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-N、13M-T(商品名: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。有機黒色色材としては、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表2010-534726号公報、特表2012-515233号公報、特表2012-515234号公報、国際公開第2014/208348号、特表2015-525260号公報などに記載の化合物が挙げられ、例えば、BASF社製の「Irgaphor Black」として入手可能である。ペリレン化合物としては、C.I.Pigment Black 31、32などが挙げられる。アゾメチン化合物としては、特開平01-170601号公報、特開平02-034664号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックA1103」として入手できる。また、有機黒色色材としては、特開2017-226821号公報の段落0016~0020に記載のペリレンブラック(Lumogen Black FK4280等)を使用しても良い。
近赤外線吸収色材は、顔料であることが好ましく、有機顔料であることがより好ましい。また、近赤外線吸収色材は、波長700nmを超え1400nm以下の範囲に極大吸収波長を有する化合物であることが好ましい。また、近赤外線吸収色材の極大吸収波長は、1200nm以下であることが好ましく、1000nm以下であることがより好ましく、950nm以下であることが更に好ましい。また、近赤外線吸収色材は、波長550nmにおける吸光度A550と極大吸収波長における吸光度Amaxとの比であるA550/Amaxが0.1以下であることが好ましく、0.05以下であることがより好ましく、0.03以下であることが更に好ましく、0.02以下であることが特に好ましい。下限は、特に限定はないが、例えば、0.0001以上とすることができ、0.0005以上とすることもできる。上述の吸光度の比が上記範囲であれば、可視透明性および近赤外線遮蔽性に優れた近赤外線吸収色材とすることができる。なお、近赤外線吸収色材の極大吸収波長および各波長における吸光度の値は、近赤外線吸収色材を含む感光性組成物を用いて形成した膜の吸収スペクトルから求めた値である。
画素形成用組成物は、エチレン性不飽和結合含有基を有する化合物(以下、重合性化合物ともいう)を含む。エチレン性不飽和結合含有基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基、スチレン基などが挙げられる。
重合性モノマーは、エチレン性不飽和結合含有基を2個以上含む化合物であることが好ましく、エチレン性不飽和結合含有基を2~15個含む化合物であることがより好ましく、エチレン性不飽和結合含有基を2~6個含む化合物であることが更に好ましい。また、重合性モノマーは、2~15官能の(メタ)アクリレート化合物であることが好ましく、2~6官能の(メタ)アクリレート化合物であることがより好ましい。重合性化合物の具体例としては、特開2009-288705号公報の段落番号0095~0108、特開2013-029760号公報の段落0227、特開2008-292970号公報の段落番号0254~0257、特開2013-253224号公報の段落番号0034~0038、特開2012-208494号公報の段落番号0477、特開2017-048367号公報、特許第6057891号公報、特許第6031807号公報に記載されている化合物が挙げられ、これらの内容は本明細書に組み込まれる。
上記式(MO-1)~(MO-6)で表される化合物の各々において、複数のRの内の少なくとも1つは、-OC(=O)CH=CH2、-OC(=O)C(CH3)=CH2、-NHC(=O)CH=CH2または-NHC(=O)C(CH3)=CH2を表す。
上記式(MO-1)~(MO-6)で表される重合性化合物の具体例としては、特開2007-269779号公報の段落0248~0251に記載されている化合物が挙げられる。
式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が特に好ましい。
また、式(Z-4)又は式(Z-5)中の-((CH2)yCH2O)-又は-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。
重合性樹脂のC=C価は、0.1~3.0mmol/gであることが好ましい。上限は、2.5mmol/g以下であることが好ましく、2.0mmol/g以下であることがより好ましい。下限は、0.2mmol/g以上であることが好ましく、0.25mmol/g以上であることがより好ましい。重合性樹脂のC=C価は、重合性樹脂の固形分1gあたりのC=C基のモル量を表した数値である。重合性樹脂のC=C価は、アルカリ処理によって重合性樹脂からC=C基部位の低分子成分(a)を取り出し、その含有量を高速液体クロマトグラフィー(HPLC)により測定し、下記式から算出することができる。また、重合性樹脂からC=C基部位をアルカリ処理で抽出することができない場合においては、NMR法(核磁気共鳴)にて測定した値を用いる。
重合性樹脂のC=C価[mmol/g]=(低分子成分(a)の含有量[ppm]/低分子成分(a)の分子量[g/mol])/(重合性樹脂の秤量値[g]×(重合性樹脂の固形分濃度[質量%]/100)×10)
上記式において、RG3は、水素原子またはメチル基を表す。
上記式において、LG1は、単結合または2価の連結基を表す。2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アルキレンオキシ基(好ましくは炭素数1~12のアルキレンオキシ基)、オキシアルキレンカルボニル基(好ましくは炭素数1~12のオキシアルキレンカルボニル基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。
RG4は、水素原子または置換基を表す。置換基としては、アルキル基、アリール基、ヘテロアリール基、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、エチレン性不飽和結合含有基、環状エーテル基及びブロックイソシアネート基などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。
式(Ar-12)中、n2は1~8の整数を表し、1~4の整数であることが好ましく、1または2であることがより好ましく、2であることが更に好ましい。
式(Ar-13)中、n3およびn4はそれぞれ独立して0~4の整数を表し、0~2の整数であることが好ましく、1または2であることがより好ましく、1であることが更に好ましい。ただし、n3およびn4の少なくとも一方は1以上の整数である。
式(Ar-13)中、Q1は、単結合、-O-、-CO-、-COOCH2CH2OCO-、-SO2-、-C(CF3)2-、上記式(Q-1)で表される基または上記式(Q-2)で表される基を表す。
式(Ar-11)~(Ar-13)中、*1はL11との結合位置を表す。
画素形成用組成物は光重合開始剤を含有することができる。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。光重合開始剤は光ラジカル重合開始剤であることが好ましい。
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す;
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。
また、光重合開始剤の含有量は、重合性化合物100質量部に対して5~30質量部が好ましい。下限は、7質量部以上が好ましく、10質量部以上がより好ましい。上限は、25質量部以下が好ましく、22.5質量部以下がより好ましい。
また、光重合開始剤の含有量は、重合性モノマー100質量部に対して30~200質量部が好ましい。下限は、40質量部以上が好ましく、50質量部以上がより好ましい。上限は、180質量部以下が好ましく、160質量部以下がより好ましい。
また、光重合開始剤の含有量は、重合性樹脂100質量部に対して10~30質量部が好ましい。下限は、11質量部以上が好ましく、12質量部以上がより好ましい。上限は、27.5質量部以下が好ましく、25質量部以下がより好ましい。
光重合開始剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。
画素形成用組成物は、上述した重合性樹脂以外の樹脂(以下、他の樹脂ともいう)を含有することができる。他の樹脂は、例えば、顔料などの粒子を画素形成用組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。
また、画素形成用組成物の全固形分中における上述した重合性樹脂と他の樹脂との合計の含有量は、10~45質量%が好ましい。下限は、15質量%以上がより好ましく、20質量%以上がさらに好ましい。上限は、40質量%以下がより好ましく、35質量%以下が更に好ましい。
また、画素形成用組成物の全固形分中における上述した重合性化合物と他の樹脂との合計の含有量は、20~50質量%であることが好ましい。上限は45質量%以下であることが好ましく、40質量%以下であることがより好ましい。下限は22質量%以上であることが好ましく、24質量%以上であることがより好ましい。
他の樹脂は、1種のみでもよく、2種以上でもよい。2種以上含む場合はそれらの合計量は上記範囲であることが好ましい。
画素形成用組成物は、1分子中に塩基性基を3個以上含み、アミン価が2.7mmol/g以上で、分子量が100以上の化合物(以下特定アミン化合物ともいう)を含有することもできる。特定アミン化合物は例えば分散助剤として用いられる。
画素形成用組成物は、溶剤を含有することが好ましい。溶剤は、有機溶剤であることが好ましい。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、3-ペンタノン、4-ヘプタノン、シクロヘキサノン、2-メチルシクロヘキサノン、3-メチルシクロヘキサノン、4-メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、シクロヘキシルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、プロピレングリコールジアセテート、3-メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、2-メチルアニソール、3-メチルアニソール、1,4-ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン-1,3-ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
画素形成用組成物は、環状エーテル基を有する化合物を含有することができる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。環状エーテル基を有する化合物は、エポキシ基を有する化合物(以下、エポキシ化合物ともいう)であることが好ましい。エポキシ化合物としては、1分子内にエポキシ基を1つ以上有する化合物が挙げられ、エポキシ基を2つ以上有する化合物が好ましい。エポキシ化合物は1分子内にエポキシ基を1~100個有することが好ましい。エポキシ基の数の上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。エポキシ基の数の下限は、2個以上が好ましい。エポキシ化合物としては、特開2013-011869号公報の段落番号0034~0036、特開2014-043556号公報の段落番号0147~0156、特開2014-089408号公報の段落番号0085~0092に記載された化合物、特開2017-179172号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。環状エーテル基を有する化合物の市販品としては、例えば、EHPE3150((株)ダイセル製)、EPICLON N-695(DIC(株)製)、マープルーフG-0150M、G-0105SA、G-0130SP、G-0250SP、G-1005S、G-1005SA、G-1010S、G-2050M、G-01100、G-01758(以上、日油(株)製、エポキシ基含有ポリマー)等が挙げられる。画素形成用組成物が環状エーテル基を有する化合物を含有する場合、画素形成用組成物の全固形分中における環状エーテル基を有する化合物の含有量は、0.1~20質量%が好ましい。下限は、0.5質量%以上が好ましく、1質量%以上がより好ましい。上限は、15質量%以下が好ましく、10質量%以下がより好ましい。環状エーテル基を有する化合物は1種のみでもよく、2種以上でもよい。2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
画素形成用組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、(メタ)アリル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、特開2009-288703号公報の段落番号0018~0036に記載の化合物、特開2009-242604号公報の段落番号0056~0066に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。画素形成用組成物の全固形分中におけるシランカップリング剤の含有量は、0.1~5質量%が好ましい。上限は、3質量%以下が好ましく、2質量%以下がより好ましい。下限は、0.5質量%以上が好ましく、1質量%以上がより好ましい。シランカップリング剤は、1種のみでもよく、2種以上でもよい。2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
画素形成用組成物は、界面活性剤を含有することができる。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、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤はフッ素系界面活性剤またはシリコン系界面活性剤であることが好ましい。
画素形成用組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。このような化合物としては、特開2009-217221号公報の段落番号0038~0052、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334、特開2016-162946号公報の段落番号0061~0080に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)、BASF社製のTinuvinシリーズ、Uvinul(ユビナール)シリーズなどが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)が挙げられる。また、紫外線吸収剤は、特許第6268967号公報の段落番号0049~0059に記載された化合物、国際公開第2016/181987号の段落番号0059~0076に記載された化合物、国際公開第2020/137819号に記載されたチオアリール基置換ベンゾトリアゾール型紫外線吸収剤を用いることもできる。画素形成用組成物の全固形分中における紫外線吸収剤の含有量は、0.01~10質量%が好ましく、0.01~5質量%がより好ましい。紫外線吸収剤は、1種のみでもよく、2種以上でもよい。2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
画素形成用組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、tert-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-tert-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塩(アンモニウム塩、第一セリウム塩等)が挙げられる。中でも、p-メトキシフェノールが好ましい。画素形成用組成物の全固形分中における重合禁止剤の含有量は、0.0001~5質量%が好ましい。重合禁止剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、それらの合計量が上記範囲となることが好ましい。
画素形成用組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類(例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、画素形成用組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
本発明の固体撮像素子の製造方法は、上述した光学フィルタの製造方法を含む。固体撮像素子の構成としては、光学フィルタを備え、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い。
(下地層用組成物1)
樹脂溶液1の0.33質量部と、界面活性剤1の0.002質量部と、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)の99.67質量部とを混合して、下地層用組成物1を製造した。
樹脂溶液2の0.33質量部と、界面活性剤1の0.002質量部と、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)の99.67質量部とを混合して、下地層用組成物2を製造した。
(隔壁用組成物1)
シリカ粒子液1を44.8質量部と、界面活性剤1を0.2質量部と、1,4-ブタンジオールジアセテートを8質量部と、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)を43質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物1を製造した。
シリカ粒子液2を26.1質量部と、界面活性剤2を0.01質量部と、シランカップリング剤1を0.6質量部と、1,4-ブタンジオールジアセテートを14質量部と、PGMEAを55質量部と、メタノールを2.3質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物2を製造した。
シリカ粒子液3を54質量部と、エチレングリコールモノ-t-ブチルエーテルを12質量部と、ジアセトンアルコールを35質量部と混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物3を製造した。
シリカ粒子液1を35質量部と、界面活性剤1を0.1質量部と、1,4-ブタンジオールジアセテートを6.2質量部と、PGMEAを34質量部と、プロピレングリコールモノメチルエーテル(PGME)を9.5質量部と、1,6-ヘキサンジオールジメタクリレートを11.2質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物4を製造した。
シリカ粒子液1を35質量部と、界面活性剤1を0.1質量部と、1,4-ブタンジオールジアセテートを6.2質量部と、PGMEAを34質量部と、プロピレングリコールモノメチルエーテル(PGME)を9.5質量部と、1,9-ノナンジオールジメタクリレートを11.2質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物5を製造した。
シリカ粒子液1を35質量部と、界面活性剤1を0.1質量部と、1,4-ブタンジオールジアセテートを6.2質量部と、PGMEAを34質量部と、プロピレングリコールモノメチルエーテル(PGME)を9.5質量部と、1,9-ノナンジオールジアクリレートを11.2質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物6を製造した。
シリカ粒子液1を35質量部と、界面活性剤1を0.1質量部と、1,4-ブタンジオールジアセテートを6.2質量部と、PGMEAを34質量部と、プロピレングリコールモノメチルエーテル(PGME)を9.5質量部と、1,10-デカンジオールジアクリレートを11.2質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物7を製造した。
シリカ粒子液1を35質量部と、界面活性剤1を0.1質量部と、1,4-ブタンジオールジアセテートを6.2質量部と、PGMEAを34質量部と、プロピレングリコールモノメチルエーテル(PGME)を9.5質量部と、イソデシルメタクリレートを11.2質量部と、メタノールを2質量部と、エタノールを1質量部と、水を1質量部とを混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物8を製造した。
・シリカ粒子液1:平均粒子径15nmの球状シリカの複数個が金属酸化物含有シリカ(連結材)によって数珠状に連結された形状のシリカ粒子(数珠状シリカ)のPGME)溶液(シリカ粒子濃度20質量%)の100.0gに疎水化処理剤としてトリメチルメトキシシランの3.0gを添加し、20℃で6時間反応させて調製したシリカ粒子液である。なお、シリカ粒子液1において、球状シリカの平均粒子径は、透過型電子顕微鏡(TEM)によって測定した50個の球状シリカの球状部分の投影像における円相当直径の数平均を算出して求めた。また、シリカ粒子液1において、TEM観察の方法で、複数個の球状シリカが数珠状に連結された形状のシリカ粒子を含むものであるかどうか調べた。
平均粒子径5nm、SiO2濃度20質量%のシリカゾル100gと純水1900gとを混合して反応液を調製し、80℃に加温した。この反応液のpHは10.5であり、同母液にSiO2として1.17質量%の珪酸ナトリウム水溶液9000gと、Al2O3として0.83質量%のアルミン酸ナトリウム水溶液9000gとを同時に添加した。その間、反応液の温度を80℃に保持した。反応液のpHは、珪酸ナトリウムおよびアルミン酸ナトリウムの添加直後、12.5に上昇し、その後、ほとんど変化しなかった。添加終了後、反応液を室温まで冷却し、限外濾過膜で洗浄して固形分濃度20質量%のSiO2・Al2O3一次粒子分散液を調製した。ついで、このSiO2・Al2O3一次粒子分散液500gを採取し、純水1700gを加えて98℃に加温し、この温度を保持しながら、濃度0.5質量%の硫酸ナトリウム50400gを添加し、ついでSiO2として濃度1.17質量%の珪酸ナトリウム水溶液3000gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液9000gを添加して複合酸化物微粒子分散液を得た。そして、これを限外濾過膜で洗浄して固形分濃度13質量%の複合酸化物微粒子分散液とした。この複合酸化物微粒子分散液500gに純水1125gを加え、さらに濃塩酸(35.5%)を滴下してpH1.0とし、脱アルミニウム処理を行った。次いで、pH3の塩酸水溶液10Lと純水5Lを加えながら限外濾過膜で溶解したアルミニウム塩を分離し、洗浄して固形分濃度20質量%のシリカ系微粒子(1)の分散液を得た。このシリカ系微粒子(1)の水分散液1500gに、純水500gと、エタノール1750gと、28%アンモニア水626gとを加え、得られた混合液を35℃に加温した後、エチルシリケート(SiO228質量%)104gを添加した。ついで、純水5Lを加えながら、限外濾過膜で洗浄して固形分濃度20質量%のシリカ系微粒子(2)の分散液を調製した。ついで、再びシリカ系微粒子(2)の分散液を200℃にて11時間水熱処理した後、純水5Lを加えながら限外濾過膜で洗浄して固形分濃度20質量%に調整した。そして、限外濾過膜を用いて、この分散液の分散媒をプロピレングリコールモノメチルエーテルに置換し、固形分濃度20質量%のオルガノゾルを調製した。このオルガノゾルは、平均粒子径が23nmの中空シリカ微粒子が分散したオルガノゾル(以下、「中空シリカゾルA」と称する。)である。中空シリカゾルA(シリカ固形分濃度20質量%)200gを用意し、限外濾過膜にて、メタノールへの溶媒置換を行い、SiO2分が20質量%のオルガノゾル100g(水分量はSiO2分に対して0.5質量%)を調製した。そこへ28%アンモニア水溶液をオルガノゾル100gに対してアンモニアとして100質量ppmとなるように加え、充分に混合し、次に、メタクリルシラン(信越化学株式会社製KBM503)4g(SiO2分100質量部に対して20質量部相当)を添加し、反応液(水分量はSiO2分に対して0.6質量%)とした。これを50℃に加温し、撹拌しながら50℃で15時間加熱を行なった。加熱終了後、反応液を常温まで冷却し、限外濾過膜で洗浄して、SiO2濃度20質量%の被覆中空微粒子からなるシリカ粒子液3を調製した。
500mlの三口フラスコに、メチルトリメトキシシラン(KBM-13、信越化学工業(株)製)を0.05g(0.4mmol)、トリフルオロプロピルトリメトキシシラン(KBM-7103、信越化学工業(株)製)を0.66g(3.0mmol)、トリメトキシシリルプロピルコハク酸無水物(KBM-967、信越化学工業(株)製)を0.10g(0.4mmol)、γ-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製)を7.97g(34mmol)、15.6質量%のシリカ粒子のイソプロピルアルコール分散液(IPA-ST-UP、日産化学工業(株)製)を224.37g混合し、エチレングリコールモノ-t-ブチルエーテル163.93gを加えた。室温で撹拌しながら、水4.09gにリン酸0.088gを溶かしたリン酸水溶液を3分間かけて添加した。その後、フラスコを40℃のオイルバスに浸けて60分間撹拌した後、オイルバスを30分間かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱撹拌し(内温は100~110℃)、シリカ粒子液3を得た。なお、昇温および加熱撹拌中、窒素を0.05l(リットル)/分流した。反応中に副生成物であるメタノール、水が合計194.01g留出した。得られたシリカ粒子液3の固形分濃度は24.3質量%、固形分中のポリシロキサンとシリカ粒子の含有量はそれぞれ15質量%、85質量%であった。
(分散液の製造)
顔料と顔料誘導体とを合計で14質量部と、樹脂と分散助剤とを固形分換算で合計で4.9質量部と、溶剤を81.1質量部との混合液を、ビーズミル(ジルコニアビーズ0.1mm径)を用いて3時間混合および分散して、分散液を調製した。その後、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、圧力2000kg/cm3および流量500g/minの条件の下、分散処理を行なった。この分散処理を全10回まで繰り返して分散液を得た。顔料、顔料誘導体、樹脂、分散助剤および溶剤はそれぞれ下記表に示す素材を用いた。また、下記表中における各素材の混合比率は固形分換算での値である。
[顔料]
P-1: C.I.Pigment Green58(緑色顔料)
P-2: C.I.Pigment Red272(赤色顔料)
P-3: C.I.Pigment Red254(赤色顔料)
P-4: C.I.Pigment Yellow185(黄色顔料)
P-5: C.I.Pigment Yellow138(黄色顔料)
P-6: C.I.Pigment Yellow150(黄色顔料)
P-7: C.I.Pigment Blue15:6(青色顔料)
P-8: C.I.Pigment Violet23(紫色顔料)
P-9: 下記構造の化合物(近赤外線吸収顔料、以下の構造式中、Meはメチル基を表し、Phはフェニル基を表す)
BET比表面積110m2/gの酸化チタン(TTO-51N、石原産業製)を120g、BET表面積300m2/gのシリカ粒子(AEROSIL300、エボニック製)を25g、及び、分散剤(Disperbyk190、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30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、窒素によって雰囲気を置換し、同温度下でアンモニアガスを100mL/minの流量で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を用いて粉砕し、Si原子を含み、粉末状の比表面積85m2/gのチタンブラックTB-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。なお、チタンブラックTB-1におけるチタンブラック粒子は、酸窒化チタンに相当する。
A-1: ポリエチレンイミン(エポミンSP-003、(株)日本触媒製、分子量300、アミン価21mmol/g)
A-2: ポリエチレンイミン(エポミンSP-006、(株)日本触媒製、分子量600、アミン価21mmol/g)
A-3: ポリエチレンイミン(エポミンSP-012、(株)日本触媒製、分子量1200、アミン価19mmol/g)
B-1:以下の方法で合成した樹脂の30質量%PGMEA溶液
1-チオグリセロール108質量部、ピロメリット酸無水物174質量部、メトキシプロピルアセテート650質量部、触媒としてモノブチルスズオキシド0.2質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した後、120℃で5時間反応させた(第一工程)。酸価の測定で95%以上の酸無水物がハーフエステル化していることを確認した。次に、第一工程で得られた化合物を固形分換算で160質量部、2-ヒドロキシプロピルメタクリレート200質量部、エチルアクリレート200質量部、t-ブチルアクリレート150質量部、2-メトキシエチルアクリレート200質量部、メチルアクリレート200質量部、メタクリル酸50質量部、PGMEA663質量部を反応容器に仕込み、反応容器内を80℃に加熱して、2,2’-アゾビス(2,4-ジメチルバレロニトリル)1.2質量部を添加し、12時間反応させた(第二工程)。固形分測定により95%が反応したことを確認した。最後に、第二工程で得られた化合物の50質量%PGMEA溶液500質量部、2-メタクリロイルオキシエチルイソシアネート(MOI)27.0質量部、ヒドロキノン0.1質量部を反応容器に仕込み、イソシアネート基に基づく2270cm-1のピークの消失を確認するまで反応を行った(第三工程)。ピーク消失の確認後、反応溶液を冷却して、酸価68mgKOH/g、エチレン性不飽和結合含有基価0.62mmol/g、重量平均分子量13000の下記構造の樹脂(酸基を有する樹脂)を得た。
S-1: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)
S-2:プロピレングリコールモノメチルエーテル(PGME)
S-3:シクロヘキサノン
S-4:3-ペンタノン
S-5:アニソール
S-6:4-メトキシトルエン
S-7:2-メチルアニソール
S-8:3-メチルアニソール
S-9:3-エトキシプロピオン酸エチル
S-10:シクロヘキシルアセテート
S-11:ジアセトンアルコール
S-12:シクロペンタノン
各素材を、以下に示す処方1~5の割合で混合し、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して各画素形成用組成物を製造した。下記表において、画素形成用組成物の全固形分中における色材(顔料と顔料誘導体の合計)の含有量の値を「色材濃度」の欄に記載する。
下記表に記載の分散液 ・・・64.3質量部
下記表に記載の重合性モノマー ・・・1.8質量部
下記表に記載の樹脂 ・・・10.4質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.9質量部
界面活性剤(F-1) ・・・0.02質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0002質量部
溶剤(PGMEA) ・・・22.6質量部
下記表に記載の分散液 ・・・70.7質量部
下記表に記載の重合性モノマー ・・・1.4質量部
下記表に記載の樹脂 ・・・7.6質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.9質量部
界面活性剤(F-1) ・・・0.02質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0002質量部
溶剤(PGMEA) ・・・19.3質量部
下記表に記載の分散液 ・・・77.1質量部
下記表に記載の重合性モノマー ・・・0.9質量部
下記表に記載の樹脂 ・・・5.9質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.7質量部
界面活性剤(F-1) ・・・0.02質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0002質量部
溶剤(PGMEA) ・・・15.3質量部
下記表に記載の分散液 ・・・83.6質量部
下記表に記載の重合性モノマー ・・・0.7質量部
下記表に記載の樹脂 ・・・2.5質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.7質量部
界面活性剤(F-1) ・・・0.02質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0002質量部
溶剤(PGMEA) ・・・12.5質量部
下記表に記載の分散液 ・・・83.6質量部
下記表に記載の重合性モノマー ・・・0.7質量部
下記表に記載の樹脂 ・・・1.3質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・1.1質量部
界面活性剤(F-1) ・・・0.02質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0002質量部
溶剤(PGMEA) ・・・13.3質量部
分散液Gー1~G-13、R-1、Y-1、Y-2、B-1、IR-1、IR-2、Bk-1:分散液Gー1、G-2、R-1、Y-1、Y-2、B-1、IR-1、IR-2、Bk-1
I-1:Irgacure OXE02(BASF社製、オキシム化合物)
I-2、I-3:下記構造の化合物
B-1~B-4:上述したB-1~B-4
B-5:下記構造の樹脂(主鎖に付記した数値はモル比である。酸基を有する樹脂、重量平均分子量11000、酸価69.2mgKOH/g)の30質量%PGMEA溶液
(実施例1~39)
支持体として、シリコンフォトダイオードが形成された直径8インチ(20.32cm)のシリコンウエハを用いた。シリコンウエハのシリコンフォトダイオードが形成された側の表面上に、下記表に記載の隔壁用組成物をポストベーク後の膜厚が0.4μmとなるようにスピンコート法で塗布した後、ホットプレートを用いて100℃で120秒加熱した後、200℃で300秒加熱して隔壁材料層を形成した。
この隔壁材料層上に、KrF用ポジ型フォトレジストをスピンコーターにて塗布し、100℃で2分間の加熱処理を行い、膜厚が1.0μmの厚さになるようにフォトレジスト層を形成した。次に対応する領域を、KrFスキャナーを用いて30mJ/cm2の露光量でパターン状に露光した後、110℃で1分間の加熱処理を行った。その後、現像液で1分間の現像処理した後、100℃で1分間のポストベーク処理を行い、画素を形成すべき領域のフォトレジストを除去した。次いで、下記のドライエッチング条件で隔壁材料層の処理を行い、幅0.12μmの隔壁を、ピッチ幅0.7μmで格子状に形成した。隔壁開口部の幅は0.58μmであった。なお、隔壁のピッチ幅は、隔壁の開口部の幅と隔壁の幅との合計のことである。
-ドライエッチング条件-
使用装置:日立ハイテクノロジーズ社製 U-621
圧力:2.0Pa
使用ガス:Ar/C4F6/O2=1000/20/50mL/min
処理温度:20℃
ソースパワー:500W
上部バイアス/電極バイアス=500/1000W
処理時間:220sec
次に、下地層が形成されたシリコンウエハの表面に、下記表に記載の種類の画素形成用組成物を膜厚がポストベーク後0.5μmになるようにスピンコートで塗布し、次いで、ホットプレートを用いて100℃で2分間加熱して、画素形成用組成物層を形成した。次いで、KrFスキャナー露光装置を用い、パターンを有するマスクを介して波長248nmの光を200mJ/cm2の露光量で照射して露光した。なお、画素形成用組成物として緑色組成物1~6を用いた場合には、マスクとしてはベイヤーパターンを有するマスクを用いた。それ以外画素形成用組成物を用いた場合には、マスクとしてアイランドパターンを有するマスクを用いた。
次に、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、画素形成用組成物層に対し23℃で60秒間パドル現像を行った。その後、スピンシャワーによるリンス、純水を用いた水洗を実施し、さらに、ホットプレートを用いて220℃で5分間を加熱して、シリコンウエハ上の隔壁で区画された領域内に画素を形成して固体撮像素子を製造した。
上記で製造した固体撮像素子について、260℃で5分間加熱処理を行い耐熱性試験を行った。加熱性試験後の固体撮像素子について走査型電子顕微鏡(SEM)を用いて隔壁に埋め込まれた画素を100個観察し、以下の基準で耐熱性を評価した。以下の評価基準でA~Cであれば実用上問題ない水準である。
A:100個の画素のすべてについて、隔壁との間に隙間がなかった。
B:1個または2個の画素について隔壁との間に隙間があった。
C:3~5個の画素について隔壁との間に隙間があった。
D:6個以上の画素について隔壁との間に隙間があった。
11:隔壁
30:組成物層
31~33:画素
Claims (9)
- 波長300nmの光に対する屈折率が1.10~1.30の隔壁を有し、前記隔壁で区画された複数の領域が設けられた支持体上に、色材とエチレン性不飽和結合含有基を有する化合物とを含み、かつ、全固形分中に色材を50質量%以上含む画素形成用組成物を塗布して組成物層を形成する工程と、
前記組成物層に波長300nm以下の光をパターン状に照射して露光する工程と、
未露光部の前記組成物層を現像除去して前記隔壁で区画された領域内に画素を形成する工程と、
を含む光学フィルタの製造方法。 - 前記隔壁は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも1種を含む、請求項1に記載の光学フィルタの製造方法。
- 前記エチレン性不飽和結合含有基を有する化合物は、エチレン性不飽和結合含有基を有する重合性モノマーと、エチレン性不飽和結合含有基を有する樹脂とを含む、請求項1または2に記載の光学フィルタの製造方法。
- 前記重合性モノマーの100質量部に対して前記エチレン性不飽和結合含有基を有する樹脂を100~1000質量部含む、請求項3に記載の光学フィルタの製造方法。
- 前記画素形成用組成物は、光重合開始剤を含む、請求項1~4のいずれか1項に記載の光学フィルタの製造方法。
- 前記光重合開始剤は、オキシム化合物を含む、請求項5に記載の光学フィルタの製造方法。
- 前記色材は、有彩色色材を含む、請求項1~6のいずれか1項に記載の光学フィルタの製造方法。
- 前記組成物層に照射する波長300nm以下の光は、波長248nmの光である、請求項1~7のいずれか1項に記載の光学フィルタの製造方法。
- 請求項1~8のいずれか1項に記載の光学フィルタの製造方法を含む固体撮像素子の製造方法。
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JP2011075691A (ja) * | 2009-09-29 | 2011-04-14 | Dainippon Printing Co Ltd | 有機エレクトロルミネッセンス表示装置用カラーフィルタ |
WO2019065477A1 (ja) * | 2017-09-29 | 2019-04-04 | 富士フイルム株式会社 | 光学フィルタの製造方法 |
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KR20110002605A (ko) * | 2009-07-02 | 2011-01-10 | 동우 화인켐 주식회사 | 초단파장 노광기를 이용한 고체 촬상 소자용 컬러 필터의 제조방법, 그 방법에 의해 제조된 컬러 필터 및 이를 포함하는 고체 촬상 소자 |
JP2011075691A (ja) * | 2009-09-29 | 2011-04-14 | Dainippon Printing Co Ltd | 有機エレクトロルミネッセンス表示装置用カラーフィルタ |
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