WO2023022122A1 - 組成物、膜、光学フィルタ、光学センサ、画像表示装置および構造体 - Google Patents

組成物、膜、光学フィルタ、光学センサ、画像表示装置および構造体 Download PDF

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WO2023022122A1
WO2023022122A1 PCT/JP2022/030853 JP2022030853W WO2023022122A1 WO 2023022122 A1 WO2023022122 A1 WO 2023022122A1 JP 2022030853 W JP2022030853 W JP 2022030853W WO 2023022122 A1 WO2023022122 A1 WO 2023022122A1
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mass
composition
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group
cyclic siloxane
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PCT/JP2022/030853
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English (en)
French (fr)
Japanese (ja)
Inventor
大貴 瀧下
貴規 田口
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202280053840.7A priority Critical patent/CN117813352A/zh
Priority to JP2023542394A priority patent/JPWO2023022122A1/ja
Priority to KR1020247002775A priority patent/KR102948778B1/ko
Publication of WO2023022122A1 publication Critical patent/WO2023022122A1/ja
Priority to US18/428,225 priority patent/US20240228746A1/en
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors

Definitions

  • the present invention relates to compositions containing inorganic particles.
  • the present invention also relates to films, optical filters, optical sensors, image display devices and structures.
  • An optical functional layer such as a low refractive index film is applied to the surface of a transparent substrate, for example, to prevent reflection of incident light.
  • Its application fields are wide, and it is applied to products in various fields such as optical instruments, building materials, observation instruments, and window glass.
  • a variety of materials, both organic and inorganic, are used as materials for such devices, and are the subject of development.
  • the development of materials applied to optical instruments has been advanced. Specifically, in display panels, optical lenses, image sensors, and the like, the search for materials having physical properties and workability suitable for the products is underway.
  • optical functional layers applied to precision optical devices such as image sensors are required to have fine and accurate processability. Therefore, conventionally, vapor phase methods such as vacuum deposition and sputtering, which are suitable for microfabrication, have been employed.
  • vapor phase methods such as vacuum deposition and sputtering, which are suitable for microfabrication, have been employed.
  • the material for example, a single layer film made of MgF2 , cryolite, or the like has been put into practical use. Attempts have also been made to apply metal oxides such as SiO 2 , TiO 2 and ZrO 2 .
  • Patent Document 1 describes the production of an antireflection film or the like using a composition containing silica particles with a hollow structure.
  • compositions containing inorganic particles such as silica particles tend to have defects such as irregularities due to aggregates of inorganic particles on the surface of the film during film formation. According to studies by the present inventors, it has been found that there is room for further improvement even in the composition described in Patent Document 1.
  • an object of the present invention is to provide a composition, a film, an optical filter, an optical sensor, an image display device, and a structure capable of forming a film with suppressed defects.
  • the present invention provides the following.
  • ⁇ 1> Including inorganic particles, a cyclic siloxane compound, and a silicone-based surfactant other than the cyclic siloxane compound, A composition, wherein the content of the cyclic siloxane compound is 0.01 to 10 parts by mass per 100 parts by mass of the silicone surfactant.
  • ⁇ 2> The composition according to ⁇ 1>, wherein the cyclic siloxane compound is a compound represented by formula (1);
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and m represents an integer of 3-20.
  • ⁇ 4> Including inorganic particles, a cyclic siloxane compound, and a silicone-based surfactant other than the cyclic siloxane compound,
  • the cyclic siloxane compound is at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane,
  • ⁇ 5> The composition according to any one of ⁇ 1> to ⁇ 4>, containing two or more of the cyclic siloxane compounds.
  • the inorganic particles include silica particles.
  • the silica particles are selected from silica particles having a shape in which a plurality of spherical silicas are connected in a beaded shape, silica particles having a shape in which a plurality of spherical silicas are connected in a plane, and silica particles having a hollow structure.
  • composition according to any one of ⁇ 1> to ⁇ 8> wherein the content of the inorganic particles in the total solid content of the composition is 20% by mass or more.
  • An optical filter comprising the film according to ⁇ 10>.
  • An optical sensor comprising the film according to ⁇ 10>.
  • An image display device comprising the film according to ⁇ 10>.
  • the present invention it is possible to provide a composition, a film, an optical filter, an optical sensor, an image display device, and a structure capable of forming a film with suppressed defects.
  • FIG. 2 is an enlarged view schematically showing silica particles having a shape in which a plurality of spherical silica particles are connected in a beaded shape.
  • 1 is a side sectional view showing one embodiment of a structure of the present invention; FIG. It is the top view seen from just above the support body in the same structure.
  • ⁇ is used to include the numerical values before and after it as lower and upper limits.
  • a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents both or either acrylate and methacrylate
  • (meth)acryl represents both or either acrylic and methacrylic
  • (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
  • Me in the structural formulas represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • total solid content refers to the total mass of all components of the composition excluding the solvent.
  • process includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • a first aspect of the composition of the present invention comprises: Including inorganic particles, a cyclic siloxane compound, and a silicone-based surfactant other than the cyclic siloxane compound,
  • the content of the cyclic siloxane compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant.
  • the second aspect of the composition of the present invention is Including inorganic particles, a cyclic siloxane compound, and a silicone-based surfactant other than the cyclic siloxane compound
  • the cyclic siloxane compound is at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane
  • the content of the cyclic siloxane compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant.
  • composition of the present invention can form a film with suppressed defects. Although the detailed reason why such an effect is obtained is unknown, it is because aggregation due to interaction between the silicone surfactant and the inorganic particles can be suppressed by adding a predetermined amount of the cyclic siloxane compound. It is assumed that there is.
  • the viscosity of the composition of the present invention at 25° C. is preferably 3.6 mPa ⁇ s or less, more preferably 3.4 mPa ⁇ s or less, and even more preferably 3.2 mPa ⁇ s or less.
  • the lower limit is preferably 1.0 mPa ⁇ s or more, more preferably 1.4 mPa ⁇ s or more, and even more preferably 1.8 mPa ⁇ s or more.
  • the solid content concentration of the composition of the present invention is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.
  • the composition of the present invention can be preferably used as a composition for optical sensors or image display devices. Specifically, it can be preferably used as a composition for forming an optical functional layer in an optical sensor or an image display device.
  • optical functional layers include antireflection layers, low refractive index layers, and waveguides.
  • the composition of the present invention is a partition-forming composition used for partitioning adjacent pixels when forming pixels on an imaging area of an optical sensor such as a solid-state imaging device or an image display device. It can also be used as Examples of pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the compositions of the present invention contain inorganic particles.
  • inorganic particles include silica particles, titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, aluminum hydroxide particles, and calcium silicate. particles, aluminum silicate particles, zinc sulfide particles, and the like.
  • silica particles are preferable because they have a high affinity with cyclic siloxane.
  • the content of silica particles in the total amount of inorganic particles contained in the composition of the present invention is preferably 20% by mass or more, more preferably 50% by mass or more, and 70% by mass or more.
  • the inorganic particles are substantially only silica particles.
  • the inorganic particles when the inorganic particles are substantially only silica particles, it means that the content of silica particles in the total amount of inorganic particles is 99% by mass or more, and 99.9% by mass or more. More preferably, it is still more preferably only silica particles.
  • silica particles examples include silica particles in which a plurality of spherical silica particles are connected in a beaded shape, silica particles in which a plurality of spherical silica particles are connected in a plane, silica particles with a hollow structure, solid silica particles, and the like. be done.
  • silica particles tend to form a film with a smaller refractive index
  • silica particles having a shape in which a plurality of spherical silicas are linked in a beaded shape silica particles having a shape in which a plurality of spherical silicas are planarly linked
  • Silica particles having a hollow structure are preferred, and silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape and silica particles in a shape in which a plurality of spherical silica particles are planarly linked are preferable.
  • a silica particle having a shape in which a plurality of spherical silica particles are linked in a beaded shape and a silica particle having a shape in which a plurality of spherical silica particles are planarly linked are collectively referred to as beaded silica.
  • the silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape may have a shape in which a plurality of spherical silica particles are planarly linked.
  • the hydroxy groups on the surface of the silica particles be treated with a hydrophobizing agent that reacts with the hydroxy groups.
  • a hydrophobizing agent a compound that has a structure that reacts with the hydroxy groups on the silica particle surface (preferably, a structure that undergoes a coupling reaction with the hydroxy groups on the silica particle surface) 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 organic silane compounds, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds, and organic silane compounds are more preferable because they can suppress the increase in refractive index.
  • the silica particles treated with such a hydrophobizing agent are materials corresponding to inorganic particles, and are materials different from silicone-based surfactants and cyclic siloxane compounds.
  • spherical in “spherical silica” means that it may be substantially spherical, and may be deformed within the scope of the effects of the present invention. For example, it includes a shape having unevenness on the surface and a flat shape having a long axis in a predetermined direction.
  • a plurality of spherical silica particles are linked in a beaded manner means a structure in which a plurality of spherical silica particles are linked in a linear and/or branched form. For example, as shown in FIG.
  • the structure in which "a plurality of spherical silica particles are linked in a beaded shape” includes not only a structure in which a ring is connected, but also a chain-like structure having an end. It also includes structures with
  • "a plurality of spherical silica particles are planarly connected” means a structure in which a plurality of spherical silica particles are connected to each other on substantially the same plane. It should be noted that “substantially the same plane” means not only the same plane, but also the vertical deviation from the same plane. For example, the vertical deviation may be within a range of 50% or less of the particle diameter of the spherical silica.
  • the beaded silica preferably has a ratio D 1 /D 2 of 3 or more between the average particle diameter D 1 measured by the dynamic light scattering method and the average particle diameter D 2 obtained by the following formula (1). Although there is no particular upper limit for D 1 /D 2 , it is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. Favorable optical properties can be exhibited by setting D 1 /D 2 within such a range.
  • the value of D 1 /D 2 in beaded silica is also an index of the degree of connection of spherical silica.
  • D2 2720/S (1)
  • D 2 is the average particle size of beaded silica in units of nm
  • S is the specific surface area of beaded silica measured by the nitrogen adsorption method in units of m 2 /g. be.
  • the average particle size D2 of the beaded silica can be regarded as an average particle size approximate to the diameter of the primary particles of the spherical silica.
  • the average particle diameter D2 is preferably 1 nm or more, more preferably 3 nm or more, still more 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, even more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less.
  • the average particle diameter D2 can be substituted 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 of 50 or more particles is evaluated as the number average of 50 or more particles.
  • D0 equivalent circle diameter
  • TEM transmission electron microscope
  • the average particle diameter D1 of beaded silica can be regarded as the number average particle diameter of secondary particles in which a plurality of spherical silica particles are aggregated. Therefore, the relationship D 1 >D 2 usually holds.
  • the average particle diameter D1 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, even more preferably 50 nm or less, and particularly preferably 45 nm or less.
  • the average particle diameter D1 of beaded silica is measured using a dynamic light scattering particle size distribution analyzer (Microtrac UPA-EX150, manufactured by Nikkiso Co., Ltd.) unless otherwise specified.
  • the procedure is as follows.
  • the beaded silica dispersion is put into a 20 ml sample bottle, and diluted with propylene glycol monomethyl ether so that the solid content concentration becomes 0.2% by mass.
  • the sample solution after dilution is irradiated with ultrasonic waves of 40 kHz for 1 minute, and used for the test immediately after that.
  • a 2 ml measurement quartz cell is used at a temperature of 25° C., data is taken in 10 times, and the obtained "number average” is taken as the average particle size.
  • JISZ8828:2013 Particle Size Analysis-Dynamic Light Scattering Method
  • the beaded silica it is preferable that a plurality of spherical silica particles 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 spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less.
  • the lower limit of the average particle size of spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more.
  • the average particle size of spherical silica is determined from the equivalent circle diameter in the projected image of the spherical portion measured by a transmission electron microscope (TEM).
  • Metal oxide-containing silica is exemplified as a connecting material for connecting spherical silica particles in the beaded silica particles.
  • metal oxides include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti.
  • metal oxide-containing silica include reaction products and mixtures of these metal oxides and silica (SiO 2 ).
  • the connecting member the description of International Publication No. WO 2000/015552 can be referred to, and the content thereof is incorporated herein.
  • the number of spherical silica connections in beaded silica is preferably 3 or more, more preferably 5 or more.
  • the upper limit is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less.
  • the number of linkages of spherical silica can be measured by TEM.
  • Examples of commercially available particle liquids containing beaded silica include the Snowtex series and the organosilica sol series (methanol dispersion, isopropyl alcohol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, etc., manufactured by Nissan Chemical Industries, Ltd., product number IPA). -ST-UP, MEK-ST-UP, etc.).
  • 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.
  • Commercially available particle liquids containing hollow silica include "Sururia 4110" manufactured by Nikki Shokubai Kasei Co., Ltd., and the like.
  • the content of inorganic particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less.
  • the content of inorganic particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 90% by mass or more, and 95% by mass or more. It is more preferably 97% by mass or more, and particularly preferably 98% by mass or more.
  • the upper limit can be 99.95% by mass or less, can be 99.9% by mass or less, or can be 99% by mass or less.
  • the content of silica particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and preferably 7% by mass or more. More preferred.
  • the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less.
  • the content of silica particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 90% by mass or more, and 95% by mass or more. It is more preferably 97% by mass or more, and particularly preferably 98% by mass or more.
  • the upper limit can be 99.95% by mass or less, can be 99.9% by mass or less, or can be 99% by mass or less. If the content of the silica particles is within the above range, it is easy to obtain a film with a low refractive index, a high antireflection effect, and suppressed defects.
  • the composition of the invention contains a cyclic siloxane compound.
  • the cyclic siloxane compound means a cyclic compound formed by a siloxane bond.
  • the cyclic siloxane compound is preferably a compound represented by Formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and m represents an integer of 3-20.
  • substituents represented by R 1 and R 2 in formula (1) include alkyl groups and aryl groups, with alkyl groups being preferred.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 1.
  • the above alkyl group may be linear or branched, but preferably linear.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 carbon atoms.
  • R 1 and R 2 are each independently preferably a hydrogen atom, a methyl group or a phenyl group, more preferably a methyl group.
  • n in formula (1) represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 8, even more preferably an integer of 3 to 6, An integer of 4-6 is particularly preferred.
  • the molecular weight of the cyclic siloxane compound is preferably 1000 or less, more preferably 800 or less, even more preferably 600 or less.
  • the lower limit can be 100 or more.
  • cyclic siloxane compounds include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethylcyclotrisiloxane, etc.
  • Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodeca It is preferably at least one selected from methylcyclohexasiloxane.
  • the composition of the present invention may contain only one cyclic siloxane compound, but preferably contains two or more cyclic siloxane compounds.
  • a compound in which m in formula (1) is 3 or 4 preferably a compound in which m is 4
  • m in formula (1) is an integer of 5 or more a compound (preferably a compound in which m is an integer of 5 to 10, more preferably a compound in which m is an integer of 5 to 8, and a compound in which m is 5 or 6).
  • the ratio of the compound in which m in the above formula (1) is 3 or 4 and the compound in which m in the above formula (1) is an integer of 5 or more is it is preferable that the compound in which m in the above formula (1) is an integer of 5 or more is 10 to 1000 parts by mass, more preferably 25 to 750 parts by mass, with respect to 100 parts by mass of a certain compound. More preferably, it is up to 500 parts by mass.
  • the cyclic siloxane compound preferably contains at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. More preferably, it contains sasiloxane.
  • the cyclic siloxane compound is preferably at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Dodecamethylcyclohexasiloxane is more preferable.
  • a cyclic siloxane compound containing octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethyl The ratio of the cyclohexasiloxane is preferably 1 to 100 parts by mass of octamethylcyclotetrasiloxane and 50 to 200 parts by mass of decamethylcyclopentasiloxane to 100 parts by mass of dodecamethylcyclohexasiloxane.
  • Octamethylcyclotetrasiloxane is preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of dodecamethylcyclohexasiloxane.
  • Decamethylcyclopentasiloxane is preferably 1 to 200 parts by mass, more preferably 50 to 150 parts by mass, per 100 parts by mass of dodecamethylcyclohexasiloxane.
  • the content of the cyclic siloxane compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant.
  • the lower limit is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less.
  • the total content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane is 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant. preferable.
  • the lower limit is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less.
  • the content of octamethylcyclotetrasiloxane is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone-based surfactant.
  • the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and 0.5 parts by mass or more. is even more preferred.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less.
  • the content of decamethylcyclopentasiloxane is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant.
  • the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and 0.5 parts by mass or more. is even more preferred.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less.
  • the content of dodecamethylcyclohexasiloxane is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicone surfactant.
  • the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and 0.5 parts by mass or more. is even more preferred.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less.
  • the composition of the present invention contains silicone-based surfactants other than cyclic siloxane compounds.
  • the silicone-based surfactant is preferably a compound containing no fluorine atoms.
  • the silicone-based surfactant is a compound having a repeating unit containing a siloxane bond in its main chain, and a compound containing a hydrophobic part and a hydrophilic part in one molecule.
  • the viscosity of the silicone surfactant at 25° C. is preferably 40 mm 2 /s or less, more preferably 38 mm 2 /s or less, and even more preferably 36 mm 2 /s or less. If the viscosity of the silicone-based surfactant is 40 mm 2 /s or less, the surface condition during application is excellent.
  • the lower limit of the viscosity of the silicone-based surfactant is preferably 10 mm 2 /s or more, more preferably 15 mm 2 /s or more, because a certain amount of chain length is required to exhibit the effect of the surfactant. is more preferably 20 mm 2 /s or more, and particularly preferably 25 mm 2 /s or more.
  • the hydroxyl value of the silicone surfactant is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, still more preferably 100 mgKOH/g or more, and particularly preferably 110 mgKOH/g or more. preferable.
  • the upper limit of the hydroxyl value of the silicone surfactant is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and even more preferably 130 mgKOH/g or less.
  • the silicone-based surfactant is preferably modified polysiloxane.
  • modified polysiloxane include compounds having a structure in which substituents are introduced into the side chains and/or terminals of polysiloxane.
  • substituents include groups containing functional groups selected from amino groups, epoxy groups, alicyclic epoxy groups, hydroxyl groups, mercapto groups, carboxy groups, fatty acid ester groups and fatty acid amide groups, and groups containing polyether chains. and is preferably a group containing a hydroxy group, more preferably a group having an alkyleneoxy group and a hydroxy group.
  • the group containing a hydroxy group is preferably a group represented by formula (G-1) or a group represented by formula (G-2).
  • G-1 a group represented by formula (G-2)
  • G-2 a group represented by formula (G-2)
  • LG1 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
  • m1 represents an integer of 0 or 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
  • R G1 represents an alkylene group.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
  • the alkylene group represented by R G1 may be linear or branched.
  • the alkylene groups represented by m1 R 1 G1 may be the same or different.
  • Groups containing polyether chains include groups represented by the following formula (G-11) and groups represented by formula (G-12).
  • LG11 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L G11 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
  • m2 represents a number of 2 or more, preferably 2-200.
  • R G11 represents an alkylene group.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
  • the alkylene group represented by R G11 may be linear or branched.
  • the alkylene groups represented by m2 R G11 may be the same or different.
  • R G12 represents an alkyl group or an aryl group.
  • the number of carbon atoms in the alkyl group represented by R 1 G12 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
  • Alkyl groups may be straight or branched.
  • the aryl group represented by R G12 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the silicone-based surfactant is preferably carbinol-modified polysiloxane, more preferably carbinol-modified dialkylpolysiloxane. Moreover, the silicone-based surfactant is preferably dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
  • the silicone-based surfactant is preferably a compound represented by Formula (Si-1) or Formula (Si-2).
  • R S1 to R S7 each independently represent an alkyl group or an aryl group
  • X S1 represents a group represented by the above formula (G-1) or a group represented by formula (G-2)
  • n1 represents a number from 2 to 200
  • R S11 to R S16 each independently represent an alkyl group or an aryl group
  • X S11 and X S12 each independently represent a group represented by formula (G-1) or a group represented by formula (G-2)
  • n11 represents a number from 2 to 200
  • the number of carbon atoms in the alkyl group represented by R S1 to R S7 in formula (Si-1) and the alkyl group represented by R S11 to R S16 in formula (Si-2) is preferably 1 to 10, more preferably 1 to 5. 1 to 3 are more preferred, and 1 is particularly preferred.
  • the above alkyl group may be linear or branched, but preferably linear.
  • the number of carbon atoms in the aryl group represented by R S1 to R S7 in formula (Si-1) and the aryl group represented by R S11 to R S16 in formula (Si-2) is preferably 6 to 20, more preferably 6 to 12. 6 is particularly preferred.
  • R S1 to R S7 and R S11 to R S16 are preferably methyl groups or phenyl groups, more preferably methyl groups.
  • silicone-based surfactants include compounds having the following structures.
  • silicone surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF8419 OIL (above, Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF -6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie Co., Ltd.) made) and the like.
  • the content of the silicone-based surfactant in the composition is preferably 1 to 2000 mass ppm.
  • the lower limit is preferably 3 ppm by mass or more, more preferably 5 ppm by mass or more.
  • the upper limit is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less.
  • composition of the present invention may contain surfactants other than silicone-based surfactants (hereinafter also referred to as other surfactants).
  • surfactants include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and the like.
  • JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
  • the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
  • fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
  • fluorosurfactant 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 as the fluorosurfactant.
  • fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant 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) (meta)
  • 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 fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
  • a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant.
  • Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K.
  • compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
  • Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
  • Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
  • the content of other surfactants in the composition is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 100 mass ppm or less. It is also preferred that the compositions of the present invention do not contain other surfactants.
  • the composition of the invention preferably contains a solvent.
  • the solvent include organic solvents and water, and it is preferable to include at least the organic solvent.
  • organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents. Examples include solvents.
  • aliphatic hydrocarbon solvents examples include hexane, cyclohexane, methylcyclohexane, pentane, cyclopentane, heptane, and octane.
  • Halogenated hydrocarbon solvents include methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichlorethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, methyl monochloroacetate, ethyl monochloroacetate, monochloroacetic acid, trichloroacetic acid, methyl bromide, tri(tetra)chloroethylene, and the like.
  • Alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2, 4-pentanediol, 3-methoxy-1-butanol, 1,3-butanediol, 1,4-butanediol and the like.
  • Ether solvents include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, and ethylene.
  • Glycol monobutyl ether ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether , diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monobutyl ether, dipropylene glycol methyl-n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triprop
  • Ester solvents include propylene carbonate, dipropylene, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, cyclohexanol acetate, dipropylene glycol methyl ether acetate, Methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, triacetin and the like.
  • Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and the like.
  • Acetonitrile and the like are examples of nitrile-based solvents.
  • Amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N-methyl formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethyl and propanamide.
  • sulfoxide solvents examples include dimethyl sulfoxide.
  • Aromatic solvents include benzene and toluene.
  • a solvent containing an alcohol-based solvent it facilitates the formation of a film in which the occurrence of thickness unevenness and defects is more suppressed.
  • the alcohol solvent is preferably at least one selected from methanol, ethanol, 1-propanol, 2-propanol and 2-butanol, more preferably at least one selected from methanol and ethanol.
  • the alcohol-based solvent preferably contains at least methanol, and more preferably contains methanol and ethanol because it facilitates formation of a film with less defects.
  • the content of the solvent in the composition is preferably 70-99% by mass.
  • the upper limit is preferably 93% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less.
  • the lower limit is preferably 75% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. Only one kind of solvent may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the content of the alcohol-based solvent in the total amount of the solvent is preferably 0.1 to 10% by mass.
  • the upper limit is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less.
  • the lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Only one type of alcohol-based solvent may be used, or two or more types may be used in combination. When the composition of the present invention contains two or more kinds of alcohol solvents, it is preferable that the total of them is within the above range.
  • the solvent preferably contains solvent A1 with a boiling point of 190°C or higher and 280°C or lower.
  • the boiling point of the solvent is the value at 1 atmosphere (0.1 MPa).
  • the boiling point of solvent A1 is preferably 200°C or higher, more preferably 210°C or higher, and more preferably 220°C or higher.
  • the boiling point of solvent A1 is preferably 270° C. or lower, more preferably 265° C. or lower.
  • the viscosity of solvent A1 is preferably 10 mPa ⁇ s or less, more preferably 7 mPa ⁇ s or less, and more preferably 4 mPa ⁇ s or less.
  • the lower limit of the viscosity of solvent A1 is preferably 1.0 mPa ⁇ s or more, more preferably 1.4 mPa ⁇ s or more, and even more preferably 1.8 mPa ⁇ s or more from the viewpoint of coating properties. .
  • the molecular weight of solvent A1 is preferably 100 or more, more preferably 130 or more, still more preferably 140 or more, and particularly preferably 150 or more.
  • the upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
  • Solvent A1 preferably has a solubility parameter of 8.5 to 13.3 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 12.5 (cal/cm 3 ) 0.5 or less, more preferably 11.5 (cal/cm 3 ) 0.5 or less, and 10.5 (cal/cm 3 ) ) is more preferably 0.5 or less.
  • the lower limit is preferably 8.7 (cal/cm 3 ) 0.5 or more, more preferably 8.9 (cal/cm 3 ) 0.5 or more, and 9.1 (cal/cm 3 ) is more preferably 0.5 or more.
  • solubility parameter of solvent A1 is within the above range, high affinity with inorganic particles such as silica particles can be obtained, and excellent coatability can be easily obtained.
  • 1 (cal/cm 3 ) 0.5 is 2.0455 MPa 0.5 .
  • Solvent solubility parameters are values calculated by HSPiP.
  • the Hansen solubility parameter is used as the solubility parameter of the solvent. Specifically, a value calculated using the Hansen solubility parameter software "HSPiP 5.0.09" is used.
  • the solvent A1 is preferably an aprotic solvent.
  • an aprotic solvent as the solvent A1, aggregation of inorganic particles such as silica particles during film formation can be more effectively suppressed, and a film with more suppressed thickness unevenness and defects can be easily formed.
  • Solvent A1 is preferably an ether-based solvent or an ester-based solvent, more preferably an ester-based solvent.
  • the ester-based solvent used as the solvent A1 is preferably a compound that does not contain a hydroxyl group or a terminal alkoxy group.
  • the solvent A1 is preferably at least one selected from alkylenediol diacetates and cyclic carbonates because it has a high affinity with inorganic particles such as silica particles and is likely to have excellent coatability.
  • Alkylene diol diacetates include propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like.
  • Cyclic carbonates include propylene carbonate and ethylene carbonate.
  • solvent A1 examples include propylene carbonate (boiling point 240°C), ethylene carbonate (boiling point 260°C), propylene glycol diacetate (boiling point 190°C), dipropylene glycol methyl-n-propyl ether (boiling point 203°C), Propylene glycol methyl ether acetate (boiling point 213°C), 1,4-butanediol diacetate (boiling point 232°C), 1,3-butylene glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C) ° C.), diethylene glycol monoethyl ether acetate (boiling point 217° C.), diethylene glycol monobutyl ether acetate (boiling point 247° C.), triacetin (boiling point 260° C.), dipropylene glycol
  • the solvent contained in the composition of the present invention preferably contains 3% by mass or more of the solvent A1, more preferably 4% by mass or more, and preferably 5% by mass or more. It is even more preferable to have The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. Only one kind of solvent A1 may be used, or two or more kinds thereof may be used in combination. When the composition of the present invention contains two or more solvents A1, it is preferable that the total is within the above range.
  • the solvent contained in the composition of the present invention preferably contains solvent A2 having a boiling point of 110°C or more and less than 190°C in addition to solvent A1 described above. According to this aspect, it is easy to form a film in which thickness unevenness is further suppressed by appropriately enhancing the drying property of the composition.
  • the boiling point of solvent A2 is preferably 115°C or higher, more preferably 120°C or higher, and more preferably 130°C or higher.
  • the boiling point of solvent A2 is preferably 170° C. or lower, more preferably 150° C. or lower. If the boiling point of the solvent A2 is within the above range, the effects described above are likely to be obtained more remarkably.
  • the molecular weight of solvent A2 is preferably 100 or more, more preferably 130 or more, even more preferably 140 or more, and even more preferably 150 or more, because the above-described effects are likely to be obtained more remarkably. is particularly preferred.
  • the upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
  • Solvent A2 preferably has a solubility parameter of 9.0 to 11.4 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 11.0 (cal/cm 3 ) 0.5 or less, more preferably 10.6 (cal/cm 3 ) 0.5 or less, and 10.2 (cal/cm 3 ) ) is more preferably 0.5 or less.
  • the lower limit is preferably 9.2 (cal/cm 3 ) 0.5 or more, more preferably 9.4 (cal/cm 3 ) 0.5 or more, and 9.6 (cal/cm 3 ) ) is more preferably 0.5 or more.
  • the absolute value of the difference between the solubility parameter of solvent A1 and the solubility parameter of solvent A2 is preferably 0.01 to 1.1 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 0.9 (cal/cm 3 ) 0.5 or less, more preferably 0.7 (cal/cm 3 ) 0.5 or less, and 0.5 (cal/cm 3 ) is more preferably 0.5 or less.
  • the lower limit is preferably 0.03 (cal/cm 3 ) 0.5 or more, more preferably 0.05 (cal/cm 3 ) 0.5 or more, and 0.08 (cal/cm 3 ) ) is more preferably 0.5 or more.
  • the solvent A2 is preferably at least one selected from ether-based solvents and ester-based solvents, more preferably includes at least an ester-based solvent, and still more preferably includes an ether-based solvent and an ester-based solvent.
  • Specific examples of solvent A2 include cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 175°C), butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), and propylene glycol monomethyl ether.
  • the content of solvent A2 is preferably 500 to 5000 parts by mass with respect to 100 parts by mass of solvent A1.
  • the upper limit is preferably 4500 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3500 parts by mass or less.
  • the lower limit is preferably 600 parts by mass or more, more preferably 700 parts by mass or more, and even more preferably 750 parts by mass or more.
  • the content of solvent A2 in the total amount of solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. Only one kind of solvent A2 may be used, or two or more kinds thereof may be used in combination. When the composition of the present invention contains two or more solvents A2, the total is preferably within the above range.
  • the solvent used in the composition of the present invention preferably contains a total of 62% by mass or more of solvent A1 and solvent A2, more preferably 72% by mass or more, and 82% by mass or more. is more preferable.
  • the upper limit can be 100% by mass, 96% by mass or less, or 92% by mass or less.
  • the solvent used in the composition of the present invention preferably further contains water. According to this aspect, high affinity with inorganic particles such as silica particles can be obtained, and excellent coatability can be easily obtained.
  • the solvent used in the composition of the present invention further contains water, the content of water in the total amount of the solvent is preferably 0.1 to 5% by mass.
  • the upper limit is preferably 4% by mass or less, more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less.
  • the lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.7% by mass or more. If the content of water is within the above range, the effects described above are likely to be obtained more remarkably.
  • the solvent used in the composition of the present invention can further contain solvent A3 with a boiling point of over 280°C. According to this aspect, it is easy to form a film in which the drying property of the composition is moderately increased and the occurrence of thickness unevenness and defects is further suppressed.
  • the upper limit of the boiling point of solvent A3 is preferably 400° C. or lower, more preferably 380° C. or lower, and even more preferably 350° C. or lower.
  • Solvent A3 is preferably at least one selected from ether-based solvents and ester-based solvents. Specific examples of solvent A3 include polyethylene glycol monomethyl ether.
  • the content of solvent A3 in the total amount of solvent is preferably 0.5 to 15% by mass.
  • the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.
  • the lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. It is also preferred that the solvent used in the composition of the present invention does not substantially contain solvent A3.
  • substantially free of solvent A3 means that the content of solvent A3 in the total amount of solvent is 0.1% by mass or less, preferably 0.05% by mass or less, and 0.1% by mass or less. It is more preferably 01% by mass or less, and more preferably not contained.
  • the content of compounds having a molecular weight (weight average molecular weight in the case of a polymer) exceeding 300 is preferably 10% by mass or less, and preferably 8% by mass or less. More preferably, it is 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this aspect, it is easy to form a film in which the occurrence of thickness unevenness and defects is further suppressed.
  • the solvent used in the composition of the present invention preferably contains 10% by mass or less, more preferably 8% by mass or less, of a compound having a viscosity of more than 10 mPa s at 25° C., and 5% by mass. % or less, even more preferably 3 mass % or less, and particularly preferably 1 mass % or less. According to this aspect, it is easy to form a film in which the occurrence of thickness unevenness and defects is further suppressed.
  • compositions of the invention may contain dispersants.
  • Dispersants include polymeric dispersants (e.g., polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymer, formalin condensate of naphthalene sulfonate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine and the like.
  • Polymeric dispersants can be further classified into straight-chain polymers, terminal-modified polymers, graft-type polymers, and block-type polymers according to their structures.
  • Polymeric dispersants adsorb to the surface of particles and act to prevent reaggregation. Therefore, a terminal-modified polymer, a graft-type polymer, and a block-type polymer having an anchor site to the particle surface are preferable structures.
  • a commercial item can also be used for a dispersing agent. Examples include the products described in paragraph 0050 of WO2016/190374, the contents of which are incorporated herein.
  • the content of the dispersant is preferably 1 to 100 parts by mass, more preferably 3 to 100 parts by mass, and even more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the inorganic particles. Moreover, the content of the dispersant is preferably 1 to 30% by mass based on the total solid content of the composition. Only one dispersant may be used, or two or more dispersants may be included. When the composition of the present invention contains two or more dispersants, it is preferable that the total of them is within the above range.
  • compositions of the invention can contain polymerizable monomers.
  • polymerizable monomer known compounds that can be crosslinked by radicals, acids or heat can be used.
  • the polymerizable monomer is preferably a radically polymerizable monomer.
  • the radical polymerizable monomer is preferably a compound having an ethylenically unsaturated bond-containing group.
  • the molecular weight of the polymerizable monomer is preferably 100-3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, even more preferably 250 or more.
  • the polymerizable monomer is preferably a compound having two or more ethylenically unsaturated bond-containing groups, more preferably a compound having three or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the number of ethylenically unsaturated bond-containing groups is, for example, preferably 15 or less, more preferably 6 or less.
  • Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group, with a (meth)acryloyl group being preferred.
  • the polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • Specific examples of polymerizable monomers include compounds described in paragraphs 0059 to 0079 of WO 2016/190374.
  • Polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the (meth)acryloyl groups of these compounds are ethylene glycol and/or propylene glycol residues.
  • trimethylolpropane tri(meth)acrylate trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate
  • Trifunctional (meth)acrylate compounds such as erythritol tri(meth)acrylate
  • Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group can also be used as the polymerizable monomer.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group and the like, and a carboxy group is preferred.
  • Commercially available polymerizable monomers having an acid group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the acid value of the polymerizable monomer having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility in the developing solution is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.
  • a compound having a caprolactone structure can also be used as the polymerizable monomer.
  • Polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60 and DPCA-120.
  • a polymerizable monomer having an alkyleneoxy group can also be used as the polymerizable monomer.
  • the polymerizable monomer having an alkyleneoxy group is preferably a polymerizable monomer having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable monomer having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups.
  • a hexafunctional (meth)acrylate compound is more preferred.
  • Examples of commercially available polymerizable monomers having an alkyleneoxy group include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and isobutyleneoxy group manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330, which is a trifunctional (meth)acrylate having three, and the like.
  • a polymerizable monomer having a fluorene skeleton can also be used as the polymerizable monomer.
  • Commercially available polymerizable monomers having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
  • the polymerizable monomer it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene.
  • environmentally regulated substances such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • the content of the polymerizable monomer in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass.
  • the above is more preferable.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less.
  • the content of the polymerizable monomer in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less.
  • the composition of the present invention may contain only one polymerizable monomer, or may contain two or more polymerizable monomers. When the composition of the present invention contains two or more polymerizable monomers, it is preferable that the total of them is within the above range. It is also preferred that the composition of the present invention is substantially free of polymerizable monomers. When the composition of the present invention does not substantially contain a polymerizable monomer, it is easy to form a film with a lower refractive index. Furthermore, it is easy to form a film with a small haze.
  • composition of the present invention does not substantially contain a polymerizable monomer
  • content of the polymerizable monomer in the total solid content of the composition of the present invention is 0.05% by mass or less. In other words, it is preferably 0.01% by mass or less, and more preferably contains no polymerizable monomer.
  • the composition of the invention can contain a photoinitiator.
  • the composition of the present invention contains a polymerizable monomer and a photopolymerization initiator
  • the composition of the present invention can be preferably used as a composition for pattern formation by photolithography.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds.
  • hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. are mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
  • ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
  • Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) and the like.
  • An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
  • 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 oxime compounds include compounds described in WO2013/083505.
  • 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 include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
  • An oxime compound having a nitro group can be used as 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 paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxyl 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.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass or more. % or more by mass is more preferable.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less.
  • the content of the photopolymerization initiator in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When the composition of the present invention contains two or more photopolymerization initiators, the total is preferably within the above range. It is also preferred that the composition of the present invention is substantially free of photopolymerization initiators.
  • the composition of the present invention does not substantially contain a photopolymerization initiator, it means that the content of the photopolymerization initiator in the total solid content of the composition is 0.005% by mass or less. However, it is preferably 0.001% by mass or less, and more preferably does not contain a photopolymerization initiator.
  • the composition of the invention can contain a resin.
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like.
  • norbornene resin is preferable from the viewpoint of improving heat resistance.
  • Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No.
  • a resin having a fluorene skeleton can also be preferably used.
  • the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.
  • the resin the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339.
  • a resin represented by the formula 1 can also be used.
  • the acid group includes a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxy group is preferred.
  • a resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the resin having an acid group preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin.
  • the upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less.
  • the lower limit of the content of repeating units having an acid group in the side chain is preferably 10 mol % or more, more preferably 20 mol % or more.
  • the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
  • the lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
  • the content of the resin in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. .
  • the upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less.
  • the resin content in the total solid content of the composition is preferably 0.2% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.2% by mass or more.
  • the upper limit is preferably 18% by mass or less, more preferably 12% by mass or less, and more preferably 5% by mass or less.
  • the composition of the present invention may contain only one type of resin, or may contain two or more types. When the composition of the present invention contains two or more resins, the total is preferably within the above range.
  • the composition of the present invention can contain an adhesion improver.
  • an adhesion improver By containing the adhesion improver, a film having excellent adhesion to the support can be formed.
  • adhesion improvers described in JP-A-05-011439, JP-A-05-341532, JP-A-06-043638 and the like are suitable.
  • a silane coupling agent is preferable as the adhesion improver.
  • a 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 bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
  • Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
  • silane coupling agents include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-
  • silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
  • the content of the adhesion improver in the total solid content of the composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 0 .1 mass % or more is particularly preferred.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the composition of the present invention may contain only one type of adhesion improver, or may contain two or more types. When the composition of the present invention contains two or more adhesion improvers, the total of them is preferably within the above range. It is also preferred that the composition of the present invention is substantially free of adhesion improvers.
  • the content of the adhesion improver in the total solid content of the composition is 0.0005% by mass or less. It is preferably 0.0001% by mass or less, and more preferably contains no adhesion improver.
  • composition of the present invention may contain coloring agents.
  • Colorants include green colorants, red colorants, yellow colorants, purple colorants, blue colorants, orange colorants, black colorants, and the like.
  • the coloring agent may be a pigment or a dye.
  • 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, and even more preferably 100 nm or less.
  • the content of the coloring agent in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the composition of the present invention may contain only one colorant, or may contain two or more colorants. When the composition of the present invention contains two or more colorants, the total is preferably within the above range. It is also preferred that the compositions of the present invention are substantially free of colorants. In addition, when the composition of the present invention does not substantially contain a coloring agent, it means that the content of the coloring agent in the total solid content of the composition is 0.1% by mass or less. 05% by mass or less, and more preferably contains no colorant.
  • composition of the present invention may optionally contain sensitizers, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, etc.). agents, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein.
  • the composition of the present invention may also contain latent antioxidants, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • perfluoroalkylsulfonic acid and its salts may be regulated.
  • perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • salts thereof and perfluoro
  • the content of the alkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb to the total solid content of the composition of the present invention.
  • composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts.
  • perfluoroalkylsulfonic acid and its salt and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected.
  • compositions of the present invention may contain perfluoroalkylsulfonic acids and their salts and perfluoroalkylcarboxylic acids and their salts within the maximum permissible range.
  • the storage container for the composition is not particularly limited, and known storage containers can be used.
  • a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing deterioration of components.
  • compositions of the present invention can be prepared by admixing the aforementioned ingredients.
  • the composition may be produced by dissolving and/or dispersing all the components in a solvent at the same time, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions.
  • a composition may be produced by mixing these at the time of use (at the time of application).
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
  • polyamide resins such as nylon (eg nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
  • PP polypropylene
  • nylon including high density polypropylene
  • nylon including high density polypropylene
  • the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
  • Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .
  • fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
  • Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
  • filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
  • the membrane of the invention is a membrane obtained from the composition of the invention as described above.
  • the refractive index of the film of the present invention for light having a wavelength of 633 nm is preferably 1.4 or less, more preferably 1.35 or less, even more preferably 1.3 or less, and 1.27 or less. is even more preferable.
  • the value of the said refractive index is a value in the measurement temperature of 25 degreeC.
  • the film of the present invention preferably has sufficient hardness.
  • the Young's modulus of the film is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more.
  • the upper limit is preferably 10 or less.
  • the thickness of the film of the present invention can be appropriately selected according to the application.
  • the thickness of the film is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1.5 ⁇ m or less. Although there is no particular lower limit, it is preferably 50 nm or more.
  • the film of the present invention can be used for optical sensors such as solid-state imaging devices and optical functional layers in image display devices.
  • optical functional layers include antireflection layers, low refractive index layers, and waveguides.
  • the film of the present invention can be used as a partition or the like used for partitioning adjacent pixels when pixels are formed on an imaging area of an optical sensor such as a solid-state imaging device or an image display device.
  • pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the membrane of the present invention can be produced through the step of coating the composition of the present invention on a support.
  • the film manufacturing method further includes the step of forming a pattern.
  • the pattern forming method include a pattern forming method by photolithography and a pattern forming method by etching.
  • Pattern formation by photolithography includes the steps of coating the composition of the present invention on a support to form a composition layer, patternwise exposing the composition layer, and developing the unexposed portion of the composition layer. and removing to form a pattern. If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided.
  • the composition of the present invention is applied to the support to form the composition layer.
  • the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include substrates such as wafers made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. It is also preferable to use an InGaAs substrate or the like. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In some cases, a black matrix made of a light shielding material such as tungsten is formed on the support. Further, an underlying layer may be provided on the support to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the surface of the substrate. A microlens can also be used for the support.
  • a known method can be used as a method for applying the composition.
  • dropping method drop cast
  • slit coating method spray method
  • roll coating method spin coating
  • methods described in publications inkjet
  • ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like.
  • the application method for inkjet is not particularly limited.
  • the composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process.
  • the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
  • the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
  • the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.
  • the composition layer is exposed in a pattern (exposure step).
  • the composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
  • Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
  • Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred.
  • a long-wave light source of 300 nm or more can also be used.
  • the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
  • the dose is, for example, 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 selected as appropriate.
  • the exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done.
  • the oxygen concentration and exposure illuminance may be appropriately combined.
  • the illuminance may be 10000 W/m 2 at an oxygen concentration of 10% by volume and 20000 W/m 2 at an oxygen concentration of 35% by volume.
  • the unexposed portion of the composition layer is removed by development to form a pattern.
  • the development and removal of the unexposed portion of the composition layer can be performed using a developer.
  • the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion.
  • the temperature of the developer is preferably 20 to 30° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
  • an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
  • alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, 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
  • examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate.
  • a compound having a large molecular weight is preferable for the alkaline agent from the standpoint 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 transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed.
  • the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
  • the moving speed of the nozzle may be gradually decreased.
  • Additional exposure processing and post-baking are post-development curing treatments for complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
  • the light used for exposure preferably has a wavelength of 400 nm or less.
  • the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • Pattern formation by an etching method includes a step of applying the composition of the present invention to a support to form a composition layer, curing the entire composition layer to form a cured product layer, and forming a cured product layer on the cured product layer. a step of forming a photoresist layer on the substrate, a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern, and a step of etching the cured product layer using the resist pattern as a mask; and removing the resist pattern from the cured product layer.
  • the resist used for forming the resist pattern is not particularly limited, but for example, the book "Polymer New Material One Point 3 Microfabrication and Resist" Author: Saburo Nonogaki, Publisher: Kyoritsu Publishing Co., Ltd. (November 15, 1987 A resist containing an alkali-soluble phenolic resin and a naphthoquinone diazide can be used, as described on pages 16 to 22 of First Edition, 1st Edition.
  • Japanese Patent No. 2568883 Japanese Patent No. 2761786, Japanese Patent No. 2711590, Japanese Patent No. 2987526, Japanese Patent No. 3133881, Japanese Patent No. 3501427, Japanese Patent No. 3373072, Japanese Patent No.
  • Resist Environmentally Stable Chemical Amplification Positive Resist, etc. are preferred.
  • the method of etching the cured material layer may be dry etching or wet etching. Dry etching is preferred.
  • Dry etching of the cured material layer is preferably performed using a mixed gas of a fluorine-based gas and O 2 as an etching gas.
  • the mixing ratio of the fluorine-based gas and O 2 is preferably 4/1 to 1/5, more preferably 1/2 to 1/4 in terms of flow rate.
  • the fluorine-based gas include CF 4 , C 2 F 6 , C 3 F 8 , C 2 F 4 , C 4 F 8 , C 4 F 6 , C 5 F 8 and CHF 3 , and C 4 F 6 , C5F8 , C4F8 , and CHF3 are preferred, C4F6 , C5F8 are more preferred, and C4F6 is even more preferred.
  • the fluorine-based gas one type of gas can be selected from the above group, and two or more types may be included in the mixed gas.
  • the mixed gas contains helium (He), neon (Ne), argon in addition to the fluorine-based gas and O2 .
  • Noble gases such as (Ar), krypton (Kr), and xenon (Xe) may also be mixed.
  • gases that may be mixed one or two or more gases can be selected from the above group.
  • the mixing ratio of other gases that may be mixed is preferably greater than 0 and 25 or less, preferably 10 or more and 20 or less, and particularly 16 when O 2 is 1 in the flow rate ratio. preferable.
  • the internal pressure of the chamber during dry etching is preferably 0.5-6.0 Pa, more preferably 1-5 Pa.
  • Dry etching conditions include the conditions described in paragraphs 0102 to 0108 of International Publication No. 2015/190374 and Japanese Patent Application Laid-Open No. 2016-014856, the contents of which are incorporated herein.
  • An optical sensor or the like can also be manufactured by applying the film manufacturing method of the present invention.
  • FIG. 2 is a side cross-sectional view showing one embodiment of the structure of the present invention
  • FIG. 3 is a plan view of the support member in the same structure viewed from directly above.
  • the structure 100 of the present invention includes a support 11, partitions 12 provided on the support 11, and regions on the support 11 partitioned by the partitions 12. and a pixel 14 provided.
  • pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer.
  • Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the type of support 11 is not particularly limited.
  • Substrates silicon wafers, silicon carbide wafers, silicon nitride wafers, sapphire wafers, glass wafers, etc.
  • a substrate for a solid-state imaging device on which a photodiode is formed, or the like can also be used.
  • an underlying layer may be provided for improving the adhesion with the upper layer, preventing diffusion of substances, or flattening the surface.
  • partition walls 12 are formed on the support 11 .
  • the partition walls 12 are formed in a grid pattern in a plan view seen from directly above the support 11 .
  • the shape of the region partitioned by the partitions 12 on the support 11 (hereinafter also referred to as the shape of the opening of the partition) is a square, but the shape of the opening of the partition is It is not particularly limited, and may be, for example, rectangular, circular, elliptical, or polygonal.
  • the partition wall 12 can be formed using the composition of the present invention. Specifically, it can be formed through a step of forming a composition layer using the composition of the present invention and a step of forming a pattern on the composition layer by photolithography or dry etching.
  • the width W1 of the partition walls 12 is preferably 20 to 500 nm.
  • the lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 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 height H1 of the partition wall 12 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more.
  • the upper limit is preferably the thickness of the pixel 14 x 200% or less, more preferably the thickness of the pixel 14 x 150% or less, and still more preferably substantially the same as the thickness of the pixel 14 .
  • the ratio of height to width (height/width) of the partition walls 12 is preferably 1-100, more preferably 5-50, even more preferably 5-30.
  • Pixels 14 are formed in regions (openings of the partition walls) on the support 11 and partitioned by the partition walls 12 .
  • the width L1 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, even more preferably 500 to 1000 nm.
  • the height (thickness) H2 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, even more preferably 300 to 600 nm.
  • the height H2 of the pixels 14 is preferably 50 to 150%, more preferably 70 to 130%, and even more preferably 90 to 110% of the height H1 of the partition walls 12.
  • a protective layer is provided on the surface of the partition wall.
  • a protective layer By providing a protective layer on the surfaces of the partition walls 12, the adhesion between the partition walls 12 and the pixels 14 can be improved.
  • Various inorganic materials and organic materials can be used as the material of the protective layer. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, organic SOG (Spin On Glass) resins, and the like. It can also be formed using a composition containing a compound having an ethylenically unsaturated bond-containing group.
  • the structure of the present invention can be preferably used for optical filters, optical sensors, image display devices, and the like.
  • the optical filter of the present invention has the film of the present invention as described above.
  • Examples of the optical filter having the film of the present invention include an optical filter having a structure in which each pixel is embedded in a region partitioned by partition walls made of the film of the present invention.
  • Examples of pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer.
  • the width of pixels included in the optical filter is preferably 0.4 to 10.0 ⁇ m.
  • the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
  • the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • Each pixel included in the optical filter preferably has high flatness.
  • the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.).
  • the volume resistance value of the pixel is high.
  • the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more.
  • the upper limit is not specified, it is preferably 10 14 ⁇ cm or less, for example.
  • the volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the pixels of the optical filter.
  • the thickness of the protective layer is preferably 0.01-10 ⁇ m, more preferably 0.1-5 ⁇ m.
  • Examples of the method of forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive.
  • the protective layer may be one formed using the composition of the present invention.
  • the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
  • optical sensor of the present invention comprises the membrane of the present invention as described above.
  • optical sensors include solid-state imaging devices.
  • the configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
  • the image display device of the invention comprises the film of the invention.
  • image display devices include liquid crystal display devices and organic electroluminescence display devices.
  • electroluminescence display devices For a definition of an image display device and details of each image display device, see, for example, “Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989).
  • Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
  • composition ⁇ Production of composition>
  • the raw materials shown in the table below were mixed and filtered using Nippon Pall's DFA4201NIEY (0.45 ⁇ m nylon filter) to produce a composition.
  • the numerical value of the compounding quantity of surfactant in the following table is a numerical value in solid content conversion.
  • the blending amount of the cyclic siloxane compound was adjusted so that the content in the composition was the value shown in the table below.
  • the value of the ratio of the cyclic siloxane compound to 100 parts by mass of the silicone-based surfactant is also shown in the column of "ratio of cyclic siloxane compound".
  • Silica particle liquid 1 A propylene glycol monomethyl ether solution (silica particles This is a silica particle liquid prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobizing agent to 100.0 g of a solution having a concentration of 20% by mass and reacting the mixture at 20° C. for 6 hours.
  • the average particle diameter of the spherical silica was obtained by calculating the number average of the equivalent circle diameters in the projected images of the spherical portions of 50 spherical silica particles 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 it contained silica particles having a shape in which a plurality of spherical silica particles were connected in a beaded shape.
  • TEM transmission electron microscope
  • W-1 compound having the following structure (hydroxyl value 120 mgKOH/g, silicone surfactant)
  • W-2 FZ-2122 (manufactured by Dow Toray Industries, Inc., silicone surfactant)
  • W-3 SH 8400 FLUID (manufactured by Dow Toray Industries, silicone surfactant)
  • W-4 compound having the following structure (hydroxyl value 62 mgKOH/g, silicone surfactant)
  • W-5 compound with the following structure (hydroxyl value 35 mgKOH/g, silicone surfactant)
  • W-6 BYK-330 (manufactured by BYK-Chemie, silicone surfactant)
  • CW-1 Futergent 710FM (manufactured by NEOS Co., Ltd., fluorine-based surfactant)
  • ⁇ Defect evaluation> Each composition was applied on a silicon wafer having a diameter of 8 inches (20.32 cm) using a spin coater so that the film thickness after prebaking was 0.6 ⁇ m, and heated using a hot plate at 100° C. for 120 seconds. Processing (pre-baking) was performed. Next, the obtained film was inspected using a wafer defect evaluation apparatus ComPLUS3 manufactured by AMAT, and defects having a size of 0.5 ⁇ m or more were counted to obtain the number of defects. The inspection range was defined as a region of the 8-inch silicon wafer that was 5 mm or more inward from the outer periphery. 5: The number of defects is 5 or less 4: The number of defects is more than 5 and 20 or less 3: The number of defects is more than 20 and 50 or less 2: The number of defects is more than 50 and 100 or less 1: Defects more than 100 in number

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JP2004203788A (ja) * 2002-12-25 2004-07-22 Kose Corp 固形状油中水型乳化化粧料
JP2005082796A (ja) * 2003-09-11 2005-03-31 Hakuto Co Ltd オルガノポリシロキサン化合物含有化粧料
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