WO2021171929A1 - Composition durcissable, film, filtre de transmission de rayonnement infrarouge, élément d'imagerie à semi-conducteurs, et capteur de rayonnement infrarouge - Google Patents

Composition durcissable, film, filtre de transmission de rayonnement infrarouge, élément d'imagerie à semi-conducteurs, et capteur de rayonnement infrarouge Download PDF

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Publication number
WO2021171929A1
WO2021171929A1 PCT/JP2021/003657 JP2021003657W WO2021171929A1 WO 2021171929 A1 WO2021171929 A1 WO 2021171929A1 JP 2021003657 W JP2021003657 W JP 2021003657W WO 2021171929 A1 WO2021171929 A1 WO 2021171929A1
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curable composition
compound
less
mass
film
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PCT/JP2021/003657
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English (en)
Japanese (ja)
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良司 折田
峻輔 北島
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富士フイルム株式会社
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Priority to JP2022503203A priority Critical patent/JPWO2021171929A1/ja
Publication of WO2021171929A1 publication Critical patent/WO2021171929A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a curable composition suitable for producing an infrared transmission filter or the like, and a film using the above-mentioned curable composition. It also relates to an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
  • the solid-state image sensor is used as an optical sensor in various applications.
  • infrared rays have a longer wavelength than visible light, so they are less likely to scatter, and can be used for distance measurement and three-dimensional measurement.
  • infrared rays are invisible to humans and animals, even if the subject is illuminated with an infrared light source at night, the subject will not be noticed, and it will not stimulate the other party for shooting nocturnal wild animals or for crime prevention. It can also be used for shooting.
  • the optical sensor infrared sensor
  • the optical sensor that senses infrared rays can be developed for various purposes, and it is desired to develop a film that can be used for the infrared sensor.
  • Patent Document 1 describes a composition containing a coloring material that transmits infrared rays to block visible light, an infrared absorber, and a curable compound, and the infrared absorber has a wavelength in the range of more than 1000 nm and less than 1200 nm.
  • a / B is the ratio of the minimum value A of the absorbance of the above composition in the wavelength range of 400 to 1100 nm to the maximum value B of the absorbance in the wavelength range of 1400 to 1500 nm.
  • Compositions of 5 or more are described.
  • an object of the present invention is to provide a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. It is also an object of the present invention to provide a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
  • the present invention provides: ⁇ 1> A curable composition containing quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound. A curable composition containing 5% by mass or more of the quantum dots in the total solid content of the curable composition. ⁇ 2> The curable composition according to ⁇ 1>, wherein the quantum dots contain Pb atoms. ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, wherein the average primary particle size of the quantum dots is 1 to 10 nm.
  • the above quantum dots are A first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm,
  • the curable composition according to ⁇ 4> which contains 10 to 80 parts by mass of the second quantum dot with respect to 100 parts by mass of the first quantum dot.
  • ⁇ 6> The curable composition according to ⁇ 4> or ⁇ 5>, wherein the difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is 30 to 200 nm.
  • ⁇ 7> The curable composition according to any one of ⁇ 1> to ⁇ 6>, wherein a ligand is coordinated to the quantum dots.
  • a ligand is a carboxylic acid compound.
  • the carboxylic acid compound has a molecular weight of 100,000 or less.
  • the content of the organic coloring material is 500 parts by mass or less with respect to 100 parts by mass of the quantum dots.
  • ⁇ 12> The curable composition according to ⁇ 10> or ⁇ 11>, wherein the organic coloring material is a compound having a maximum absorption wavelength in a wavelength range of more than 700 nm and 1400 nm or less.
  • the curable compound contains a resin and contains a resin.
  • the curable composition according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the resin having an amine value in the total amount of the resin is 30% by mass or less.
  • ⁇ 15> A / B which is the ratio of the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm, of the curable composition is 4.5 or more
  • ⁇ 17> A film obtained from the curable composition according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 19> A solid-state image sensor having the film according to ⁇ 17>.
  • a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor can be provided.
  • the total solid content refers to the total mass of the components of the curable composition excluding the solvent.
  • infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
  • the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • EUV light extreme ultraviolet rays
  • (meth) acrylate” represents both acrylate and methacrylate, or either
  • (meth) acrylic represents both acrylic and methacrylic, or either.
  • Acryloyl "represents both acryloyl and / or methacryloyl.
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the term "process” is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) is used as a column. It can be determined by using a 0.0 mm ID (inner diameter) x 15.0 cm) and using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • HLC-8220 manufactured by Tosoh Corporation
  • TSKgel Super AWM-H manufactured by Tosoh Corporation
  • the curable composition of the present invention contains quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound, and contains 5% by mass or more of the quantum dots in the total solid content of the curable composition. It is characterized by containing.
  • Quantum dots have a discontinuous energy level of quantum effect and a bandgap type continuous energy level.
  • the maximum absorption wavelength (absorption peak) of a quantum dot corresponds to a discontinuous energy level expressed by the quantum effect, and the energy level changes depending on the particle size.
  • the quantum dots have a light-shielding property due to bandgap type absorption for light having a wavelength shorter than the maximum absorption wavelength of the quantum dots. Therefore, for example, a quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm has a high light-shielding property for light in the vicinity of the maximum absorption wavelength and light having a wavelength shorter than that.
  • the present inventors By incorporating such quantum dots in the total solid content of the curable composition in an amount of 5% by mass or more, the present inventors have a high light-shielding property in the visible region, which is higher than the maximum absorption wavelength of the quantum dots. It has been found that a film having high transparency to light having a wavelength on the long wavelength side can be formed. Therefore, it has been found that the curable composition of the present invention can form a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, the present inventors have found that the maximum absorption wavelength can be adjusted by adjusting the size of the quantum dot or the like.
  • the maximum absorption wavelength can be shifted to the long wave side, and by reducing the size of the quantum dots, the maximum absorption wavelength can be shifted to the short wave side. .. Therefore, it has been found that the spectroscopic design of infrared rays transmitted through the film can be easily changed and adjusted, and the design can be changed according to the purpose.
  • the curable composition of the present invention is preferably used as a curable composition for an infrared transmission filter.
  • the ratio of the minimum value A of the absorbance of the curable composition of the present invention in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm is preferably 4.5 or more, and preferably 10 or more. It is preferably 20 or more, more preferably 30 or more, and even more preferably 30 or more.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 650 nm is 20% or less, and the light having a wavelength of 2200 nm in the film thickness direction. It is possible to preferably form a film having a spectral characteristic of 70% or more in transmittance.
  • composition of the present invention satisfies any of the following spectral characteristics (IR1) to (IR12).
  • (IR1) A1 / B1 which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 830 nm and the maximum absorbance B1 in the wavelength range of 1000 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1000 to 2200 nm.
  • the ratio of the minimum absorbance A2 in the wavelength range of 400 to 950 nm and the maximum absorbance B2 in the wavelength range of 1100 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 940 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1100 to 2200 nm.
  • the ratio of the minimum absorbance A3 in the wavelength range of 400 to 1050 nm and the maximum absorbance B3 in the wavelength range of 1200 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1200 to 2200 nm.
  • IR4 A4 / B4 which is the ratio of the minimum absorbance A4 in the wavelength range of 400 to 1150 nm and the maximum absorbance B4 in the wavelength range of 1300 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1300 to 2200 nm.
  • the ratio of the minimum absorbance A5 in the wavelength range of 400 to 1250 nm and the maximum absorbance B5 in the wavelength range of 1400 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1400 to 2200 nm.
  • IR6 A6 / B6 which is the ratio of the minimum absorbance A6 in the wavelength range of 400 to 1350 nm and the maximum absorbance B6 in the wavelength range of 1500 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1500 to 2200 nm.
  • the ratio of the minimum absorbance A7 in the wavelength range of 400 to 1450 nm and the maximum absorbance B7 in the wavelength range of 1600 to 2200 nm of the curable composition, A7 / B7, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1600 to 2200 nm.
  • the ratio of the minimum absorbance A8 in the wavelength range of 400 to 1550 nm and the maximum absorbance B8 in the wavelength range of 1700 to 2200 nm of the curable composition, A8 / B8, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1700 to 2200 nm.
  • the ratio of the minimum absorbance A9 in the wavelength range of 400 to 1650 nm and the maximum absorbance B9 in the wavelength range of 1800 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1800 to 2200 nm.
  • IR10 A10 / B10 which is the ratio of the minimum absorbance A10 in the wavelength range of 400 to 1750 nm and the maximum absorbance B10 in the wavelength range of 1900 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1900 to 2200 nm.
  • IR11 A11 / B11, which is the ratio of the minimum absorbance A11 in the wavelength range of 400 to 1850 nm and the maximum absorbance B11 in the wavelength range of 2000 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less, and the light transmittance in the film thickness direction.
  • a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2000 to 2200 nm can be preferably formed.
  • IR12 A12 / B12 which is the ratio of the minimum absorbance A12 in the wavelength range of 400 to 1950 nm and the maximum absorbance B12 in the wavelength range of 2100 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
  • the upper limit can be, for example, 90 or less.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2100 to 2200 nm.
  • the above absorbance condition can be achieved, for example, by adjusting the type and content of quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ -log (T ⁇ / 100) ...
  • a ⁇ is the absorbance at the wavelength ⁇
  • T ⁇ is the transmittance (%) at the wavelength ⁇ .
  • the absorbance value may be a value measured in a solution state or a value in a film formed by using the curable composition of the present invention.
  • a curable composition is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a membrane prepared by drying at 100 ° C. for 120 seconds.
  • the thickness of the film can be measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC, Inc.) for the substrate having the film.
  • the absorbance can be measured using a conventionally known spectrophotometer.
  • the measurement condition of the absorbance is not particularly limited, but the absorbance B at the wavelength of 2200 nm is measured under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 650 nm is adjusted to 0.1 to 3.0. Is preferable. By measuring the absorbance under such conditions, the measurement error can be further reduced.
  • the method for adjusting the minimum absorbance A in the wavelength range of 400 to 650 nm to be 0.1 to 3.0 is not particularly limited. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell can be mentioned. Further, when measuring the absorbance in the state of a film, a method of adjusting the film thickness and the like can be mentioned.
  • the curable composition of the present invention is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and dried at 100 ° C. for 120 seconds using a hot plate. ..
  • the thickness of the film is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.
  • the transmittance of the dried substrate having this film is measured using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
  • the total solid content (solid content concentration) of the curable composition of the present invention varies depending on the method of application to the substrate, but is preferably 1 to 50% by mass, for example.
  • the lower limit is more preferably 10% by mass or more.
  • the upper limit is more preferably 30% by mass or less.
  • the curable composition of the present invention is the above-mentioned film when a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed. At least one of the thicknesses, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength is 2200 nm. It is preferable that the light transmittance of the light is 70% or more (preferably 75% or more, more preferably 80% or more).
  • composition of the present invention satisfies the spectral characteristics of any of the following aspects (1) to (12).
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
  • a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
  • a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
  • a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
  • a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
  • a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
  • An embodiment in which the minimum value of the rate in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
  • the curable composition of the present invention transmits infrared rays, it can also be said to be an infrared transmissive composition.
  • each component that can constitute the curable composition of the present invention will be described.
  • Quantum dots The curable composition of the present invention contains quantum dots (hereinafter, also referred to as quantum dot IR) having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.
  • quantum dot IR quantum dots
  • the value of the maximum absorption wavelength of a quantum dot is a value in a solution.
  • the maximum absorption wavelength of the quantum dots can be determined by preparing a toluene solution of quantum dots of 10 mg / mL and measuring the absorbance of the toluene solution using an ultraviolet-visible near-infrared spectrophotometer.
  • the quantum dot IR may be a semiconductor particle.
  • Examples of the quantum dot material constituting the quantum dot include general semiconductor crystals [a) group IV semiconductors, b) group IV-IV, group III-V, or group II-VI compound semiconductors, c) group II, and the like. Nanoparticles (particles having a size of 0.5 nm or more and less than 100 nm) of a compound semiconductor composed of a combination of three or more of group III, group IV, group V, and group VI elements can be mentioned.
  • the quantum dot IR preferably contains at least one metal atom selected from Pb atom, In atom, Ge atom, Si atom, Cd atom, Zn atom, Hg atom, Al atom, Sn atom and Ga atom. It is more preferable that it contains at least one metal atom selected from Pb atom, In atom, Ge atom and Si atom, and it is further preferable that it contains Pb atom.
  • quantum dot material constituting the quantum dot IR, PbS, PbSe, InN, InAs, Ge, InAs, InGaAs, CuInS, CuInSe, CuInGaSe, InSb, HgTe, HgCdTe, Ag 2 S, Ag 2 Se, Ag 2 Te, SnS, SnSe, SnTe , Si, narrow semiconductor material having relatively bandgap such InP can be mentioned, preferably a PbS or PbSe, more preferably PbS.
  • the maximum absorption wavelength of the quantum dot IR can be appropriately selected according to the application and purpose. For example, when a quantum dot having a maximum absorption wavelength in the wavelength range of 1000 to 1100 nm is used as the quantum dot IR, a film that blocks light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more. Can be formed.
  • the average primary particle size of the quantum dot IR is preferably 1 to 10 nm.
  • the average primary particle size of the quantum dot IR is an average value of the primary particle size of 10 arbitrarily selected quantum dots.
  • a transmission electron microscope may be used to measure the particle size of the quantum dots.
  • a ligand is coordinated to the quantum dot IR.
  • the quantum dot IR includes the first quantum dot and the second quantum dot described later, it is preferable that the ligand is coordinated to at least one quantum dot, and the ligand is coordinated to both quantum dots. It is more preferable that the position is coordinated. According to this aspect, the dispersibility of the quantum dots in the curable composition is good.
  • the ligand include a carboxylic acid compound, an amine compound, a phosphonic acid compound, and a thiol compound, and a carboxylic acid compound is preferable from the viewpoint of dispersibility of the quantum dot IR.
  • the molecular weight of the carboxylic acid compound is preferably 100,000 or less, more preferably 60 to 10,000, and even more preferably 100 to 1,000.
  • Specific examples of the carboxylic acid compound include oleic acid, 3-mercaptopropionic acid, 4-mercaptobenzoic acid and the like.
  • the curable composition of the present invention has a first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm as a quantum dot IR, and a maximum absorption on the wavelength side longer than the maximum absorption wavelength of the first quantum dot. It is also preferable to use a second quantum dot having a wavelength. According to this aspect, it is possible to form a film having a better light-shielding property of light having a wavelength on the short wave side than the maximum absorption wavelength of the second quantum dot. Two or more types of second quantum dots may be included.
  • the difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is preferably 1 to 500 nm because the visible light-shielding property of the obtained film can be further enhanced. It is more preferably 20 to 300 nm, and even more preferably 30 to 200 nm.
  • the difference between the maximum absorption wavelength of the second quantum dot having the maximum absorption wavelength on the shortest wavelength side and the maximum absorption wavelength of the first quantum dot is large. It is preferably in the above range.
  • the maximum absorption wavelength of the second quantum dot A a where the maximum absorption wavelength exists in a long wavelength side in a th is preferably 1 to 500 nm, more preferably 20 to 300 nm. It is more preferably 30 to 200 nm.
  • a represents an integer of 1 to n-1
  • n represents an integer of 3 or more.
  • the content of the quantum dot IR in the total solid content of the curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more. It is even more preferably 25% by mass or more, and particularly preferably 30% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.
  • the second quantum dots are added to 100 parts by mass of the first quantum dots. It is preferable to contain 100 parts by mass.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.
  • the curable composition of the present invention may further contain quantum dots having a maximum absorption wavelength in the wavelength range of 400 nm or more and less than 700 nm (hereinafter, also referred to as quantum dots Vl).
  • quantum dots Vl quantum dots having a maximum absorption wavelength in the wavelength range of 400 nm or more and less than 700 nm
  • Examples of the material of the quantum dot Vl include those explained in the quantum dot IR.
  • the maximum absorption wavelength of the quantum dot Vl is preferably in the wavelength range of 450 nm or more and less than 700 nm, more preferably in the wavelength range of 500 nm or more and less than 700 nm, and more preferably in the wavelength range of 600 nm or more and less than 700 nm. More preferred.
  • the content of the quantum dot Vl in the total solid content of the curable composition is preferably more than 0% by mass and 10% by mass or less.
  • the lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more.
  • the upper limit is preferably 8% by mass or less, and more preferably 5% by mass or less.
  • the total content of the quantum dot IR and the quantum dot Vl in the total solid content of the curable composition is preferably 5 to 80% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more.
  • the upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
  • the curable composition of the present invention can contain an organic coloring material. According to this aspect, it is easy to enhance the light blocking property and form a film capable of selectively transmitting the target light.
  • the organic color material include a chromatic color material, a black color material, and a near-infrared absorbing color material.
  • the organic color material means a color material composed of an organic compound.
  • the organic coloring material in the present specification includes a coloring material composed of an organic compound containing a metal atom such as a metal complex. Examples of the coloring material composed of an organic compound containing a metal atom include a phthalocyanine compound containing a metal atom such as copper, zinc, and aluminum as a central metal.
  • the organic coloring material may be a pigment or a dye. Pigments and dyes may be used in combination.
  • the organic coloring material preferably contains a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. Examples of such a color material include a near-infrared absorbing color material.
  • 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 primary particle size of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is an arithmetic mean value of the primary particle size for the primary particles of 400 pigments.
  • the primary particles of the pigment refer to independent particles without agglomeration.
  • chromatic color material examples include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.
  • a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Pigments can also be used. Specific examples include the compounds described in WO 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069009027, the phthalocyanine compound having a phosphate ester described in International Publication No. 2012/10395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraphs 0047 of JP2011-157478A.
  • the quinophthalone compound described in Kai 2019-008014 can also be used.
  • red color material a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole pigment described in paragraphs 0016 to 0022 of Patent No. 6248838.
  • the red color material described in Japanese Patent No. 6516119, the red color material described in Japanese Patent No. 6525101, and the like can also be used.
  • a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom, or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.
  • a dye can be used as a chromatic color material.
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethine compound, xanthene compound Examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds.
  • the thiazole compound described in JP2012-158649A, the azo compound described in JP2011-184493, and the azo compound described in JP2011-145540 can also be used.
  • a dye multimer can also be used.
  • the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures.
  • the upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures contained in one molecule may have the same dye structure or different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
  • the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers are available from JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, JP-A-2016-102191, International Publication No. 2016 / Compounds described in 031442 and the like can also be used.
  • Two or more kinds of chromatic color materials may be used in combination. Further, when two or more kinds of chromatic color materials are used in combination, black may be formed by a combination of two or more kinds of chromatic color materials. Examples of such a combination include the following aspects (1) to (8). (1) An embodiment containing a yellow color material, a blue color material, a purple color material, and a red color material. (2) An embodiment containing a yellow color material, a blue color material, and a red color material. (3) An embodiment containing a yellow color material, a purple color material, and a red color material. (4) An embodiment containing a yellow color material and a purple color material.
  • An embodiment containing a green color material, a blue color material, a purple color material, and a red color material An embodiment containing a purple color material and an orange color material.
  • An embodiment containing a green color material, a purple color material, and a red color material An embodiment containing a green color material and a red color material.
  • the black color material is not particularly limited, and known materials can be used.
  • bisbenzofuranone compound, azomethine compound, perylene compound, azo compound and the like can be mentioned, and bisbenzofuranone compound and perylene compound are preferable.
  • Examples of the bisbenzofuranone compound are described in JP-A-2010-534726, JP-A-2012-515233, App. Compounds are mentioned and are available, for example, as "Irgaphor Black” manufactured by BASF.
  • Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned.
  • the azomethine compound include the compounds described in JP-A-01-170601 and JP-A-02-0346664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.
  • the near-infrared absorbing color material is preferably an organic coloring material having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less.
  • the maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less.
  • the near-infrared absorbing color material preferably has A 550 / A max, which is the ratio of the absorbance A 550 at a wavelength of 550 nm and the absorbance A max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less.
  • the absorbance ratio is in the above range, a near-infrared absorbing color material having excellent visible transparency and near-infrared shielding property can be obtained.
  • the near-infrared absorbing color material is preferably a pigment.
  • the maximum absorption wavelength of the near-infrared absorbing color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the composition containing the near-infrared absorbing color material.
  • the near-infrared absorbing coloring material is not particularly limited, but is pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonor compound, iminium compound, dithiol compound, and tria.
  • Examples thereof include a reelmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex.
  • Examples of the pyrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-066731, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033.
  • Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph number 0072 of International Publication No.
  • JP2012-077153 the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480.
  • vanadium phthalocyanine compound described in Japanese Patent No. 6081771.
  • examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP2012-077153.
  • Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
  • Examples of the near-infrared absorbing coloring material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953.
  • Squarylium compound described in Japanese Patent Publication No. 60366689 Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, paragraph numbers 0090 to 0107, special feature.
  • Linked squalylium compound compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazolebis-type squalylium compound described in JP-A-2017-082029, JP-A-2017-068120
  • the asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017, the pyrrole ring-containing compound (carbazole type) described in JP-A-2017-067963, the phthalocyanine compound described in Japanese Patent No. 6251530, and the like are used. You can also do it.
  • the content of the organic coloring material is preferably 500 parts by mass or less, preferably 100 parts by mass or less, with respect to 100 parts by mass of the quantum dot IR (quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm). More preferably, it is more preferably 50 parts by mass or less.
  • the lower limit may be 1 part by mass or more, or 10 parts by mass or more.
  • the curable composition of the present invention contains a curable compound.
  • the curable compound include polymerizable compounds, resins, and natural polymers such as gelatin and cellulose.
  • the gelatin there are acid-treated gelatin and alkali-treated gelatin (lime treatment and the like) depending on the synthesis method, and both of them can be preferably used.
  • the molecular weight of gelatin is preferably 10,000 to 1,000,000.
  • modified gelatin modified by utilizing an amino group or a carboxyl group of gelatin can also be used (for example, phthalated gelatin).
  • the resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group).
  • the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, and a methylol group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, and a (meth) acryloyl group.
  • the polymerizable resin (resin having a polymerizable group) is also a polymerizable compound.
  • the curable compound preferably contains at least a resin, more preferably a resin and a monomer-type polymerizable compound, and a monomer-type compound having an ethylenically unsaturated bond with the resin. It is more preferable to use a polymerizable compound.
  • the content of the curable compound in the total solid content of the curable composition of the present invention is preferably 0.1 to 80% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more.
  • the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.
  • the curable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
  • polymerizable compound examples include a compound having an ethylenically unsaturated bond-containing group, a compound having an epoxy group, and a compound having a methylol group.
  • the polymerizable compound may be a monomer or a resin.
  • a monomer-type polymerizable compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound.
  • the compound having an epoxy group can be preferably used as a cationically polymerizable compound.
  • the molecular weight of the monomer-type polymerizable compound is preferably less than 2000, more preferably 100 or more and less than 2000, and even more preferably 200 or more and less than 2000.
  • the upper limit of the molecular weight of the monomer-type polymerizable compound is preferably 1500 or less.
  • the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3000 or more, and more preferably 5000 or more.
  • Examples of the resin type polymerizable compound include an epoxy resin and a resin containing a repeating unit having a polymerizable group.
  • Examples of the repeating unit having a polymerizable group include the following formulas (A2-1) to (A2-4).
  • R 1 represents a hydrogen atom or an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • L 51 represents a single bond or a divalent linking group.
  • the divalent linking group includes an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , -NR 10- (R 10 is a hydrogen atom or (Representing an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof can be mentioned.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • the alkylene group may have a substituent, but is preferably unsubstituted.
  • the alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic.
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more
  • P 1 represents a polymerizable group.
  • the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, a methylol group, and an alkoxymethyl group.
  • the compound having a monomer-type ethylenically unsaturated bond-containing group is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.
  • a compound containing a monomer-type ethylenically unsaturated bond-containing group the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification.
  • Examples of the compound having a group having a monomer-type ethylenically unsaturated bond include ethylene oxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol tri.
  • Acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (Meta) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A- DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues and / or propylene glycol residues are preferable.
  • oligomer types can be used. Further, the polymerization described in paragraph numbers 0034 to 0038 of JP2013-253224A and paragraph number 0477 of JP2012-208494A (paragraph number 0585 of the corresponding US Patent Application Publication No. 2012/0235099). Sexual monomers and the like can also be used and these contents are incorporated herein.
  • Compounds having a monomer-type ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic) and pentaerythritol tetraacrylate (Shin-Nakamura).
  • the compound containing a monomer-type ethylenically unsaturated bond-containing group may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
  • an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
  • Examples of commercially available products include the Aronix series manufactured by Toagosei Co., Ltd. (for example, M-305, M-510, M-520).
  • the compound containing a monomer-type ethylenically unsaturated bond-containing group is preferably a compound having a caprolactone structure.
  • the compound having a caprolactone structure the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
  • a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used.
  • the compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and / or a propyleneoxy group is preferable, and a group having an ethylenically unsaturated bond.
  • a compound having an ethyleneoxy group and an ethyleneoxy group is more preferable, and a 3 to 6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups is further preferable.
  • SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and three isobutyleneoxy groups.
  • examples thereof include KAYARAD TPA-330, which is a trifunctional (meth) acrylate having.
  • Examples of the compound containing an ethylenically unsaturated bond-containing group are described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Patent Application Laid-Open No. 51-0371993, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-0176765.
  • Urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Is also suitable.
  • addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. Can be done.
  • Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (Kyoeisha Chemical Co., Ltd.).
  • the compound containing an ethylenically unsaturated bond-containing group the compounds described in Japanese Patent Application Laid-Open No. 2017-0438367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used. Further, as the compound containing an ethylenically unsaturated bond-containing group, it is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like. ..
  • the content of the compound containing an ethylenically unsaturated bond-containing group in the total solid content of the curable composition is 0. It is preferably 1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 5% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
  • Examples of the compound having an epoxy group include a monofunctional or polyfunctional glycidyl ether compound, a polyfunctional aliphatic glycidyl ether compound, and the like. Further, as the epoxy compound, a compound having an alicyclic epoxy group can also be used.
  • Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less.
  • the lower limit of the epoxy group is preferably two or more.
  • the epoxy compound may be either a small molecule compound (for example, a molecular weight of less than 1000) or a high molecular compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the weight average molecular weight of the epoxy compound is preferably 2000 to 100,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
  • epoxy compounds include EHPE3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), ADEKA Glycyrrol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), and marproof.
  • the content of the epoxy compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
  • Examples of the compound having a methylol group include a compound in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
  • Compounds in which the methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylated benzoguanamine, alkoxymethylated glycol uryl, methylated glycol uryl, alkoxymethylated urea and methylol.
  • Urea compound and the like are preferable. Further, the description of paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 095 to 0126 of JP-A-2014-089408 can be referred to, and these contents are incorporated in the present specification.
  • the content of the methylol compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
  • a resin in the curable composition of the present invention, can be used as the curable compound. It is preferable to use a curable compound containing at least a resin.
  • the resin can also be used as a dispersant.
  • the resin used to disperse pigments and the like is also referred to as a dispersant.
  • such an application of the resin is an example, and the resin can be used for a purpose other than such an application.
  • the resin having a polymerizable group also corresponds to a polymerizable compound.
  • the weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3000 or more, and more preferably 5000 or more.
  • Examples of the resin include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide resin.
  • Examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin.
  • Examples of the epoxy resin include polymer-type compounds among the compounds exemplified as the epoxy compounds described in the above-mentioned section of polymerizable compounds.
  • Examples of commercially available cyclic olefin resins include ARTON F4520 (manufactured by JSR Corporation).
  • the resin described in Japanese Patent Application Laid-Open No. 2017-066240 can also be used, and the contents thereof are incorporated in the present specification. Further, a resin having a fluorene skeleton can also be used.
  • the resin used in the present invention may have an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. These acid groups may be only one kind or two or more kinds.
  • the resin having an acid group can also be used as an alkali-soluble resin.
  • a polymer having a carboxyl group in the side chain is preferable.
  • Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins.
  • examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
  • alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate.
  • Examples thereof include ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like.
  • N-substituted maleimide monomers described in JP-A-10-300922 for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used.
  • the other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.
  • the resin having an acid group may further contain a repeating unit having a polymerizable group.
  • the content of the repeating unit having a polymerizable group in all the repeating units is preferably 10 to 90 mol%, and 20 to 20 to 90 mol%. It is more preferably 90 mol%, further preferably 20 to 85 mol%.
  • the content of the repeating unit having an acid group in all the repeating units is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and preferably 5 to 30 mol%. More preferred.
  • the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the polymer contains repeating units derived from the components.
  • R 1 and R 2 represent hydrocarbon groups having 1 to 25 carbon atoms, which may each independently have a hydrogen atom or a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description of JP-A-2010-168539 can be referred to.
  • ether dimer for example, paragraph number 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.
  • the ether dimer may be of only one type or of two or more types.
  • the resin having an acid group may contain a repeating unit derived from the compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms.
  • n represents an integer from 1 to 15.
  • the acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g.
  • the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
  • the upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
  • Examples of the resin having an acid group include a resin having the following structure.
  • Me represents a methyl group.
  • the composition of the present invention may also contain a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
  • the basic group contained in the basic dispersant is preferably an amino group.
  • the dispersant is preferably an acidic dispersant (acidic resin).
  • the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity with a solvent due to the graft chain, it is excellent in the dispersibility of the pigment and the dispersion stability after aging.
  • the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
  • the resin used as the dispersant is an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain.
  • a resin having a basic nitrogen atom on at least one of them is preferable.
  • the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • the description in paragraphs 0102 to 0174 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
  • the dispersant is also available as a commercially available product, and specific examples thereof include BYK2000 (manufactured by Big Chemie Japan Co., Ltd.). Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersant.
  • the content of the resin having an amine value in the total amount of the resin contained in the curable composition is 30% by mass from the viewpoint of storage stability of the curable composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. It is more preferably 0.1% by mass or less, and particularly preferably 0.1% by mass or less.
  • the content of the resin in the total solid content of the curable composition is preferably 0.1 to 50% by mass.
  • the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less.
  • the content of the resin having an amine value in the total solid content of the curable composition is preferably 30% by mass or less, preferably 20% by mass or less. Is more preferable, and 10% by mass or less is further preferable.
  • the curable composition of the present invention contains substantially no resin having an amine value.
  • the content of the resin having an amine value in the total solid content of the curable composition is 0.05% by mass or less. It is preferably 0.01% by mass or less, and particularly preferably does not contain a resin having an amine value.
  • the curable composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
  • the mass ratio of the polymerizable compound to the resin is polymerizable.
  • the compound / resin is preferably 0.4 to 1.4.
  • the lower limit of the mass ratio is preferably 0.5 or more, more preferably 0.6 or more.
  • the upper limit of the mass ratio is preferably 1.3 or less, more preferably 1.2 or less.
  • the curable composition of the present invention can contain a photopolymerization initiator.
  • the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable to select and use it according to the type of the polymerizable compound. When a radically polymerizable compound such as a compound having an ethylenically unsaturated bond-containing group is used as the polymerizable compound, it is preferable to use a photoradical polymerization initiator as the photopolymerization initiator.
  • a photocationic polymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators.
  • a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
  • the content of the photopolymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
  • the curable composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.
  • Photoradical polymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds examples include hexaarylbiimidazole, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
  • It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound, and an oxime compound and an ⁇ -hydroxyketone compound.
  • ⁇ -Aminoketone compound, and an acylphosphine compound are more preferable, and an oxime compound is further preferable.
  • the photoradical polymerization initiator the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacare 1173, Irgacure29. (Manufactured by the company) and the like.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacare 907, Irgacare 369, Irgacure 369, Irgacure 369, Irgar (Made) and so on.
  • acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
  • Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166.
  • oxime compound examples 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-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photoradical polymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
  • an oxime compound having a nitro group can be used as the photoradical polymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
  • an oxime compound having a benzofuran skeleton can also be used.
  • Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the curable composition with time is improved.
  • Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication No.
  • the photoradical polymerization initiator contains an oxime compound and an ⁇ -aminoketone compound.
  • the developability is improved and it is easy to form a pattern having excellent rectangularity.
  • the ⁇ -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
  • the content of the photoradical polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
  • the curable composition of the present invention may contain only one kind of photoradical polymerization initiator, or may contain two or more kinds of photoradical polymerization initiators. When two or more kinds of photoradical polymerization initiators are contained, the total amount thereof is preferably in the above range.
  • Photocationic polymerization initiator examples include a photoacid generator.
  • the photoacid generator include onium salt compounds such as diazonium salt, phosphonium salt, sulfonium salt, and iodonium salt, which are decomposed by light irradiation to generate acid, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl.
  • sulfonate compounds such as sulfonate.
  • the content of the photocationic polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
  • the curable composition of the present invention may contain only one type of photocationic polymerization initiator, or may contain two or more types of photocationic polymerization initiators. When two or more types of photocationic polymerization initiators are contained, the total amount thereof is preferably in the above range.
  • the curable composition of the present invention can contain a polyfunctional thiol.
  • a polyfunctional thiol is a compound having two or more thiol (SH) groups.
  • the polyfunctional thiol acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen.
  • the sensitivity can be increased.
  • a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
  • polyfunctional thiol examples include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio.
  • the content of polyfunctional thiol in the total solid content of the curable composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass.
  • the curable composition of the present invention may contain only one type of polyfunctional thiol, or may contain two or more types of polyfunctional thiols. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
  • Epoxy resin curing agent When the curable composition of the present invention contains an epoxy resin, it is preferable that the curable composition further contains an epoxy resin curing agent.
  • the epoxy resin curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polyvalent carboxylic acids.
  • a polyvalent carboxylic acid is preferable from the viewpoint of heat resistance and transparency of the cured product, and a compound having two or more carboxylic acid anhydride groups in the molecule is most preferable.
  • Specific examples of the epoxy resin curing agent include butane diic acid.
  • the content of the epoxy resin curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy resin. ..
  • the curable composition of the present invention can further contain a pigment derivative.
  • the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to the pigment skeleton.
  • the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, inimium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonor pigment skeleton, and pyrolopyrrolop pigment.
  • Examples of the acid group include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, an imic acid group and salts thereof.
  • a carboxylic acid amide group a group represented by -NHCOR X1 is preferable.
  • the sulfonic acid amide group preferably a group represented by -NHSO 2 R X2.
  • a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable.
  • RX1 to RX6 independently represent a hydrocarbon group or a heterocyclic group.
  • Hydrocarbon or heterocyclic group R X1 ⁇ R X6 represents may further have a substituent.
  • alkali metal ions Li + , Na + , K +, etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+, etc.
  • ammonium ions imidazolium ions, pyridinium ions, etc.
  • Examples include phosphonium ions.
  • the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group.
  • the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • pigment derivative examples include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-2170777, Japanese Patent Application Laid-Open No. 03-009961, and Japanese Patent Application Laid-Open No. 03-026767.
  • the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
  • the curable composition of the present invention can contain a solvent.
  • the solvent include organic solvents.
  • the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the curable composition.
  • organic solvents include, for example, esters, ethers, ketones, aromatic hydrocarbons, hydrocarbons and the like.
  • paragraph No. 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference.
  • an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • hydrocarbon solvent having 5 to 30 carbon atoms can be preferably used.
  • the hydrocarbon solvent may be a mixture of a linear compound and a branched compound, or may be a mixture of two or more compounds having different carbon atoms.
  • Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and the like.
  • Examples thereof include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and the like.
  • the organic solvent may be used alone or in combination of two or more.
  • 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility.
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent of mass ppt (parts per parts) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the solvent is preferably 10 to 99% by mass with respect to the total amount of the curable composition of the present invention.
  • the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the curable composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass.
  • the curable composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group and a phenyl group.
  • the (meth) acryloyl group and the epoxy group are preferable.
  • Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. Incorporated into the specification.
  • the content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass.
  • the silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • the surfactant include the surfactants described in paragraphs 0238 to 0245 of WO2015 / 166779, the contents of which are incorporated herein by reference.
  • the surfactant is preferably a fluorine-based surfactant.
  • a fluorine-based surfactant in the curable composition, the liquid properties (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in a curable composition.
  • fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding international publication No. 2014/017669), and Japanese Patent Application Laid-Open No. 2011-.
  • the surfactants described in paragraphs 0117 to 0132 of JP 132503 are mentioned and their contents are incorporated herein by reference.
  • Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut and the fluorine atom is volatilized.
  • fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3000-50000, for example 14000.
  • % indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
  • the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation, RS-72-K and the like can be mentioned.
  • the fluorine-based surfactant the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
  • the content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass.
  • the surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indol compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-068814.
  • Examples include the compounds described in paragraphs 0061 to 0080 of JP 2016-162946, the contents of which are incorporated herein.
  • Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
  • the content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain an antioxidant.
  • the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • the antioxidant a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • a phosphorus-based antioxidant can also be preferably used.
  • a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600 can also be used.
  • the content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.
  • the curable composition of the present invention can be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent), if necessary. , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs of JP-A-2008-250074.
  • the curable composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
  • the storage container for the curable composition of the present invention is not particularly limited, and a known storage container can be used.
  • a storage container a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin have a 7-layer structure for the purpose of suppressing impurities from being mixed into raw materials and curable compositions. It is also preferable to use a bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the curable composition, and suppressing deterioration of components.
  • the curable composition of the present invention can be prepared by mixing the above-mentioned components.
  • all the components may be dissolved or dispersed in a solvent at the same time to prepare a curable composition, or if necessary, two or more solutions in which each component is appropriately blended or
  • the dispersion may be prepared in advance and mixed at the time of use (at the time of application) to prepare a curable composition.
  • the curable composition of the present invention contains a pigment
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
  • the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial. Practical application The process and disperser described in Paragraph No.
  • the pigment may be miniaturized in the salt milling step.
  • the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
  • PP polypropylene
  • a filter using a material such as (including the polyolefin resin of) is mentioned.
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
  • fibrous filter medium examples include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of 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 Co., Ltd.
  • filters for example, a first filter and a second filter
  • the filtration with each filter may be performed only once or twice or more.
  • filters having different pore diameters may be combined within the above-mentioned range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
  • the film of the present invention is a film obtained from the above-mentioned composition of the present invention.
  • the film of the present invention can be preferably used as an infrared transmission filter.
  • the film thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m, and even more preferably 0.5 to 10 ⁇ m.
  • the film of the present invention preferably has the spectral characteristics of any of the following aspects (1) to (12).
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the minimum value of the transmittance in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
  • the film of the present invention can be produced through a step of applying the curable composition of the present invention.
  • the curable composition is applied onto a support.
  • the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass.
  • An organic film, an inorganic film, or the like may be formed on these substrates.
  • the material of the organic film include the resin described in the section of the curable composition described above.
  • a substrate made of resin can also be used as the support.
  • the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like.
  • the support may be formed with a black matrix that separates each pixel.
  • the support may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.
  • the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the curable composition has good coatability.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • a known method can be used as a method for applying the curable composition.
  • a dropping method drop casting
  • a slit coating method for example, a spray method; a roll coating method; a rotary coating method (spin coating method); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
  • Inkjet for example, on-demand method, piezo method, thermal method
  • ejection system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Various printing methods transfer method using a mold or the like; nano-imprint method and the like.
  • the method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, the application by the spin coating method is preferably performed at a rotation speed of 1000 to 2000 rpm.
  • the curable composition layer formed by applying the curable composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process.
  • the prebaking 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, or 80 ° C. or higher.
  • the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
  • the film manufacturing method further includes a step of forming a pattern.
  • the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable.
  • the film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern.
  • the process of forming the pattern will be described in detail.
  • the pattern forming method in the photolithography method includes a step of exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern (exposure step) and a curable composition of an unexposed portion. It is preferable to include a step of developing and removing the layer to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
  • the curable composition layer is exposed in a pattern.
  • a pattern exposure can be performed by exposing the curable composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like.
  • the exposed portion can be cured.
  • radiation (light) that can be used for exposure include g-line and i-line.
  • light having a wavelength of 300 nm or less preferably light having a wavelength of 180 to 300 nm
  • Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable.
  • pulse exposure is an exposure method of a method of repeatedly irradiating and pausing light in a cycle of a short time (for example, a millisecond level or less).
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2, most preferably 0.08 ⁇ 0.5J / cm 2 ..
  • the oxygen concentration at the time of exposure can be appropriately selected. For example, it may be exposed in the atmosphere, or it may be exposed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic), and the oxygen concentration is high. Exposure may be carried out in a high oxygen atmosphere exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be appropriately set and is preferably selected from the range of 1000 to 100,000 W / m 2. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the curable composition layer in the unexposed portion of the curable composition layer after exposure is developed and removed to form a pattern.
  • Development and removal of the curable composition layer in the unexposed portion can be performed using a developing solution.
  • the curable composition layer of the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains on the support.
  • the temperature of the developing solution is preferably, for example, 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
  • Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
  • the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic substances.
  • alkaline compounds examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable.
  • the developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times.
  • the rinsing is performed by supplying the rinsing liquid to the developed curable composition layer while rotating the support on which the developed curable composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center to the peripheral edge of the support.
  • Additional exposure treatment and post-baking are post-development curing treatments to complete the curing.
  • the heating temperature in the post-baking is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to meet the above conditions. ..
  • the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • the curable composition layer formed by applying the curable composition of the present invention on a support is cured to form a cured product layer, and then on the cured product layer.
  • a patterned resist layer is formed, and then the cured product layer is dry-etched with an etching gas using the patterned resist layer as a mask.
  • the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.
  • the infrared transmission filter of the present invention has the above-mentioned film of the present invention.
  • the infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic colorant.
  • the color filter can be produced by using a coloring composition containing a chromatic colorant.
  • the infrared transmission filter of the present invention has pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless.
  • the solid-state image sensor of the present invention includes the above-mentioned film of the present invention.
  • the configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
  • a transfer electrode formed of a plurality of photodiodes forming the light receiving area of the solid-state image sensor and polysilicon or the like is provided, and from tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode.
  • the present invention has a light-shielding film to be formed, a device protective film formed of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and a photodiode light receiving portion, and the present invention is provided on the device protective film. It is a configuration having a membrane in.
  • a configuration having a condensing means for example, a microlens or the like; the same applies hereinafter
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall in this case preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.
  • the infrared sensor of the present invention includes the above-mentioned film of the present invention.
  • the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
  • an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.
  • reference numeral 110 is a solid-state image sensor.
  • the image pickup region provided on the solid-state image sensor 110 includes an infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the infrared cut filter 111.
  • a microlens 115 is arranged on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
  • the flattening layer 116 is formed so as to cover the microlens 115.
  • the infrared cut filter 111 is a filter that transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm) and shields light in the infrared region.
  • the color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be referred to, and this content is incorporated in the present specification.
  • the infrared transmission filter 114 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength.
  • an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116.
  • Other infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. These details include those mentioned above. Further, as another infrared cut filter, a dual bandpass filter may be used.
  • the color filter 112 is provided on the incident light h ⁇ side of the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to cut infrared rays.
  • the filter 111 may be provided on the incident light h ⁇ side of the color filter 112.
  • the infrared cut filter 111 and the color filter 112 are laminated adjacent to each other, but both filters do not necessarily have to be adjacent to each other, and another layer is provided between them. Is also good.
  • another infrared transmission filter having a spectral characteristic different from that of the infrared transmission filter 114 may be further provided.
  • the film of the present invention can also be used in an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
  • an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
  • an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
  • an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
  • electroluminescence (organic EL) display device for details on the definition of display devices and the details of each display device, see, for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)” (Issued in the first year) ”and so on.
  • the liquid crystal display device is described in, for example, “Next
  • the image display device may be an image display device having a white organic EL element as the display element.
  • the white organic EL element preferably has a tandem structure.
  • Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like.
  • the spectrum of white light emitted by the organic EL device preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm-700 nm).
  • ⁇ Measurement of maximum absorption wavelength of quantum dots For the measurement of the maximum absorption wavelength of the quantum dots, a toluene solution of 10 mg / mL of the quantum dots was prepared, and the absorbance of this solution was measured using an ultraviolet-visible-near-infrared spectrophotometer.
  • Quantum dot dispersion liquid [Quantum dot dispersion having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm]
  • QD-900 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.2 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 900 nm.
  • QD-1000 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.5 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1000 nm.
  • QD-1100 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.0 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1100 nm.
  • QD-1200 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.5 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1200 nm.
  • QD-1300 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.0 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1300 nm.
  • QD-1400 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.5 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1400 nm.
  • QD-1500 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.0 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1500 nm.
  • QD-1600 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.5 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1600 nm.
  • QD-1700 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 7.0 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1700 nm.
  • QD-1800 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.0 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1800 nm.
  • QD-1900 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.5 nm.
  • the maximum absorption wavelength of the PbS quantum dots was 1900 nm.
  • QD-2000 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 9.0 nm.
  • the maximum absorption wavelength of PbS quantum dots was 2000 nm.
  • QD-450 PbS quantum dot dispersion liquid (PbS quantum dot concentration 10% by mass) in which oleic acid is coordinated as a ligand on the surface of perovskite (CsPb (Cl / Br) 3) quantum dots with an average primary particle diameter of 7 nm. solution).
  • the maximum absorption wavelength of perovskite quantum dots was 450 nm.
  • C-1 A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
  • C-2 A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
  • I-1 Irgacure OXE01 (manufactured by BASF)
  • I-2 Compound with the following structure
  • I-3 Omnirad 907 (manufactured by IGM Resins BV)
  • Each curable composition was spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate. Place the obtained film on a piece of paper on which characters (character "A") with a font size of 9 to 20 points (pt) are written, observe the characters from above the film, and visually identify the characters. The visible shading property was evaluated by. In addition, the spectrum of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer to evaluate the infrared transparency.
  • Unidentifiable 3 Characters on the back side of the film can be identified when the font size of the characters is 15 pt, but characters on the back side of the film cannot be identified when the font size of the characters is 10 pt 2: Membrane when the font size of the characters is 10 pt Characters on the back side can be identified, but characters on the back side of the film cannot be identified when the font size of the characters is 9pt 1: Characters on the back side of the film can be identified even if the font size of the characters is 9pt.
  • Transmittance at 2200 nm is 70% or more 4: Transmittance at 2200 nm is 65% or more and less than 70% 3: Transmittance at 2200 nm is 60% or more and less than 65% 2: Transmittance at 2200 nm is 50% or more and less than 60% 1 : Transmittance at 2200 nm is 0% or more and less than 50%
  • the curable composition of the example had high visible light-shielding property and excellent infrared transparency. Further, the same effect can be obtained by mixing the solvent S-1 and the solvent S-2. Further, the curable compositions of Examples 1 to 54 were spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate.
  • the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured, respectively, and the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured.
  • the ratio A / B minimum value of absorbance A in the wavelength range of 400 to 650 nm / absorbance B in the wavelength range of 2200 nm
  • the film obtained by using the curable compositions of Examples 1, 14, 15, 28 to 36, 38, 40 to 42, 53 and 54 shields light having a wavelength of 400 to 1000 nm and has a wavelength of 1100 nm or more. It was intended to transmit light of the same wavelength. Further, the film obtained by using the curable compositions of Examples 2, 12, 16 and 43 shields light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more. Further, the film obtained by using the curable compositions of Examples 3, 17, and 44 shields light having a wavelength of 400 to 1200 nm and transmits light having a wavelength of 1300 nm or more.
  • the films obtained by using the curable compositions of Examples 4, 18 and 45 shielded light having a wavelength of 400 to 1300 nm and transmitted light having a wavelength of 1400 nm or more. Further, the film obtained by using the curable composition of Examples 5, 13, 19, 26, 27, 37, 39, 46 blocks light having a wavelength of 400 to 1400 nm, and light having a wavelength of 1500 nm or more. Was to be transmitted. Further, the film obtained by using the curable compositions of Examples 6, 20 and 47 shields light having a wavelength of 400 to 1500 nm and transmits light having a wavelength of 1600 nm or more.
  • the film obtained by using the curable compositions of Examples 7, 21, and 48 shields light having a wavelength of 400 to 1600 nm and transmits light having a wavelength of 1700 nm or more. Further, the film obtained by using the curable compositions of Examples 8, 22, and 49 shields light having a wavelength of 400 to 1700 nm and transmits light having a wavelength of 1800 nm or more. Further, the film obtained by using the curable compositions of Examples 9, 23 and 50 shields light having a wavelength of 400 to 1800 nm and transmits light having a wavelength of 1900 nm or more.
  • the film obtained by using the curable compositions of Examples 10, 24 and 51 shields light having a wavelength of 400 to 1900 nm and transmits light having a wavelength of 2000 nm or more. Further, the films obtained by using the curable compositions of Examples 11, 25 and 52 shielded light having a wavelength of 400 to 2000 nm and transmitted light having a wavelength of 2100 nm or more.
  • 110 Solid-state image sensor
  • 111 Infrared cut filter
  • 112 Color filter
  • 114 Infrared transmission filter
  • 115 Microlens
  • 116 Flattening layer

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Abstract

L'invention fournit une nouvelle composition durcissable qui permet de former un film permettant la transmission de rayonnement infrarouge dans un état de faible bruit dérivé de la lumière visible. En outre, l'invention fournit un film, un filtre de transmission de rayonnement infrarouge, un élément d'imagerie à semi-conducteurs et un capteur de rayonnement infrarouge. La composition durcissable de l'invention contient des points quantiques présentant une longueur d'onde d'absorption maximale dans une plage de ７００ à ２０００ｎｍ de longueur d'onde, et un composé durcissable. La teneur en points quantiques dans la matière solide totale de la composition durcissable, est supérieure ou égale à 5% en masse.
PCT/JP2021/003657 2020-02-26 2021-02-02 Composition durcissable, film, filtre de transmission de rayonnement infrarouge, élément d'imagerie à semi-conducteurs, et capteur de rayonnement infrarouge WO2021171929A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2023120215A1 (fr) * 2021-12-24 2023-06-29 住友化学株式会社 Composition, film et dispositif d'affichage

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JP2014058036A (ja) * 2012-09-17 2014-04-03 Boeing Co フッ素化ナノ粒子を含むｉｒ吸収コーティング
WO2014084353A1 (fr) * 2012-11-30 2014-06-05 住友金属鉱山株式会社 Filtre d'absorption infrarouge proche et élément de capture d'images
WO2019054281A1 (fr) * 2017-09-15 2019-03-21 富士フイルム株式会社 Composition, film, stratifié, filtre de transmission infrarouge, dispositif d'imagerie à semi-conducteurs et capteur infrarouge
CN110784312A (zh) * 2019-09-25 2020-02-11 宁波大学 一种puf器件的制备方法及其密钥生成方法
WO2020059509A1 (fr) * 2018-09-20 2020-03-26 富士フイルム株式会社 Composition durcissable, film durci, filtre de transmission infrarouge, stratifié, élément d'imagerie à l'état solide, capteur, et procédé de formation de motif

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JP2017147324A (ja) * 2016-02-17 2017-08-24 日本電気株式会社 赤外線検出器およびその製造方法
JP2018100959A (ja) * 2016-12-16 2018-06-28 シャープ株式会社 検出器、ならびに、検出器の校正方法、補正方法、検出装置

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Publication number Priority date Publication date Assignee Title
JP2014058036A (ja) * 2012-09-17 2014-04-03 Boeing Co フッ素化ナノ粒子を含むｉｒ吸収コーティング
WO2014084353A1 (fr) * 2012-11-30 2014-06-05 住友金属鉱山株式会社 Filtre d'absorption infrarouge proche et élément de capture d'images
WO2019054281A1 (fr) * 2017-09-15 2019-03-21 富士フイルム株式会社 Composition, film, stratifié, filtre de transmission infrarouge, dispositif d'imagerie à semi-conducteurs et capteur infrarouge
WO2020059509A1 (fr) * 2018-09-20 2020-03-26 富士フイルム株式会社 Composition durcissable, film durci, filtre de transmission infrarouge, stratifié, élément d'imagerie à l'état solide, capteur, et procédé de formation de motif
CN110784312A (zh) * 2019-09-25 2020-02-11 宁波大学 一种puf器件的制备方法及其密钥生成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120215A1 (fr) * 2021-12-24 2023-06-29 住友化学株式会社 Composition, film et dispositif d'affichage

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