WO2018056127A1 - 近赤外線吸収有機顔料、顔料分散液、硬化性組成物、膜、近赤外線カットフィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ - Google Patents

近赤外線吸収有機顔料、顔料分散液、硬化性組成物、膜、近赤外線カットフィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ Download PDF

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WO2018056127A1
WO2018056127A1 PCT/JP2017/032947 JP2017032947W WO2018056127A1 WO 2018056127 A1 WO2018056127 A1 WO 2018056127A1 JP 2017032947 W JP2017032947 W JP 2017032947W WO 2018056127 A1 WO2018056127 A1 WO 2018056127A1
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group
infrared absorbing
organic pigment
absorbing organic
infrared
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PCT/JP2017/032947
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English (en)
French (fr)
Japanese (ja)
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和敬 高橋
恭平 荒山
拓也 鶴田
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富士フイルム株式会社
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Priority to JP2018540991A priority Critical patent/JPWO2018056127A1/ja
Publication of WO2018056127A1 publication Critical patent/WO2018056127A1/ja

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00Other synthetic dyes of known constitution
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details

Definitions

  • the present invention relates to a near-infrared absorbing organic pigment, a pigment dispersion, a curable composition, a film, a near-infrared cut filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor.
  • Video cameras, digital still cameras, mobile phones with camera functions, etc. use CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor), which are solid-state imaging devices for color images. Since these solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in their light receiving portions, visual sensitivity correction may be performed using a near-infrared cut filter.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • a method for producing a near infrared cut filter using a curable composition containing a near infrared absorbent such as a near infrared absorbing organic pigment is known in order to enhance infrared shielding properties (for example, Patent Documents 1 and 2). .
  • Near-infrared absorbers such as near-infrared absorbing organic pigments are required to have excellent infrared shielding properties and excellent visible transparency. Moreover, when manufacturing a near-infrared cut filter etc. using the curable composition containing a near-infrared absorption organic pigment etc., it may heat for drying and hardening. However, when the near-infrared absorbing organic pigment has low heat resistance, coloring may occur due to heating, and the visible transparency may deteriorate.
  • an object of the present invention is to provide a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance. Another object of the present invention is to provide a pigment dispersion, a curable composition, a film, a near infrared cut filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor.
  • the present invention provides the following.
  • ⁇ 1> The powder X-ray diffraction spectrum has a diffraction intensity peak in the region where the diffraction angle 2 ⁇ is 5 to 12 °, and the full width at half maximum of the peak having the highest diffraction intensity in the above region is 0.3 to 0.6.
  • ⁇ 2> The near-infrared absorbing organic pigment according to ⁇ 1>, wherein the full width at half maximum is 0.3 to 0.45 °.
  • ⁇ 3> The near-infrared absorbing organic pigment according to ⁇ 1> or ⁇ 2>, wherein the average primary particle diameter of the near-infrared absorbing organic pigment is 10 to 100 nm.
  • ⁇ 4> The near-infrared absorbing organic pigment according to ⁇ 1> or ⁇ 2>, wherein the near-infrared absorbing organic pigment has an average primary particle size of 20 to 45 nm.
  • ⁇ 5> The near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 4>, wherein the variation coefficient of the primary particle diameter of the near-infrared absorbing organic pigment is 20 to 35%.
  • ⁇ 6> The near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 5>, wherein the near-infrared absorbing organic pigment has an average long / short side ratio of 0.5 to 0.9.
  • ⁇ 7> The near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 6>, wherein the variation coefficient of the long-short side ratio of the near-infrared absorbing organic pigment is 10 to 30%.
  • ⁇ 9> The near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 8>, wherein the near-infrared absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squarylium compound.
  • ⁇ 10> A pigment dispersion containing the near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 9>, a resin, and a solvent.
  • ⁇ 12> A curable composition comprising the near-infrared absorbing organic pigment according to any one of ⁇ 1> to ⁇ 9>, a resin, a curable compound, and a solvent.
  • ⁇ 13> A film using the curable composition according to ⁇ 12>.
  • ⁇ 14> A near-infrared cut filter having the film according to ⁇ 13>.
  • ⁇ 15> A laminate having the film according to ⁇ 13> and a color filter containing a chromatic colorant.
  • ⁇ 16> A solid-state imaging device having the film according to ⁇ 13>.
  • ⁇ 17> An image display device having the film according to ⁇ 13>.
  • ⁇ 18> An infrared sensor having the film according to ⁇ 13>.
  • the present invention it is possible to provide a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance.
  • a pigment dispersion it has become possible to provide a pigment dispersion, a curable composition, a film, a near-infrared cut filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor.
  • is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic 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 electron beams and ion beams.
  • the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth) acrylate” represents both and / or acrylate and methacrylate
  • (meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
  • Acryloyl represents both and / or acryloyl and methacryloyl.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID (inner diameter) ⁇ 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
  • near-infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
  • the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the pigment means a compound that is difficult to dissolve in a specific solvent.
  • the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
  • the near-infrared absorbing organic pigment of the present invention has a diffraction intensity peak in the region where the diffraction angle 2 ⁇ is 5 to 12 ° in the powder X-ray diffraction spectrum, and the full width at half maximum of the peak having the highest diffraction intensity in the above region is It is 0.3 to 0.6 °.
  • the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment has a diffraction intensity peak in the region where the diffraction angle 2 ⁇ is 5 to 12 °, and the diffraction intensity in the region described above. It has been found that a near-infrared absorbing organic pigment having a maximum full width at half maximum of 0.3 to 0.6 ° is excellent in visible transparency and heat resistance.
  • the full width at half maximum of the peak with the highest diffraction intensity is 0.3 to 0.6 °, so that the near-infrared absorbing organic pigment crystallite has an appropriate size, and the scattering is On the other hand, the proportion of pigment molecules forming aggregates is increased, and as a result, it is assumed that visible transparency and heat resistance can be improved.
  • the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment can be measured by the method described in Examples described later.
  • the peak having the highest diffraction intensity is preferably in the region where the diffraction angle 2 ⁇ is 6 to 10 °, more preferably in the region of 6 to 9 °. More preferably, it is in the range of 5 to 8.5 °. According to this aspect, visible transparency and heat resistance can be further improved.
  • the full width at half maximum of the peak having the highest diffraction intensity is preferably 0.3 to 0.45 °. According to this embodiment, visible transparency and heat resistance are particularly good.
  • y is the intensity
  • A is the peak height
  • x is 2 ⁇
  • x0 is the peak position
  • w is the peak width (half width at half maximum)
  • h is the baseline.
  • the average primary particle diameter of the near infrared absorbing organic pigment of the present invention is preferably 10 to 100 nm.
  • the lower limit is preferably 15 nm or more, more preferably 20 nm or more, further preferably 25 nm or more, and particularly preferably 30 nm or more.
  • the upper limit is preferably 90 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, and particularly preferably 45 nm or less.
  • the average primary particle diameter of the near-infrared absorbing organic pigment is preferably 20 to 45 nm, and particularly preferably 30 to 45 nm. Visible transparency can be further improved by setting the average primary particle diameter of the near-infrared absorbing organic pigment to 100 nm or less.
  • the effect that a dispersion stability improves by the average primary particle diameter of a near-infrared absorption organic pigment being 10 nm or more is acquired.
  • the average primary particle diameter of the near-infrared absorbing organic pigment decreases, the heat resistance tends to decrease, but the near-infrared absorbing organic pigment having the above-mentioned diffraction characteristics has a small average primary particle diameter. It has excellent heat resistance.
  • the variation coefficient of the primary particle size of the near infrared absorbing organic pigment of the present invention is preferably 20 to 35%.
  • the lower limit is preferably 21% or more, and more preferably 22% or more.
  • the upper limit is preferably 33% or less, more preferably 30% or less, still more preferably 29% or less, and even more preferably 28% or less. If the variation coefficient of the primary particle diameter of the near-infrared absorbing organic pigment is within the above range, the visible transparency can be further improved.
  • the coefficient of variation of the primary particle diameter of the near infrared absorbing organic pigment is defined by the following formula.
  • Coefficient of variation of primary particle diameter of near-infrared absorbing organic pigment (standard deviation of primary particle diameter of near-infrared absorbing organic pigment / arithmetic average value of primary particle diameter of near-infrared absorbing organic pigment) ⁇ 100
  • the average long / short side ratio of the near-infrared absorbing organic pigment of the present invention is preferably 0.5 to 0.9.
  • the lower limit is preferably 0.53 or more, and more preferably 0.56 or more.
  • the upper limit is preferably 0.8 or less, and more preferably 0.7 or less. If the average long-short side ratio of the near-infrared absorbing organic pigment is within the above range, the effect of improving heat resistance can be expected.
  • the coefficient of variation of the long / short side ratio of the near infrared absorbing organic pigment of the present invention is preferably 10 to 30%.
  • the lower limit is preferably 13% or more, and more preferably 16% or more.
  • the upper limit is preferably 28% or less, and more preferably 26% or less. If the variation coefficient of the long-short side ratio of the near-infrared absorbing organic pigment is within the above range, an effect of improving the visible transparency can be expected.
  • the coefficient of variation of the long / short side ratio of the near infrared absorbing organic pigment is defined by the following equation.
  • Variation coefficient of long-short side ratio of near-infrared absorbing organic pigment (standard deviation of long-short side ratio of near-infrared absorbing organic pigment / arithmetic average value of long-short side ratio of near-infrared absorbing organic pigment) ⁇ 100
  • the primary particle diameter and the long / short side ratio of the near-infrared absorbing organic pigment can be determined from a photograph obtained by observing the primary particles of the near-infrared absorbing organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the near-infrared absorbing organic pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle size of the near-infrared absorbing organic pigment. Further, the ratio of the short side to the long side (short side / long side) of the primary particle is obtained from the projected photograph, and the long / short side ratio is calculated.
  • the average primary particle diameter and average long-short side ratio in this invention be an arithmetic mean value of the primary particle diameter and long-short side ratio about the primary particle of 400 near-infrared absorption organic pigments.
  • the longest diameter of the primary particles is called the long side, and the shortest diameter is called the short side. That is, in the case of an ellipse, the long axis is the long side and the short axis is the short side.
  • grains of a near-infrared absorption organic pigment mean the independent particle
  • the value of crystallinity represented by the following formula of the near-infrared absorbing organic pigment is preferably 0.9 to 0.99, more preferably 0.91 to 0.98, More preferably, it is .93 to 0.96. If the value of crystallinity is in the above range, the heat resistance can be further improved.
  • Crystallinity [Ic / (Ia + Ic)]
  • Ic is a region where the diffraction angle 2 ⁇ is 15 ° or more, and is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum
  • Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
  • the peak derived from the crystal in the present invention means a sharp peak having a full width at half maximum of 1 ° or less in the peak of diffraction intensity.
  • the peak derived from amorphous means a peak whose full width at half maximum exceeds 3 ° in the peak of diffraction intensity.
  • the values of Ic and Ia are such that the diffraction intensity in the region where the diffraction angle 2 ⁇ of the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment is 5 to 15 ° is the lowest, and 25 to 35 °. This is a value calculated using a spectrum correction value obtained by subtracting the baseline value from the measured spectrum value of the powder X-ray diffraction spectrum, with the straight line connecting the lowest diffraction intensity in the region as the baseline.
  • the type of the near-infrared absorbing organic pigment of the present invention is not particularly limited as long as it is an organic pigment having a maximum absorption wavelength in the near-infrared region (preferably 700 to 1000 nm).
  • the organic pigment is a pigment composed of an organic compound.
  • the near-infrared absorbing organic pigment of the present invention is preferably at least one selected from a pyrrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound, and a pyrrolopyrrole compound, a squarylium compound and a cyanine compound It is more preferable that it is at least one selected from the group consisting of pyrrolopyrrole compounds and squarylium compounds, and it is particularly preferable that they are pyrrolopyrrole compounds. Particularly in the case of a pyrrolopyrrole compound, visible transparency and heat resistance can be improved more effectively.
  • the pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
  • R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R 2 and R 3 are R 4 may be bonded to each other to form a ring
  • each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 4A R 4B , or a metal atom
  • R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded
  • R 4A and R 4B each independently represent a substituent.
  • R 1a and R 1b each independently represents an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
  • the alkyl group represented by R 1a and R 1b preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • the number of carbon atoms of the aryl group represented by R 1a and R 1b is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12.
  • the number of carbon atoms constituting the heteroaryl group represented by R 1a and R 1b is preferably 1 to 30, and more preferably 1 to 12.
  • heteroaryl group As a kind of hetero atom which comprises heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2.
  • the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the alkyl group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. It preferably has a substituent. Examples of the substituent include the groups described for the substituent T described later.
  • the alkoxy group is preferably an alkoxy group having a branched alkyl group.
  • the group represented by R 1a or R 1b is preferably an aryl group having an alkoxy group having a branched alkyl group as a substituent or an aryl group having a hydroxy group as a substituent.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
  • R 2 and R 3 each independently represents a hydrogen atom or a substituent.
  • R 2 and R 3 may be bonded to form a ring.
  • At least one of R 2 and R 3 is preferably an electron withdrawing group.
  • R 2 and R 3 preferably each independently represent a cyano group or a heteroaryl group.
  • substituents include those described in JP-A 2009-263614, paragraphs 0020 to 0022. The above contents are incorporated in the present specification.
  • substituent T examples of the substituent T.
  • Alkyl group (preferably 1 to 30 carbon atoms), alkenyl group (preferably 2 to 30 carbon atoms), alkynyl group (preferably 2 to 30 carbon atoms), aryl group (preferably 6 to 30 carbon atoms), amino group (Preferably 0 to 30 carbon atoms), alkoxy group (preferably 1 to 30 carbon atoms), aryloxy group (preferably 6 to 30 carbon atoms), heteroaryloxy group (preferably 1 to 30 carbon atoms), acyl A group (preferably having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), an acyloxy group (preferably having 2 to 30 carbon atoms), Acylamino group (preferably having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms), aryloxycarbonylamino group Preferably 7 to 30 carbon atoms
  • At least one of R 2 and R 3 is preferably an electron withdrawing group.
  • a substituent having a positive Hammett's substituent constant ⁇ value acts as an electron-attracting group.
  • the substituent constant obtained by Hammett's rule includes a ⁇ p value and a ⁇ m value. These values can be found in many common books.
  • substituents having Hammett's substituent constant ⁇ value of 0.2 or more can be exemplified as electron-attracting groups.
  • the ⁇ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more.
  • the upper limit is not particularly limited, but is preferably 0.80 or less.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • Hammett's substituent constant ⁇ value for example, paragraph numbers 0017 to 0018 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated in the present specification.
  • R 2 and R 3 are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring).
  • the ring formed is preferably a merocyanine dye that is used as an acidic nucleus, and specific examples thereof can include, for example, paragraphs 0019 to 0021 of JP 2011-68731 A, the contents of which are incorporated herein. It is.
  • R 2 represents an electron withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • R 4 represents an alkyl group, an aryl group or a heteroaryl group
  • the alkyl group, aryl group and heteroaryl group are the same as those described for R 1a and R 1b , and the preferred ranges are also the same.
  • R 4A and R 4B each independently represent a substituent.
  • substituent represented by R 4A and R 4B include the substituent T described above, and a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, and an alkyl group, an aryl group, or a hetero group is preferable.
  • An aryl group is more preferable, and an aryl group is particularly preferable.
  • —BR 4A R 4B Specific examples of the group represented by —BR 4A R 4B include a difluoroboron group, a diphenylboron group, a dibutylboron group, a dinaphthylboron group, and a catecholboron group. Of these, a diphenylboron group is particularly preferred.
  • R 4 represents a metal atom
  • examples of the metal atom include magnesium, aluminum, calcium, barium, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, and platinum, and aluminum, zinc, vanadium. Iron, copper, palladium, iridium and platinum are particularly preferred.
  • R 4 may be covalently bonded or coordinated to at least one of R 1a , R 1b and R 3 , and it is particularly preferable that R 4 is coordinated to R 3 .
  • R 4 is preferably a hydrogen atom or a group represented by —BR 4A R 4B (particularly a diphenylboron group).
  • the near-infrared absorbing organic pigment having the above-described characteristics can be produced by, for example, a method of adjusting the pulverizing conditions of the near-infrared absorbing organic pigment.
  • a method of adjusting the pulverizing conditions of the near-infrared absorbing organic pigment For example, the method of kneading
  • the near-infrared absorbing organic pigment is kneaded and polished so that the average primary particle diameter is in the range of 10 to 100 nm, and more preferably, the near-infrared absorbing organic pigment has an average primary particle diameter in the range of 20 to 45 nm. Kneading and polishing.
  • the water-soluble inorganic salt serves as an attritor and is kneaded with the near-infrared absorbing organic pigment to promote the miniaturization of the near-infrared absorbing organic pigment.
  • the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, sodium sulfate, aluminum sulfate, sodium hydrogen carbonate and the like, preferably sodium chloride and sodium sulfate. These water-soluble inorganic salts can be pulverized. These water-soluble inorganic salts can be used alone or in a mixture of two or more.
  • the average particle diameter D50 of the water-soluble inorganic salt is preferably 15 ⁇ m or more, and more preferably 18 ⁇ m or more.
  • the upper limit is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • Near-infrared-absorbing organic pigments are kneaded and polished using a chromatic organic pigment or a water-soluble inorganic salt that has a lower hardness and a smaller particle size than inorganic pigments.
  • the crystal structure of the near-infrared absorbing organic pigment may be changed to reduce the visible transparency, but the water-soluble inorganic salt having an appropriately large particle size (preferably having an average particle size of By using a water-soluble inorganic salt of 15 ⁇ m or more, crystallinity (crystallinity) can be appropriately adjusted while suppressing distortion of the crystal structure of the near-infrared absorbing organic pigment.
  • the near-infrared absorbing organic pigment can be refined (for example, the average primary particle size is 10 to 100 nm).
  • the amount of the water-soluble inorganic salt is preferably 2.5 to 20 times, more preferably 4 to 18 times, still more preferably 7 to 18 times the mass of the near infrared absorbing organic pigment.
  • the lower limit is particularly preferably 8 times or more, and most preferably 10 times or more.
  • the upper limit is particularly preferably 17 times or less, and most preferably 16 times or less.
  • the water-soluble organic solvent acts as a binder for the near-infrared absorbing organic pigment and the water-soluble inorganic salt.
  • the crystal growth and crystal transition of the near-infrared absorbing organic pigment can be suppressed.
  • the solubility of the water-soluble organic solvent in 100 g of water at 23 ° C. is preferably 20 g or more, more preferably 50 g or more, and further preferably 100 g or more. According to this aspect, the water-soluble inorganic salt can be efficiently washed with water.
  • the water-soluble organic solvent include alkylene glycols such as ethylene glycol and propylene glycol, condensates of alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, and polyethylene-propylene glycol, methoxyethanol, and polyethylene glycol.
  • alkylene glycols such as ethylene glycol and propylene glycol
  • condensates of alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, and polyethylene-propylene glycol, methoxyethanol, and polyethylene glycol.
  • Examples include (poly) alkylene glycol alkyl ethers such as monomethyl ether, glycerin, and the like, and because the mixture containing a near-infrared absorbing organic pigment, a water-soluble inorganic salt and a water-soluble organic solvent gives an appropriate hardness and viscosity.
  • Highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol, and polyethylene glycol are preferred.
  • One type of water-soluble organic solvent can be used alone, or a mixture of two or more types can be used.
  • the amount of the water-soluble organic solvent varies depending on the amount of the near-infrared absorbing organic pigment, the amount of the water-soluble inorganic salt, the kneading conditions (temperature, kneading speed, etc.), the characteristics of the kneader used, etc. It is preferably 0.10 to 0.35 times, more preferably 0.12 to 0.30 times, still more preferably 0.15 to 0.25 times the total mass of the pigment and the water-soluble inorganic salt. If the amount of the water-soluble organic solvent is within the above range, it is possible to give an appropriate hardness and stickiness to the mixture containing the near-infrared absorbing organic pigment, the water-soluble inorganic salt and the water-soluble organic solvent.
  • the kneader it is only necessary to have the ability to knead the above mixture, and a double-arm kneader, a flasher, a planetary mixer, or the like can be used.
  • a double-arm kneader having a strong shearing force is more preferable.
  • Kneading temperature (milling temperature) is set according to the temperature dependence and crystal transition of the crystal growth rate of the near infrared absorbing organic pigment. In general, the lower the temperature, the lower the crystal growth rate. On the other hand, the wettability of the water-soluble organic solvent to the pigment surface and the penetration rate of the water-soluble organic solvent into the pigment mass are faster as the temperature is higher.
  • the sizing of near-infrared absorbing organic pigments proceeds by a balance between both miniaturization and crystal growth. For example, 0 ° C. or higher is preferable, 10 ° C. or higher is more preferable, 20 ° C. or higher is further preferable, 30 ° C. or higher is even more preferable, and 40 ° C. or higher is even more preferable.
  • 50 ° C. or higher is particularly preferable because it is easy to produce a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance while adjusting the average primary particle diameter in the range of 10 to 100 nm.
  • the upper limit is preferably 120 ° C. or lower, and more preferably 100 ° C. or lower.
  • a water-soluble inorganic salt or a water-soluble organic solvent can be added in accordance with the progress of miniaturization and sizing of the near-infrared absorbing organic pigment. Further, the discharge and re-kneading of the pigment kneaded material is not limited to once, and may be performed a plurality of times.
  • crystal transition can be performed together with the miniaturization of the near-infrared absorbing organic pigment.
  • a pigment derivative or a surface treatment agent can be added for the purpose of miniaturizing the near-infrared absorbing organic pigment or controlling the crystal form.
  • the kneaded product after kneading and polishing is purified by a known purification method such as washing with water, acid, alkali or the like, so that a fine near-infrared absorbing organic pigment is isolated. It is preferable to isolate by performing a water washing treatment for the reason of reducing environmental load.
  • the near-infrared absorbing organic pigment containing water may be used as it is, or a water treatment may be performed by performing a drying treatment.
  • the drying method is not particularly limited, but it is preferably performed by hot air drying for the purpose of improving productivity.
  • the pigment dispersion of the present invention contains the above-described near-infrared absorbing organic pigment, a resin, and a solvent.
  • the viscosity (23 ° C.) of the pigment dispersion of the present invention is preferably 2 to 30 mPa ⁇ s.
  • the lower limit is preferably 3 mPa ⁇ s or more, and more preferably 4 mPa ⁇ s or more.
  • the upper limit is preferably 20 mPa ⁇ s or less, and more preferably 15 mPa ⁇ s or less.
  • the thixotropic property of the pigment dispersion of the present invention is low.
  • the thixotropic property can be expressed by an index of Ti value.
  • an index of Ti value For example, in the viscosity measured using an E-type viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.) when the rotational speeds are 20 rpm and 50 rpm, respectively, ⁇ (20 rpm) and ⁇ (50 rpm), ⁇ (20 rpm) / ⁇ Let the value of (50 rpm) be Ti value. The closer the Ti value is to 1, the lower the thixotropic property.
  • the Ti value at 23 ° C. is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, More preferably, it is -1.1.
  • the pigment dispersion of the present invention preferably has a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
  • the absorbance A550 / absorbance Amax which is the ratio of the absorbance A550 at a wavelength of 550 nm and the absorbance Amax at the maximum absorption wavelength, is preferably 0.002 to 0.040, and preferably 0.003 to 0.030. More preferred is 0.004 to 0.020.
  • the absorbance A400 / absorbance Amax which is the ratio between the absorbance A400 at a wavelength of 400 nm and the absorbance Amax at the maximum absorption wavelength, is preferably 0.005 to 0.150, more preferably 0.020 to 0.100. Preferably, it is 0.050 to 0.070.
  • the maximum absorption wavelength in the pigment dispersion of the present invention is more preferably in the range of 720 to 980 nm, and still more preferably in the range of 740 to 960 nm.
  • the pigment dispersion of the present invention contains the above-described near infrared absorbing organic pigment.
  • the content of the near-infrared absorbing organic pigment is preferably 30 to 99% by mass, more preferably 50 to 99% by mass, and 60 to 99% by mass with respect to the total solid content of the pigment dispersion. More preferably.
  • the dispersion of the present invention contains a solvent.
  • the solvent include organic solvents.
  • the organic solvent include the following organic solvents.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyalkyl acetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (Eg,
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol Examples thereof include monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
  • aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be better reduced for environmental reasons (for example, 50 mass ppm (parts per to the total amount of organic solvent)). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).
  • Organic solvents may be used alone or in combination of two or more.
  • a mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • 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 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry 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 size of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.
  • 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 60 to 92% by mass, more preferably 70 to 90% by mass, and further preferably 75 to 89% by mass with respect to the total amount of the pigment dispersion. Only one type of solvent may be used, or two or more types of solvents may be used. When two or more types of solvents are included, the total amount is preferably within the above range.
  • the pigment dispersion of the present invention contains a resin.
  • the resin is blended for the purpose of dispersing pigments and the like.
  • a resin used mainly for dispersing pigments is also referred to as a dispersant.
  • such use of the resin is an example, and the resin can be used for purposes other than such use.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
  • the resin used as the dispersant is preferably at least one selected from acidic resins, basic resins and amphoteric resins, and more preferably at least one selected from acidic resins and amphoteric resins.
  • the acidic resin means a resin having an acid group and having an acid value of 5 mgKOH / g or more and an amine value of less than 5 mgKOH / g.
  • the acidic resin preferably does not have a basic group.
  • As an acid group which acidic resin has, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable.
  • the acid value of the acidic resin is preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 100 mgKOH / g or less, and still more preferably 60 mgKOH / g or less.
  • the amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less.
  • the basic resin means a resin having a basic group and having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g. The basic resin preferably does not have an acid group.
  • an amino group is preferable.
  • the amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and still more preferably 5 to 100 mgKOH / g.
  • the amphoteric resin means a resin having an acid group and a basic group and having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • the acid group include those described above, and a carboxyl group is preferable.
  • an amino group is preferable.
  • the amphoteric resin preferably has an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • the acid value is more preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
  • the amine value is preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
  • the resin preferably contains a repeating unit having an acid group.
  • Resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the terminal-modified polymer include a polymer having a phosphate group at the terminal end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191.
  • examples thereof include a polymer having a sulfo group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994.
  • polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
  • the graft polymer include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like.
  • block polymer block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • a graft copolymer containing a repeating unit represented by any of the following formulas (11) to (14) can also be used.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent group
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent group
  • R 3 represents an alkylene group
  • R 4 represents a hydrogen atom or a monovalent group
  • n, m, p, and q are each independently an integer of 1 to 500 J and k each independently represents an integer of 2 to 8.
  • R 3 when p is 2 to 500, a plurality of R 3 may be the same or different from each other. In the formula (14), when q is 2 to 500, a plurality of R 3 are present. 5 and R 4 may be the same as or different from each other.
  • graft copolymer the description of paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
  • Specific examples of the graft copolymer include the following resins. Further, there are resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
  • an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can also be used.
  • the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain.
  • a resin having at least one basic nitrogen atom is preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • the oligoimine dispersant is represented by, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a formula (I-2a). Examples thereof include a resin containing a repeating unit.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
  • a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
  • R 8 and R 9 are the same groups as R 1 .
  • L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms).
  • an imino group preferably having a carbon number of 0 to 6
  • an ether group preferably having a carbon number of 0 to 6
  • a thioether group preferably having a carbonyl group, or a combination group thereof.
  • a single bond or —CR 5 R 6 —NR 7 — is preferable.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms).
  • R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • L a is a structural site to form a ring structure together with CR 8 CR 9 and N, be combined with the carbon atoms of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms preferable. More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed, and a structural part to form pyrrolidine is particularly preferable. This structural part may further have a substituent such as an alkyl group.
  • X represents a group having a functional group of pKa14 or less.
  • Y represents a side chain having 40 to 10,000 atoms.
  • the oligoimine dispersant further contains, as a copolymerization component, one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5). Also good. When the oligoimine dispersant contains such a repeating unit, the dispersion performance can be further improved.
  • R 1 , R 2 , R 8 , R 9 , L, La, a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
  • Ya represents a side chain having an anionic group having 40 to 10,000 atoms.
  • the repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.
  • oligoimine-based dispersant the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the oligoimine dispersant include the following. In addition, resins described in JP-A-2012-255128, paragraph numbers 0168 to 0174 can be used.
  • the resin is also available as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie).
  • pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
  • alkali-soluble resin etc. which are demonstrated by curable composition mentioned later can also be used for resin.
  • the content of the resin in the pigment dispersion of the present invention is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less.
  • the lower limit is more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more.
  • the pigment dispersion of the present invention preferably further contains a pigment derivative.
  • the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a group having a salt structure, or a phthalimidomethyl group, and the pigment derivative represented by the formula (B1) is preferable. .
  • P represents a dye structure
  • L represents a single bond or a linking group
  • X represents an acidic group, a basic group, a group having a salt structure, or a phthalimidomethyl group
  • m is an integer of 1 or more.
  • N represents an integer of 1 or more.
  • P represents a dye structure, and pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzoisoindole dye structure, thiazine indigo dye structure Azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye structure, benzimidazole dye structure and benzoxazole dye structure At least one selected from the group consisting of pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure and benzoimidazolone dye structure is more preferable. Pyrrole dye structure is particularly preferred.
  • L represents a single bond or a linking group.
  • the linking group is preferably a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. , May be unsubstituted or may further have a substituent. Specific examples include an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, —O—, —S—, —NR′—, —CO—, —SO 2 —, or a combination thereof.
  • R ′ represents a hydrogen atom, an alkyl group or an aryl group.
  • X represents an acidic group, a basic group, a group having a salt structure, or a phthalimidomethyl group.
  • the acidic group include a carboxyl group and a sulfo group.
  • the basic group an amino group is preferable, and a tertiary amino group is particularly preferable.
  • the group having a salt structure include the above-mentioned acidic group salts and basic group salts.
  • the atoms or atomic groups constituting the salt include metal atoms and tetrabutylammonium.
  • the metal atom an alkali metal atom or an alkaline earth metal atom is preferable.
  • the alkali metal atom include lithium, sodium, potassium and the like.
  • alkaline earth metal atoms include calcium and magnesium.
  • pigment derivative examples include the following compounds. Also, JP-A-56-118462, JP-A-63-264673, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, JP-A-3-153780. JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, JP-A-10-30063, JP-A-10-195326, International Publication WO2011 / 024896, Paragraph Nos. 0086 to 0098, International Publication WO2012 / 102399, Paragraph Nos. 0063 to 0094, etc., International Publication No.
  • WO2016 / 035695 Paragraph It is also possible to use the compound described in No. 0053, the contents of which are incorporated herein. Murrell.
  • the pigment derivative include the following compounds (B-1), (B-2), (B-3), (B-6), (B-15), (B-16), (B-18), (B-30), (B-61), and (B-62) are particularly preferred.
  • 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, and more preferably 30 parts by mass or less. If content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one type of pigment derivative may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range.
  • the pigment dispersion of the present invention can be prepared by mixing the aforementioned components.
  • the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent.
  • a pigment dispersion may be prepared by simultaneously dissolving or dispersing all components in a solvent.
  • the preparation of the pigment dispersion preferably includes a process for dispersing the pigment.
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion.
  • any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration.
  • fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • PP polypropylene
  • polypropylene including high density polypropylene
  • nylon are preferable.
  • the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is in the above range, fine foreign matters can be reliably removed. It is also preferable to use a fiber-shaped filter medium.
  • the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber.
  • filter cartridges of SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno Co., Ltd. may be mentioned.
  • filters for example, a first filter and a second filter
  • filtration with each filter may be performed only once or may be performed twice or more.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.) can do.
  • the second filter a filter formed of the same material as the first filter can be used.
  • the curable composition of this invention contains the near-infrared absorption organic pigment mentioned above, resin, a sclerosing
  • the curable composition of the present invention is also preferably a composition containing the above-described pigment dispersion and a curable compound.
  • the curable composition of the present invention may be a photocurable composition or a thermosetting composition. In the case of a photocurable composition, it is preferably a composition comprising a polymerizable compound (preferably a radical polymerizable compound) and a photopolymerization initiator (preferably a photo radical polymerization initiator).
  • the curable composition of this invention contains the near-infrared absorption organic pigment mentioned above.
  • the content of the near-infrared absorbing organic pigment is preferably 0.1 to 60% by mass with respect to the total solid content of the curable composition.
  • the lower limit is preferably 1% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the composition of the present invention may further contain a near-infrared absorbing compound (also referred to as other near-infrared absorbing compound) other than the above-described near-infrared absorbing organic pigment.
  • a near-infrared absorbing compound also referred to as other near-infrared absorbing compound
  • other near infrared absorbing compounds include dyes.
  • compound species include phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diiminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, and dibenzofuranone compounds. Is mentioned.
  • phthalocyanine compound naphthalocyanine compound, diiminium compound, and croconium compound
  • compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used, the contents of which are incorporated herein.
  • IRA868 manufactured by Exiton
  • IRG-068 manufactured by Nippon Kayaku Co., Ltd.
  • the like can also be used.
  • inorganic particles can also be used as other near infrared absorbing compounds.
  • the inorganic particles are preferably metal oxide particles or metal particles in terms of better infrared shielding properties.
  • the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped).
  • ITO indium tin oxide
  • ATO antimony tin oxide
  • ZnO zinc oxide
  • Al-doped zinc oxide Al-doped zinc oxide
  • F-doped fluorine-doped tin dioxide
  • SnO 2 niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, and the like.
  • the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles.
  • a tungsten oxide compound can be used as the inorganic fine particles.
  • the tungsten oxide compound is preferably cesium tungsten oxide.
  • paragraph No. 0080 of JP-A-2016-006476 can be referred to, the contents of which are incorporated herein.
  • the shape of the inorganic particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.
  • the average particle size of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less.
  • the average particle diameter of the inorganic particles is within such a range, the visible transparency is good.
  • the average particle size is preferably as small as possible.
  • the average particle size of the inorganic particles is usually 1 nm or more.
  • the content of the other near infrared absorbing compound is preferably 0.1 to 80 parts by mass with respect to 100 parts by mass of the near infrared absorbing organic pigment. 5 to 60 parts by mass is more preferable, and 10 to 40 parts by mass is further preferable.
  • the curable composition of the present invention can contain a chromatic colorant.
  • the chromatic colorant means a colorant other than the white colorant and the black colorant.
  • the chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.
  • the chromatic colorant may be a pigment or a dye.
  • the pigment is preferably an organic pigment.
  • C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 22
  • the dye is not particularly limited, and a known dye can be used.
  • the chemical structure includes pyrazole azo, anilino azo, triaryl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
  • the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the curable composition of the present invention.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the content of the chromatic colorant is preferably 10 to 1000 parts by mass and more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the near infrared absorbing organic pigment.
  • the total amount of the chromatic colorant and the near-infrared absorbing organic pigment is preferably 1 to 80% by mass with respect to the total solid content of the curable composition of the present invention.
  • the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the curable composition of the present invention can also contain a colorant that transmits infrared rays and blocks visible light (hereinafter also referred to as a colorant that blocks visible light).
  • the color material that blocks visible light is preferably a color material that absorbs light in the wavelength range from purple to red.
  • the color material that blocks visible light is preferably a color material that blocks light in the wavelength region of 450 to 650 nm.
  • the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm.
  • the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2).
  • the organic black colorant as a colorant that blocks visible light absorbs visible light but transmits at least part of infrared rays. Therefore, in the present invention, the organic black colorant as a colorant that blocks visible light does not include a black colorant that absorbs both visible light and infrared rays, such as carbon black and titanium black.
  • Examples of chromatic colorants include those described above.
  • Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
  • Examples of the bisbenzofuranone compounds include compounds described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
  • Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
  • Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-34664 and the like, and for example, “chromofine black A1103” manufactured by Dainichi Seika Co., Ltd. can be obtained.
  • the colorant that blocks visible light has, for example, an A / B that is a ratio of the minimum absorbance A in the wavelength range of 450 to 650 nm and the minimum absorbance B in the wavelength range of 900 to 1300 nm. It is preferable that it is 4.5 or more.
  • the above characteristics may be satisfied by one kind of material, or may be satisfied by a combination of a plurality of materials.
  • the organic black colorant may satisfy the above spectral characteristics.
  • the above-described spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
  • Examples of combinations of chromatic colorants in the case of forming black with a combination of two or more chromatic colorants include the following. (1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant and a red colorant. (2) An embodiment containing a yellow colorant, a blue colorant and a red colorant. (3) An embodiment containing a yellow colorant, a purple colorant and a red colorant. (4) An embodiment containing a yellow colorant and a purple colorant. (5) An embodiment containing a green colorant, a blue colorant, a purple colorant and a red colorant. (6) An embodiment containing a purple colorant and an orange colorant. (7) An embodiment containing a green colorant, a purple colorant and a red colorant. (8) An embodiment containing a green colorant and a red colorant.
  • ratio (mass ratio) of each colorant examples include the following.
  • the content of the color material that blocks visible light is preferably 30% by mass or less based on the total solid content of the curable composition. 20 mass% or less is more preferable, and 15 mass% or less is still more preferable.
  • the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
  • the curable composition of this invention can also be set as the aspect which does not contain the coloring material which shields visible light substantially.
  • the content of the color material that blocks visible light is preferably 0.005% by mass or less in the total solid content of the curable composition of the present invention, as it contains substantially no color material that blocks visible light. 0.001 mass% or less is still more preferable, and it is still more preferable not to contain the coloring material which shields visible light.
  • the curable composition of the present invention preferably contains a pigment derivative.
  • the pigment derivative include the pigment derivatives described in the above-described pigment dispersion.
  • 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, and more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range.
  • the curable composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing a pigment or the like in the curable composition and the purpose of a binder.
  • a resin used mainly for dispersing pigments is also called a dispersant.
  • such use of the resin is an example, and the resin can be used for purposes other than such use.
  • As resin
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
  • the resin examples include the resins described in the pigment dispersion described above. Also, (meth) acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, It is also preferable to use a resin such as a polyolefin resin, a cyclic olefin resin, a polyester resin, or a styrene resin. One of these resins may be used alone, or two or more thereof may be mixed and used.
  • the resin used in the present invention may have an acid group.
  • the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins. It can also be used as a dispersant.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000.
  • the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
  • alkali-soluble resin a polymer having a carboxyl group in the side chain is preferable.
  • Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and alkali-soluble resins such as novolac resins.
  • alkali-soluble resins such as novolac 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 hydroxyl 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, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used.
  • only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
  • the alkali-soluble resin includes a monomer component including 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 dimers”). It is also preferable to include a polymer obtained by polymerization.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP 2010-168539 A can be referred to.
  • the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl and the like An alkyl group substituted with an aryl group of
  • ether dimer for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • the resin having an acid group may contain a repeating unit derived from a 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 has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring.
  • n represents an integer of 1 to 15.
  • alkali-soluble resin examples include those described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding to US Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408. In paragraph Nos. 0076 to 0099, the contents of which are incorporated herein.
  • an alkali-soluble resin having a polymerizable group may be used as the alkali-soluble resin.
  • the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
  • the alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin having a polymerizable group in the side chain.
  • the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106 (KS resist 106).
  • the resin content is preferably 14 to 70% by mass with respect to the total solid content of the curable composition of the present invention.
  • the lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more.
  • the upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.
  • the content of the resin having an acid group is preferably 14 to 70% by mass with respect to the total solid content of the curable composition of the present invention.
  • the lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more.
  • the upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.
  • the content of the alkali-soluble resin is preferably 14 to 70% by mass with respect to the total solid content of the curable composition of the present invention.
  • the lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more.
  • the upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.
  • the curable composition of the present invention contains 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 applicability of the curable composition, but is preferably selected in consideration of applicability and safety of the curable composition.
  • the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. About these details, the organic solvent demonstrated with the pigment dispersion liquid mentioned above can be used.
  • organic solvent examples include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol.
  • Acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred.
  • the content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 25 to 75% by mass with respect to the total amount of the curable composition.
  • the curable composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are included, the total amount is preferably within the above range.
  • the curable composition of the present invention contains a curable compound.
  • a curable compound known compounds that can be cross-linked by radicals, acids, and heat can be used.
  • the curable compound include a polymerizable compound and a compound having an epoxy group.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound is preferably a radical polymerizable compound.
  • the content of the curable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the curable composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
  • One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, and an oligomer, but is preferably a monomer.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, and further preferably 250 or more.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of these compounds include those described in paragraph Nos.
  • Polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, Sartomer) (SR454, SR499, commercially available
  • oligomer types can also be used.
  • trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • Commercially available products of trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
  • M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.
  • a polymerizable compound having an acid group can also be used as the polymerizable compound.
  • the polymerizable compound having an acid group By using the polymerizable compound having an acid group, the unexposed portion of the polymerizable compound is easily removed during development, and the generation of development residues can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable.
  • Examples of commercially available polymerizable compounds having an acid group include Aronix M-510 and M-520 (manufactured by Toagosei Co., Ltd.).
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, it is excellent in curability.
  • a polymerizable compound having a caprolactone structure can also be used as the polymerizable compound.
  • the polymeric compound which has an alkyleneoxy group can also be used as a polymeric compound.
  • the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. More preferred are hexafunctional (meth) acrylate compounds.
  • Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 which is an acrylate.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58.
  • Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
  • urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types of polymeric compounds together, it is preferable that a total amount becomes the said range.
  • the curable composition of this invention can contain the compound which has an epoxy group as a sclerosing
  • a compound having two or more epoxy groups in one molecule is preferable.
  • the compound having an epoxy group is preferably a compound having 2 to 100 epoxy groups.
  • the upper limit of the epoxy group can be, for example, 10 or less, or 5 or less.
  • the compound having an epoxy group may be either a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
  • the content of the compound having an epoxy group is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • the compound which has an epoxy group may be single 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the curable composition of the present invention can contain a photopolymerization initiator.
  • the curable composition of the present invention contains a polymerizable compound, it preferably contains a photopolymerization initiator.
  • a photoinitiator There is no restriction
  • a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
  • the halogenated hydrocarbon compound having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc.
  • Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity.
  • Compounds selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.
  • ⁇ -hydroxyketone compounds As the photopolymerization initiator, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and acylphosphine compounds can also be suitably used.
  • ⁇ -aminoketone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898 can also be used.
  • ⁇ -hydroxyketone compound IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF) can be used.
  • ⁇ -aminoketone compound IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF) can be used.
  • ⁇ -aminoketone compound compounds described in JP2009-191179A can be used.
  • acylphosphine compound commercially available products such as IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF) can be used.
  • the photopolymerization initiator is preferably an oxime compound.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. The description is given in the publication.
  • Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979, pp. 1653-1660) J. MoI. C.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 manufactured by ADEKA Corporation
  • Adeka Arcles NCI-930 manufactured by ADEKA Corporation
  • Adekaoptomer N -1919 manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP2012-14052A
  • oxime compounds other than those described above compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
  • the oxime compound a compound represented by the following formula (OX-1) can be preferably used.
  • the oxime compound may be an oxime compound in which the oxime N—O bond is an (E) isomer, or the oxime N—O bond may be a (Z) oxime compound. Z) It may be a mixture with the body.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the description of paragraph numbers 0276 to 0304 in JP 2013-029760 A can be referred to, and the contents thereof are incorporated in this specification.
  • an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Compound (C-3). This content is incorporated herein.
  • an oxime compound having a nitro group can be used as a photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
  • oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having an absorption maximum in a wavelength region of 350 nm to 500 nm, and more preferably a compound having an absorption maximum in a wavelength region of 360 nm to 480 nm.
  • the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000 from the viewpoint of sensitivity, and 5,000 to 200,000. 000 is particularly preferred.
  • the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • the photopolymerization initiator preferably contains an oxime compound and an ⁇ -aminoketone compound. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed.
  • the oxime compound and the ⁇ -aminoketone compound are used in combination, 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 photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the curable composition. If the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formability can be obtained.
  • the curable composition of this invention may contain only 1 type of photoinitiators, and may contain 2 or more types. When two or more types of photopolymerization initiators are included, the total amount is preferably within the above range.
  • the curable composition of the present invention can contain a chain transfer agent. According to this aspect, curing of the film surface (pattern surface) can be promoted by exposure. For this reason, it is possible to suppress a decrease in film thickness during exposure, and it is easy to form a pattern with more excellent rectangularity.
  • chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, with thiol compounds being preferred.
  • the thiol compound is preferably a compound having 2 or more (preferably 2 to 8, more preferably 3 to 6) thiol groups in the molecule.
  • thiol compound examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other thiol compounds having a heterocyclic ring, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) And aliphatic thiol compounds such as butyryloxy) butane. Moreover, it is also preferable to use the following compound.
  • chain transfer agents include PEMP (manufactured by Nagase Sangyo Co., Ltd., thiol compound), Sunseller M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), Karenz MT BD1 (Showa Denko Co., Ltd.) And thiol compounds).
  • the content of the chain transfer agent is preferably 0.2 to 5.0 mass%, more preferably 0.4 to 3.0 mass%, based on the total solid content of the curable composition.
  • the content of the chain transfer agent is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound.
  • the curable composition of the present invention can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition. Further, the content of the polymerization inhibitor is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polymerizable compound.
  • the upper limit is preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass or less.
  • the lower limit is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more.
  • the curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds of polymerization inhibitors are included, the total amount is preferably within the above range.
  • the curable composition of this invention contains a ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds and diketone compounds.
  • the conjugated diene compound include a compound represented by the formula (UV-1).
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 May be the same as or different from each other, but do not represent a hydrogen atom at the same time.
  • UV-1 Description of the substituents of the compound represented by the formula (UV-1) can be referred to the description of paragraph numbers 0024 to 0033 of International Publication WO2009 / 123109, the contents of which are incorporated herein.
  • Specific examples of the compound represented by the formula (UV-1) include Exemplified Compounds (1) to (14) in Paragraph Nos. 0034 to 0037 of International Publication WO2009 / 123109, the contents of which are described in the present specification. Incorporated into.
  • Examples of commercially available ultraviolet absorbers represented by the formula (UV-1) include UV503 (manufactured by Daito Chemical Co., Ltd.).
  • Examples of the diketone compound include compounds represented by the following formula (UV-2).
  • R 101 and R 102 each independently represent a substituent
  • m1 and m2 each independently represent 0 to 4.
  • Substituents are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, acyloxy groups, Amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl group, aryl Sulfonyl, heteroaryls
  • the alkyl group preferably has 1 to 20 carbon atoms.
  • Examples of the alkyl group include linear, branched, and cyclic, and linear or branched is preferable, and branched is more preferable.
  • the number of carbon atoms of the alkoxy group is preferably 1-20.
  • Examples of the alkoxy group include straight chain, branched, and cyclic, and straight chain or branched is preferable, and branched is more preferable.
  • a combination in which one of R 101 and R 102 is an alkyl group and the other is an alkoxy group is preferable.
  • m1 and m2 each independently represents 0-4.
  • m1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.
  • Examples of the compound represented by the formula (UV-2) include the following compounds.
  • UV absorber Yubinal A (manufactured by BASF) can be used.
  • an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a triazine compound, and the like can be used. Is mentioned.
  • MYUA series Chemical Industry Daily, February 1, 2016 manufactured by Miyoshi Oil and Fat may be used.
  • the content of the ultraviolet absorber is preferably 0.01 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition of the present invention. Further, the content of the ultraviolet absorber is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 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 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 bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • the functional group other than the hydrolyzable group is preferably a group that exhibits affinity by forming an interaction or bond with the resin.
  • examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, and an isocyanate group, and a (meth) acryloyl group and an epoxy group are preferable.
  • silane coupling agent compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, compounds described in paragraph Nos. 0056 to 0066 of JP-A-2009-242604, and international publication WO2015 / 166679 Examples include the compounds described in paragraphs 0229-0236, the contents of which are incorporated herein.
  • the content of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the total solid content of the curable composition.
  • the curable composition of the present invention may contain only one type of silane coupling agent or two or more types. When two or more types of silane coupling agents are included, the total amount is preferably within the above range.
  • the curable composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved.
  • the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability
  • the fluorine content in the fluorosurfactant 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 in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a curable composition.
  • fluorosurfactant examples include surfactants described in JP-A-2014-41318, paragraph numbers 0060 to 0064 (corresponding to paragraph numbers 0060 to 0064 of international publication 2014/17669), and the like. Examples include surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, the contents of which are incorporated herein.
  • fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc. are mentioned.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated is suitably used.
  • a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, which can be used.
  • a block polymer can be used. Examples thereof include compounds described in JP2011-89090A.
  • 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 group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. % Which shows the ratio of a repeating unit in said compound is the mass%.
  • a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used.
  • Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like.
  • the fluorine-based surfactant compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 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, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS) Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure
  • the content of the surfactant is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the curable composition.
  • the curable composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, and other auxiliary agents (for example, conductive). Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents and the like. With respect to these components, descriptions in paragraph numbers 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074 can be referred to, and the contents thereof are incorporated in the present specification.
  • the antioxidant examples include a phenol compound, a phosphite compound, and a thioether compound.
  • a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. You may use these in mixture of 2 or more types.
  • the phenol compound any phenol compound known as a phenol-based antioxidant can be used.
  • Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule.
  • phosphorus antioxidant can also be used suitably for antioxidant.
  • phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine and ethyl bis (2,4-di-tert-butyl-6-methylphenyl) phosphite. These are available as commercial products.
  • the content of the antioxidant is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass, based on the total solid content of the composition. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the viscosity (23 ° C.) of the curable composition of the present invention is preferably in the range of 1 to 3000 mPa ⁇ s, for example, when a film is formed by coating.
  • the lower limit is preferably 3 mPa ⁇ s or more, and more preferably 5 mPa ⁇ s or more.
  • the upper limit is preferably 2000 mPa ⁇ s or less, and more preferably 1000 mPa ⁇ s or less.
  • the Ti value at 23 ° C. of the curable composition of the present invention is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, and 0.9 to 1.1. More preferably it is. Ti value of a curable composition can be measured by the method demonstrated in the column of the pigment dispersion liquid mentioned above.
  • the curable composition of the present invention can be preferably used for forming a near-infrared cut filter, an infrared transmission filter, or the like.
  • the curable composition of this invention can be prepared by mixing each component mentioned above. Moreover, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. With respect to the type of filter and the filtration method, those described in the column for preparing the pigment dispersion can be mentioned, and the preferred ranges are also the same.
  • the film of the present invention is formed using the above-described curable composition of the present invention.
  • the film of the present invention can be preferably used as an optical filter such as a near-infrared cut filter and an infrared transmission filter.
  • an aspect in which the optical filter includes a pixel using the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable aspect.
  • the film of the present invention can also be used as a heat ray shielding filter.
  • the film of the present invention may have a pattern, or may be a film without a pattern (flat film).
  • the film of the present invention may be used by being laminated on a support, or the film of the present invention may be peeled off from a support.
  • examples of the infrared transmission filter include a filter that blocks visible light and transmits light having a wavelength of 900 nm or more.
  • the film of the present invention When the film of the present invention is used as an infrared transmission filter, a near-infrared absorbing organic pigment and a colorant that blocks visible light (preferably a colorant containing two or more chromatic colorants, or an organic black coloration) A filter using a curable composition containing at least an agent), or a filter having a layer of a color material that blocks visible light in addition to a layer containing a near infrared absorbing organic pigment. Preferably there is.
  • the near-infrared absorbing organic pigment has a role of limiting transmitted light (near-infrared light) to a longer wavelength side.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
  • a color filter can be manufactured using the coloring composition containing a chromatic colorant.
  • the chromatic colorant include the chromatic colorant described in the curable composition of the present invention.
  • the coloring composition can further contain a resin, a curable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. About these details, the material demonstrated by the curable composition of this invention is mentioned, These can be used. Moreover, it is good also as a filter provided with the function as a near-infrared cut filter and a color filter by making the film
  • membrane of this invention contain a chromatic colorant.
  • the near-infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and shields at least a part of light having a wavelength in the near-infrared region (near-infrared light). .
  • the near-infrared cut filter may transmit all light having a wavelength in the visible region, and transmits light in a specific wavelength region out of light having a wavelength in the visible region, and blocks light in the specific wavelength region. You may do.
  • the color filter means a filter that allows light in a specific wavelength region to pass and blocks light in a specific wavelength region out of light having a wavelength in the visible region.
  • the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least part of light having a wavelength in the near infrared region (near infrared).
  • the film of the present invention preferably has a maximum absorption wavelength in the range of 700 to 1000 nm.
  • the absorbance A550 / absorbance Amax which is the ratio of the absorbance A550 at a wavelength of 550 nm to the absorbance Amax at the maximum absorption wavelength, is preferably 0.002 to 0.040, more preferably 0.003 to 0.030. Preferably, it is 0.004 to 0.020.
  • the absorbance A400 / absorbance Amax which is the ratio between the absorbance A400 at a wavelength of 400 nm and the absorbance Amax at the maximum absorption wavelength, is preferably 0.005 to 0.150, more preferably 0.020 to 0.100. Preferably, it is 0.050 to 0.070.
  • the maximum absorption wavelength of the film is more preferably in the range of 720 to 980 nm, and still more preferably in the range of 740 to 960 nm.
  • the near-infrared cut filter of the present invention preferably satisfies at least one of the following conditions (1) to (4) with respect to light transmittance, and satisfies all the conditions (1) to (4): Is more preferable.
  • the transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.
  • the transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the near-infrared cut filter preferably has a film thickness of 20 ⁇ m or less and a transmittance of 70% or more, more preferably 80% or more, and 90% or more in the entire wavelength range of 400 to 650 nm. It is still more preferable that it is above. Further, the transmittance at at least one point in the wavelength range of 700 to 1000 nm is preferably 20% or less.
  • the near-infrared cut filter of the present invention may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorption layer and the like in addition to the film of the present invention.
  • a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained.
  • it can be set as the near-infrared cut filter excellent in ultraviolet-shielding property because a near-infrared cut filter has an ultraviolet absorption layer further.
  • the ultraviolet absorbing layer for example, the absorbing layer described in paragraph Nos.
  • the glass substrate (copper containing glass substrate) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex can also be used.
  • the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper.
  • Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott), CD5000 (manufactured by HOYA Co., Ltd.), and the like.
  • a copper complex content layer the layer formed using the composition containing a copper complex is mentioned.
  • the copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm.
  • the maximum absorption wavelength of the copper complex is more preferably in the wavelength region of 720 to 1200 nm, and still more preferably in the wavelength region of 800 to 1100 nm.
  • the film and near-infrared cut filter of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.
  • a solid-state imaging device such as a CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor)
  • CMOS complementary metal oxide semiconductor
  • the laminate of the present invention has the film of the present invention and a color filter containing a chromatic colorant.
  • the film of the present invention and the color filter may or may not be adjacent in the thickness direction.
  • the film of the present invention may be formed on a support different from the support on which the color filter is formed.
  • other members for example, a microlens, a flattening layer, etc.
  • the pattern forming method includes a step of forming a composition layer on a support using the curable composition of the present invention, a step of forming a pattern on the composition layer by a photolithography method or a dry etching method, It is preferable to contain.
  • the pattern forming method by the photolithography method includes a step of forming a composition layer on a support using a curable composition, a step of exposing the composition layer in a pattern, and developing and removing an unexposed portion. Forming a pattern. If necessary, a step of baking the composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided.
  • the pattern formation method by the dry etching method includes a step of forming a composition layer on a support using a curable composition and curing to form a cured product layer, and forming a photoresist layer on the cured product layer.
  • a step of patterning the photoresist layer by exposure and development to obtain a resist pattern and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask.
  • Step of Forming Composition Layer In the step of forming the composition layer, the composition layer is formed on the support using the curable composition.
  • a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
  • the pattern may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
  • an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • a known method can be used as a method for applying the curable composition to the support.
  • a dropping method drop casting
  • a slit coating method for example, a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A).
  • Methods described in the publication inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • the application method in the ink jet is not particularly limited.
  • the composition layer formed on the support may be dried (prebaked).
  • pre-baking may not be performed.
  • the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
  • the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
  • the prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.
  • Exposure process When forming a pattern by photolithography, ⁇ Exposure process >> Next, the composition layer is exposed in a pattern (exposure process).
  • pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
  • Radiation (light) that can be used for exposure is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferable.
  • Irradiation dose (exposure 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.
  • the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (eg, 5000 W / m 2 , 15000 W / m 2 , 35000 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 development removal of the unexposed portion can be performed using a developer.
  • the developer is preferably an alkaline developer that does not damage the underlying solid-state imaging device or circuit.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate Inorganic alkaline compounds such as arm and the like.
  • an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
  • concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
  • a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable.
  • clean (rinse) with a pure water after image development.
  • Post-baking is a heat treatment after development for complete film curing.
  • the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C is more preferable.
  • the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable.
  • the lower limit can be, for example, 50 ° C. or higher.
  • Post-bake is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions for the developed film. Can do.
  • the pattern forming method of the present invention may further include a step of exposing after development (after development) of the unexposed portion (after development) (hereinafter, exposure after development is also referred to as post-exposure).
  • exposure after development is also referred to as post-exposure.
  • post-exposure is preferably performed.
  • the composition layer in two stages before and after the pattern formation, the composition can be appropriately cured by the first exposure (exposure before forming the pattern), and the next exposure (after forming the pattern)
  • the entire composition can be almost cured by the above exposure).
  • the post-bake temperature is 180 ° C. or lower, the curable composition can be effectively cured.
  • post-baking may be further performed after the post-exposure.
  • the post-bake temperature is preferably 100 to 240 ° C., for example.
  • the pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask for the obtained cured product layer. Etching gas can be used.
  • a pre-bake treatment it is preferable to further perform a pre-bake treatment.
  • the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in this specification.
  • the solid-state imaging device of the present invention has the above-described film of the present invention.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration having the film of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.
  • the device On the support, there are a plurality of photodiodes that constitute the light receiving area of the solid-state imaging device, and transfer electrodes made of polysilicon, etc., and light shielding made of tungsten or the like that opens only the light receiving part of the photodiodes on the photodiodes and transfer electrodes.
  • the device has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, and the film of the present invention is formed on the device protective film. is there.
  • the device protective film has a condensing means (for example, a microlens, etc., the same applies hereinafter) under the film of the present invention (on the side close to the support), or condensing on the film of the present invention.
  • the structure etc. which have a means may be sufficient.
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel.
  • Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
  • the film of the present invention can also be used for image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices.
  • image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices.
  • the film of the present invention is added to each colored pixel for the purpose of blocking infrared light contained in the backlight (for example, white light emitting diode (white LED)) of the image display device, the purpose of preventing malfunction of peripheral devices.
  • infrared light contained in the backlight for example, white light emitting diode (white LED)
  • white LED white light emitting diode
  • the image display device for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)”, “Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989) ) "Etc.
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the image display device may have a white organic EL element.
  • the white organic EL element preferably has a tandem structure.
  • JP 2003-45676 A supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc.
  • the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
  • the infrared sensor of the present invention has the above-described film of the present invention.
  • the configuration of the infrared sensor of the present invention is not particularly limited as long as it is a configuration having the film of the present invention and functions as an infrared sensor.
  • reference numeral 110 denotes a solid-state image sensor.
  • the imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114.
  • a color filter 112 is laminated on the near infrared cut filter 111.
  • a micro lens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
  • a planarization layer 116 is formed so as to cover the microlens 115.
  • the near-infrared cut filter 111 can be formed using the composition of the present invention.
  • the color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used.
  • a color filter in which red (R), green (G), and blue (B) pixels are formed is used.
  • R red
  • G green
  • B blue
  • paragraph numbers 0214 to 0263 in Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the present specification.
  • the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.
  • the infrared transmission filter 114 preferably has a maximum light transmittance of 30% or less in the wavelength range of 400 to 650 nm in the thickness direction of the film. % Or less, more preferably 10% or less, and particularly preferably 0.1% or less. This transmittance preferably satisfies the above conditions throughout the wavelength range of 400 to 650 nm.
  • the maximum value in the wavelength range of 400 to 650 nm is usually 0.1% or more.
  • the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 nm or more is preferably 70% or more, more preferably 80% or more. More preferably, it is 90% or more.
  • This transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above condition at a wavelength corresponding to the emission wavelength of the infrared LED.
  • the minimum value of light transmittance in the wavelength range of 900 to 1300 nm is usually 99.9% or less.
  • the film thickness of the infrared transmission filter 114 is preferably 100 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the lower limit is preferably 0.1 ⁇ m.
  • a method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
  • the film thickness was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film.
  • the spectral characteristic of the film is a value obtained by measuring the transmittance in the wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
  • the infrared transmission filter 114 has a maximum light transmittance in the thickness direction of the film in the wavelength range of 450 to 650 nm of 20% or less.
  • the transmittance of light having a wavelength of 835 nm is preferably 20% or less
  • the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more.
  • the average primary particle diameter of the obtained near-infrared absorbing organic pigment, the coefficient of variation of the primary particle diameter, the average long / short side ratio, the coefficient of variation of the long / short side ratio, and the powder X-ray diffraction spectrum were measured. Further, based on the powder X-ray diffraction spectrum, the full width at half maximum and the crystallinity value of the peak having the highest diffraction intensity in the region where the diffraction angle 2 ⁇ is 5 to 12 ° were obtained.
  • Pigment 2 Compound having the following structure (near infrared absorbing organic pigment)
  • Pigment 4 Compound having the following structure (near-infrared absorbing organic pigment)
  • Coefficient of variation of primary particle diameter of near-infrared absorbing organic pigment (standard deviation of primary particle diameter of near-infrared absorbing organic pigment / arithmetic average value of primary particle diameter of near-infrared absorbing organic pigment) ⁇ 100
  • the primary particles of the near-infrared absorbing organic pigment were observed with a transmission electron microscope and determined from the obtained photograph. Specifically, the ratio of the short side to the long side (short side / long side) of the primary particles of the near-infrared absorbing organic pigment was determined from the projected photograph, and the long / short side ratio was calculated. Further, the coefficient of variation of the long / short side ratio was determined based on the following formula.
  • Variation coefficient of long-short side ratio of near-infrared absorbing organic pigment (standard deviation of long-short side ratio of near-infrared absorbing organic pigment / arithmetic average value of long-short side ratio of near-infrared absorbing organic pigment) ⁇ 100
  • the measured value of the powder X-ray diffraction spectrum is based on the straight line connecting the lowest point in the region where the diffraction angle 2 ⁇ is 5 to 15 ° and the lowest point in the region of 25 to 35 °.
  • the spectrum correction value obtained by subtracting the baseline value from the value was measured using the following formula.
  • Ic is a region where the diffraction angle 2 ⁇ is 15 ° or more, and is the maximum value of the peak diffraction intensity derived from the crystal in the powder X-ray diffraction spectrum
  • Ia is amorphous in the powder X-ray diffraction spectrum. It is the maximum value of the diffraction intensity of the derived peak.
  • a peak having a full width at half maximum of 1 ° or less is regarded as a peak derived from a crystal.
  • a peak whose full width at half maximum exceeds 3 ° is defined as a peak derived from amorphous.
  • PMEA ether acetate
  • the numerical value attached to the main chain represents the molar ratio of repeating units, and the numerical value attached to the side chain represents the number of repeating units.
  • the sample solution was applied onto a glass wafer by spin coating so that the film thickness after application was 0.3 ⁇ m, and then heated at 100 ° C. for 2 minutes using a hot plate. Next, exposure was performed at 1000 mJ / cm 2 using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Furthermore, it heated at 220 degreeC for 5 minute (s) using the hotplate, and formed the film
  • the absorption wavelength at the maximum absorption wavelength, the absorbance Amax at the wavelength of 550 nm, the absorbance A550 at the wavelength of 400 nm, and the absorbance at the wavelength of 400 nm are measured on the substrate on which the film is formed.
  • A400 is obtained, and the ratio of absorbance A550 at the wavelength of 550 nm to absorbance Amax at the maximum absorption wavelength (absorbance A550 / absorbance Amax), and the ratio of absorbance A400 at wavelength 400 nm to absorbance Amax at the maximum absorption wavelength (absorbance A400 / absorbance Amax) Calculated.
  • the Examples had low absorbance A400 and absorbance A550, and were excellent in visible transparency. Moreover, heat resistance was also favorable.
  • the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment has a diffraction intensity peak in the region where the diffraction angle 2 ⁇ is 5 to 12 °, and the full width at half maximum of the peak having the highest diffraction intensity in this region is 0.3 to 0. .6 °.
  • 110 Solid-state imaging device
  • 111 Near-infrared cut filter
  • 112 Color filter
  • 114 Infrared transmission filter
  • 115 Micro lens
  • 116 Flattening layer

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US20210179809A1 (en) * 2018-06-01 2021-06-17 Toray Industries, Inc. Colored resin composition, preparing method for same, near-infrared transmission light shielding film, and decorative substrate
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WO2018168789A1 (ja) * 2017-03-15 2018-09-20 富士フイルム株式会社 樹脂組成物、樹脂成形体及び樹脂成形体の製造方法
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