WO2018056127A1 - Near-infrared absorbing organic pigment, pigment dispersion, curable composition, film, near-infrared cut filter, laminate, solid state imaging element, image display device, and infrared sensor - Google Patents

Near-infrared absorbing organic pigment, pigment dispersion, curable composition, film, near-infrared cut filter, laminate, solid state imaging element, image display device, and infrared sensor 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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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/en
Publication of WO2018056127A1 publication Critical patent/WO2018056127A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/02—Details

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

Abstract

Provided is a near-infrared ray absorbing organic pigment having exceptional transparency in the visible ray region and exceptional heat resistance. In addition, provided are a pigment dispersion, a curable composition, a film, a near-infrared cut filter, a laminate, a solid state imaging element, an image display device, and an infrared sensor. In a powder X-ray diffraction spectrum, this near-infrared ray absorbing organic pigment has a peak of diffraction intensity in a region in which the diffraction angle 2θ is 5 to 12°, and the full width at half maximum of a peak at which the diffraction intensity in said region is highest is 0.3 to 0.6°.

Description

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Near-infrared absorbing organic pigment, pigment dispersion, curable composition, film, near-infrared cut filter, laminate, solid-state imaging device, image display device, and infrared sensor
　本発明は、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に関する。 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.
　ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などには、カラー画像の固体撮像素子である、ＣＣＤ（電荷結合素子）や、ＣＭＯＳ（相補型金属酸化膜半導体）が用いられている。これら固体撮像素子は、その受光部において赤外線に感度を有するシリコンフォトダイオードを使用しているために、近赤外線カットフィルタを使用して視感度補正を行うことがある。 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.
　近赤外線カットフィルタは、赤外線遮蔽性を高めるため、近赤外線吸収有機顔料などの近赤外線吸収剤を含む硬化性組成物を用いて製造する方法が知られている（例えば、特許文献１、２）。 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). .
特開２０１４－１９１１９０号公報JP 2014-191190 A 国際公開ＷＯ２０１４／１８５５１８号公報International Publication WO2014 / 185518
　近赤外線吸収有機顔料などの近赤外線吸収剤は、赤外線遮蔽性に優れるとともに、可視透明性に優れることが求められている。また、近赤外線吸収有機顔料などを含む硬化性組成物を用いて近赤外線カットフィルタなどを製造する際は、乾燥や硬化のために加熱を施すことがある。しかしながら、近赤外線吸収有機顔料の耐熱性が低い場合、加熱により着色が生じて、可視透明性が低下することがあった。 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.
　よって、本発明の目的は、可視透明性および耐熱性に優れた近赤外線吸収有機顔料を提供することにある。また、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を提供することにある。 Therefore, 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.
　かかる状況のもと、本発明者らが鋭意検討を行った結果、後述する近赤外線吸収有機顔料が可視透明性および耐熱性に優れることを見出し、本発明を完成するに至った。本発明は以下を提供する。
　＜１＞　粉末Ｘ線回折スペクトルにおいて回折角度２θが５～１２°の領域に回折強度のピークを有し、前述の領域での回折強度が最も大きいピークの半値全幅が０．３～０．６°である、近赤外線吸収有機顔料。
　＜２＞　前述の半値全幅が０．３～０．４５°である、＜１＞に記載の近赤外線吸収有機顔料。
　＜３＞　近赤外線吸収有機顔料の平均一次粒子径が１０～１００ｎｍである、＜１＞または＜２＞に記載の近赤外線吸収有機顔料。
　＜４＞　近赤外線吸収有機顔料の平均一次粒子径が２０～４５ｎｍである、＜１＞または＜２＞に記載の近赤外線吸収有機顔料。
　＜５＞　近赤外線吸収有機顔料の一次粒子径の変動係数が２０～３５％である、＜１＞～＜４＞のいずれか１つに記載の近赤外線吸収有機顔料。
　＜６＞　近赤外線吸収有機顔料の平均長短辺比が０．５～０．９である、＜１＞～＜５＞のいずれか１つに記載の近赤外線吸収有機顔料。
　＜７＞　近赤外線吸収有機顔料の長短辺比の変動係数が１０～３０％である、＜１＞～＜６＞のいずれか１つに記載の近赤外線吸収有機顔料。
　＜８＞　近赤外線吸収有機顔料の下記式で表される結晶化度の値が０．９～０．９９である、＜１＞～＜７＞のいずれか１つに記載の近赤外線吸収有機顔料；
　結晶化度＝［Ｉｃ／（Ｉａ＋Ｉｃ）］
　式中、Ｉｃは、回折角度２θが１５°以上の領域であって、粉末Ｘ線回折スペクトルにおける結晶に由来するピークの回折強度の最大値であり、
　Ｉａは、粉末Ｘ線回折スペクトルにおけるアモルファスに由来するピークの回折強度の最大値である。
　＜９＞　近赤外線吸収有機顔料が、ピロロピロール化合物およびスクアリリウム化合物から選ばれる少なくとも１種である、＜１＞～＜８＞のいずれか１つに記載の近赤外線吸収有機顔料。
　＜１０＞　＜１＞～＜９＞のいずれか１つに記載の近赤外線吸収有機顔料と、樹脂と、溶剤とを含む顔料分散液。
　＜１１＞　更に顔料誘導体を含む、＜１０＞に記載の顔料分散液。
　＜１２＞　＜１＞～＜９＞のいずれか１つに記載の近赤外線吸収有機顔料と、樹脂と、硬化性化合物と、溶剤とを含む硬化性組成物。
　＜１３＞　＜１２＞に記載の硬化性組成物を用いた膜。
　＜１４＞　＜１３＞に記載の膜を有する近赤外線カットフィルタ。
　＜１５＞　＜１３＞に記載の膜と、有彩色着色剤を含むカラーフィルタとを有する積層体。
　＜１６＞　＜１３＞に記載の膜を有する固体撮像素子。
　＜１７＞　＜１３＞に記載の膜を有する画像表示装置。
　＜１８＞　＜１３＞に記載の膜を有する赤外線センサ。 Under such circumstances, as a result of intensive studies by the present inventors, it has been found that a near-infrared absorbing organic pigment described later is excellent in visible transparency and heat resistance, and the present invention has been completed. 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 2θ 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. ° Near-infrared absorbing organic pigment.
<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%.
<8> The near-infrared absorbing organic material according to any one of <1> to <7>, wherein the near-infrared absorbing organic pigment has a crystallinity value of 0.9 to 0.99 represented by the following formula: Pigments;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is a region where the diffraction angle 2θ 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.
<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.
<11> The pigment dispersion according to <10>, further comprising a pigment derivative.
<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>.
　本発明によれば、可視透明性および耐熱性に優れた近赤外線吸収有機顔料を提供することが可能になった。また、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を提供することが可能になった。 According to the present invention, it is possible to provide a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance. In addition, 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.
赤外線センサの一実施形態を示す概略図である。It is the schematic which shows one Embodiment of an infrared sensor.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定でのポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ（内径）×１５．０ｃｍ）を用い、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ（Ｎ－メチルピロリジノン）溶液を用いることによって求めることができる。
　本明細書において、近赤外線とは、波長７００～２５００ｎｍの光（電磁波）をいう。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において顔料とは、特定の溶剤に対して溶解しにくい化合物を意味する。例えば、顔料は、２３℃の水１００ｇおよび２３℃のプロピレングリコールモノメチルエーテルアセテート１００ｇに対する溶解度が０．１ｇ以下であることが好ましく、０．０１ｇ以下であることがより好ましい。 Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “˜” 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.
In the notation of a group (atomic group) in the present specification, 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. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of 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.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement. In this specification, 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.
In this specification, near-infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
In this specification, 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. .
In the present specification, the pigment means a compound that is difficult to dissolve in a specific solvent. For example, 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.
＜近赤外線吸収有機顔料＞
　本発明の近赤外線吸収有機顔料は、粉末Ｘ線回折スペクトルにおいて回折角度２θが５～１２°の領域に回折強度のピークを有し、前述の領域での回折強度が最も大きいピークの半値全幅が０．３～０．６°であることを特徴とする。 <Near-infrared absorbing organic pigment>
The near-infrared absorbing organic pigment of the present invention has a diffraction intensity peak in the region where the diffraction angle 2θ 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 °.
　本発明者らが鋭意検討を行った結果、近赤外線吸収有機顔料の粉末Ｘ線回折スペクトルにおいて回折角度２θが５～１２°の領域に回折強度のピークを有し、前述の領域での回折強度が最も大きいピークの半値全幅が０．３～０．６°である近赤外線吸収有機顔料は、可視透明性および耐熱性に優れることを見出した。詳細な理由は不明であるが、前述の回折強度が最も大きいピークの半値全幅が０．３～０．６°であることにより、近赤外線吸収有機顔料の結晶子が適度なサイズとなり、散乱は少ない一方で会合体を形成する顔料分子の割合が高くなり、その結果、可視透明性および耐熱性を向上できたと推測する。近赤外線吸収有機顔料の粉末Ｘ線回折スペクトルは、後述する実施例に記載の方法で測定することができる。 As a result of intensive studies by the present inventors, 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 2θ 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 detailed reason is unknown, but 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.
　本発明の近赤外線吸収有機顔料における、前述の回折強度が最も大きいピークは、回折角度２θが６～１０°の領域に有することが好ましく、６～９°の領域に有することがより好ましく、６．５～８．５°の領域に有することが更に好ましい。この態様によれば、可視透明性および耐熱性をさらに向上できる。また、前述の回折強度が最も大きいピークの半値全幅は、０．３～０．４５°であることが好ましい。この態様によれば、可視透明性および耐熱性が特に良好である。なお、本発明において、粉末Ｘ線回折スペクトルにおける上述の回折強度が最も大きいピークの半値全幅は、回折角度２θが５～１２°の領域における回折強度が最も大きいピークを、ローレンツ関数［ｙ＝Ａ／（１＋（（ｘ－ｘ０）／ｗ）２）＋ｈ］にフィッティングして求めることができる。ここで、ｙは強度、Ａはピーク高さ、ｘは２θ、ｘ０はピーク位置、ｗはピーク幅（半値半幅）、ｈはベースラインである。 In the near-infrared absorbing organic pigment of the present invention, the peak having the highest diffraction intensity is preferably in the region where the diffraction angle 2θ 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. In the present invention, the full width at half maximum of the peak having the highest diffraction intensity in the powder X-ray diffraction spectrum is the Lorentz function [y = A / (1 + ((x−x0) / w) 2 ) + h]. Here, y is the intensity, A is the peak height, x is 2θ, x0 is the peak position, w is the peak width (half width at half maximum), and h is the baseline.
　本発明の近赤外線吸収有機顔料の平均一次粒子径は、１０～１００ｎｍであることが好ましい。下限は、１５ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、２５ｎｍ以上が更に好ましく、３０ｎｍ以上が特に好ましい。上限は、９０ｎｍ以下が好ましく、８０ｎｍ以下がより好ましく、６０ｎｍ以下が更に好ましく、４５ｎｍ以下が特に好ましい。近赤外線吸収有機顔料の平均一次粒子径は、２０～４５ｎｍが好ましく、３０～４５ｎｍであることが特に好ましい。近赤外線吸収有機顔料の平均一次粒子径を１００ｎｍ以下とすることで、可視透明性を更に向上することができる。また、近赤外線吸収有機顔料の平均一次粒子径を１０ｎｍ以上とすることで、分散安定性が向上するという効果が得られる。なお、近赤外線吸収有機顔料の平均一次粒子径が小さくなるに伴い、耐熱性が低下しやすい傾向にあるが、上述の回折特性を有する近赤外線吸収有機顔料は、平均一次粒子径が小さくても、優れた耐熱性を有している。 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. Moreover, 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. As 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.
　本発明の近赤外線吸収有機顔料の一次粒子径の変動係数は、２０～３５％であることが好ましい。下限は２１％以上が好ましく、２２％以上がより好ましい。上限は３３％以下が好ましく、３０％以下がより好ましく、２９％以下が更に好ましく、２８％以下が一層好ましい。近赤外線吸収有機顔料の一次粒子径の変動係数が上記範囲であれば、可視透明性を更に向上できる。なお、近赤外線吸収有機顔料の一次粒子径の変動係数は、下記式にて定義される。
　近赤外線吸収有機顔料の一次粒子径の変動係数＝（近赤外線吸収有機顔料の一次粒子径の標準偏差／近赤外線吸収有機顔料の一次粒子径の算術平均値）×１００ 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
　本発明の近赤外線吸収有機顔料の平均長短辺比は、０．５～０．９であることが好ましい。下限は０．５３以上が好ましく、０．５６以上がより好ましい。上限は０．８以下が好ましく、０．７以下がより好ましい。近赤外線吸収有機顔料の平均長短辺比が上記範囲であれば、耐熱性が向上するという効果が期待できる。 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.
　本発明の近赤外線吸収有機顔料の長短辺比の変動係数は、１０～３０％であることが好ましい。下限は１３％以上が好ましく、１６％以上がより好ましい。上限は２８％以下が好ましく、２６％以下がより好ましい。近赤外線吸収有機顔料の長短辺比の変動係数が上記範囲であれば、可視透明性が向上するという効果が期待できる。なお、近赤外線吸収有機顔料の長短辺比の変動係数は、下記式にて定義される。
　近赤外線吸収有機顔料の長短辺比の変動係数＝（近赤外線吸収有機顔料の長短辺比の標準偏差／近赤外線吸収有機顔料の長短辺比の算術平均値）×１００ 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
　本発明において、近赤外線吸収有機顔料の一次粒子径および長短辺比は、近赤外線吸収有機顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。具体的には、近赤外線吸収有機顔料の一次粒子の投影面積を求め、それに対応する円相当径を近赤外線吸収有機顔料の一次粒子径として算出する。また、投影された写真から、一次粒子の短辺と長辺の比（短辺／長辺）を求めて長短辺比を算出する。また、本発明における平均一次粒子径および平均長短辺比は、４００個の近赤外線吸収有機顔料の一次粒子についての一次粒子径および長短辺比の算術平均値とする。また、一次粒子の最も長い直径を長辺といい、最も短い直径を短辺という。すなわち、楕円の場合は長軸が長辺であり、短軸が短辺である。また、近赤外線吸収有機顔料の一次粒子とは、凝集のない独立した粒子をいう。 In the present invention, 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. Moreover, let 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. Moreover, the primary particle | grains of a near-infrared absorption organic pigment mean the independent particle | grains without aggregation.
　本発明において、近赤外線吸収有機顔料の下記式で表される結晶化度の値が０．９～０．９９であることが好ましく、０．９１～０．９８であることがより好ましく、０．９３～０．９６であることが更に好ましい。結晶化度の値が上記範囲であれば、耐熱性を更に向上できる。
　結晶化度＝［Ｉｃ／（Ｉａ＋Ｉｃ）］
　式中、Ｉｃは、回折角度２θが１５°以上の領域であって、粉末Ｘ線回折スペクトルにおける結晶に由来するピークの回折強度の最大値であり、
　Ｉａは、粉末Ｘ線回折スペクトルにおけるアモルファスに由来するピークの回折強度の最大値である。 In the present invention, 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)]
In the formula, Ic is a region where the diffraction angle 2θ 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.
　なお、本発明における結晶に由来するピークとは、回折強度のピークにおける半値全幅が１°以下の鋭いピークを意味する。また、アモルファスに由来するピークとは、回折強度のピークにおける半値全幅が３°を超えるピークを意味する。また、本発明において、ＩｃおよびＩａの値は、近赤外線吸収有機顔料の粉末Ｘ線回折スペクトルの回折角度２θが５～１５°の領域での回折強度が最も低い点と、２５～３５°の領域で回折強度が最も低い点とを結んだ直線をベースラインとし、粉末Ｘ線回折スペクトルのスペクトル実測値からベースラインの値を引いたスペクトル補正値を用いて計算した値である。 It should be noted that 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. In addition, the peak derived from amorphous means a peak whose full width at half maximum exceeds 3 ° in the peak of diffraction intensity. In the present invention, the values of Ic and Ia are such that the diffraction intensity in the region where the diffraction angle 2θ 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.
　本発明の近赤外線吸収有機顔料の種類は、近赤外線領域（好ましくは７００～１０００ｎｍの範囲）に極大吸収波長を有する有機顔料であればよく、特に限定はない。なお、有機顔料とは、有機化合物で構成された顔料である。本発明の近赤外線吸収有機顔料は、ピロロピロール化合物、スクアリリウム化合物、シアニン化合物、フタロシアニン化合物、ナフタロシアニン化合物およびジイモニウム化合物から選ばれる少なくとも１種であることが好ましく、ピロロピロール化合物、スクアリリウム化合物およびシアニン化合物から選ばれる少なくとも１種であることがより好ましく、ピロロピロール化合物またはスクアリリウム化合物であることが更に好ましく、ピロロピロール化合物であることが特に好ましい。特にピロロピロール化合物の場合においては、可視透明性および耐熱性をより効果に向上させることができる。 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.
　ピロロピロール化合物としては、式（ＰＰ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000001
 　式中、Ｒ１ａおよびＲ１ｂは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ２およびＲ３は、各々独立に水素原子または置換基を表し、Ｒ２およびＲ３は、互いに結合して環を形成してもよく、Ｒ４は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲ４ＡＲ４Ｂ、または金属原子を表し、Ｒ４は、Ｒ１ａ、Ｒ１ｂおよびＲ３から選ばれる少なくとも一つと、共有結合もしくは配位結合していてもよく、Ｒ４ＡおよびＲ４Ｂは、各々独立に置換基を表す。 The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
Figure JPOXMLDOC01-appb-C000001
 In the formula, 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, and R 2 and R 3 are R 4 may be bonded to each other to form a ring, and 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, and R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded, and R 4A and R 4B each independently represent a substituent.
　Ｒ１ａおよびＲ１ｂは、各々独立に、アルキル基、アリール基またはヘテロアリール基を表し、アリール基またはヘテロアリール基が好ましく、アリール基がより好ましい。
　Ｒ１ａ、Ｒ１ｂが表すアルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０が特に好ましい。
　Ｒ１ａ、Ｒ１ｂが表すアリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が特に好ましい。
　Ｒ１ａ、Ｒ１ｂが表すヘテロアリール基を構成する炭素原子の数は、１～３０が好ましく、１～１２がより好ましい。ヘテロアリール基を構成するヘテロ原子の種類としては、例えば、窒素原子、酸素原子および硫黄原子が挙げられる。ヘテロアリール基を構成するヘテロ原子の数としては、１～３が好ましく、１～２がより好ましい。ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。
　上述したアルキル基、アリール基およびヘテロアリール基は、置換基を有していてもよく、無置換であってもよい。置換基を有していることが好ましい。置換基としては、後述する置換基Ｔで説明した基が挙げられる。なかでも、アルコキシ基、ヒドロキシ基が好ましい。アルコキシ基は、分岐アルキル基を有するアルコキシ基であることが好ましい。Ｒ１ａ、Ｒ１ｂで表される基としては、分岐アルキル基を有するアルコキシ基を置換基として有するアリール基、または、ヒドロキシ基を置換基として有するアリール基であることが好ましい。分岐アルキル基の炭素数は、３～３０が好ましく、３～２０がより好ましい。 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. 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. Of these, an alkoxy group and a hydroxy group are preferable. 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.
　Ｒ２およびＲ３は各々独立に水素原子または置換基を表す。Ｒ２およびＲ３は結合して環を形成していてもよい。Ｒ２およびＲ３の少なくとも一方は電子求引性基であることが好ましい。Ｒ２およびＲ３は各々独立にシアノ基またはヘテロアリール基を表すことが好ましい。置換基としては例えば、特開２００９－２６３６１４号公報の段落番号００２０～００２２に記載された置換基が挙げられる。本明細書には、上記内容が組み込まれる。置換基としては、以下の置換基Ｔが挙げられる。
（置換基Ｔ）
　アルキル基（好ましくは炭素数１～３０）、アルケニル基（好ましくは炭素数２～３０）、アルキニル基（好ましくは炭素数２～３０）、アリール基（好ましくは炭素数６～３０）、アミノ基（好ましくは炭素数０～３０）、アルコキシ基（好ましくは炭素数１～３０）、アリールオキシ基（好ましくは炭素数６～３０）、ヘテロアリールオキシ基（好ましくは炭素数１～３０）、アシル基（好ましくは炭素数１～３０）、アルコキシカルボニル基（好ましくは炭素数２～３０）、アリールオキシカルボニル基（好ましくは炭素数７～３０）、アシルオキシ基（好ましくは炭素数２～３０）、アシルアミノ基（好ましくは炭素数２～３０）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０）、スルファモイル基（好ましくは炭素数０～３０）、カルバモイル基（好ましくは炭素数１～３０）、アルキルチオ基（好ましくは炭素数１～３０）、アリールチオ基（好ましくは炭素数６～３０）、ヘテロアリールチオ基（好ましくは炭素数１～３０）、アルキルスルホニル基（好ましくは炭素数１～３０）、アリールスルホニル基（好ましくは炭素数６～３０）、ヘテロアリールスルホニル基（好ましくは炭素数１～３０）、アルキルスルフィニル基（好ましくは炭素数１～３０）、アリールスルフィニル基（好ましくは炭素数６～３０）、ヘテロアリールスルフィニル基（好ましくは炭素数１～３０）、ウレイド基（好ましくは炭素数１～３０）、リン酸アミド基（好ましくは炭素数１～３０）、ヒドロキシ基、メルカプト基、ハロゲン原子、シアノ基、スルホ基、カルボキシ基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基（好ましくは炭素数１～３０）。
　これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。さらなる置換基としては、上述した置換基Ｔで説明した基が挙げられる。 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. Examples of the substituent include those described in JP-A 2009-263614, paragraphs 0020 to 0022. The above contents are incorporated in the present specification. Examples of the substituent include the following substituent T.
(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, sulfamoyl group (preferably 0 to 30 carbon atoms), carbamoyl group (preferably 1 to 30 carbon atoms), alkylthio group (preferably 1 to 30 carbon atoms), arylthio group (preferably 6-30 carbon atoms), heteroarylthio group (preferably 1-30 carbon atoms), alkylsulfonyl group (preferably 1-30 carbon atoms), arylsulfonyl group (preferably 6-30 carbon atoms), heteroarylsulfonyl Group (preferably having 1 to 30 carbon atoms), alkylsulfinyl group (preferably having 1 to 30 carbon atoms), arylsulfinyl group (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably having 1 to 30 carbon atoms) Ureido group (preferably having 1 to 30 carbon atoms), phosphoramide group (preferably having 1 to 30 carbon atoms), hydro Shi group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms).
When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described for the substituent T described above.
　Ｒ２およびＲ３のうち、少なくとも一方は電子求引性基であることが好ましい。ハメットの置換基定数σ値（シグマ値）が正の置換基は、電子求引性基として作用する。ここで、ハメット則で求められた置換基定数にはσｐ値とσｍ値がある。これらの値は多くの一般的な成書に見出すことができる。本発明においては、ハメットの置換基定数σ値が０．２以上の置換基を電子求引性基として例示することができる。σ値は、０．２５以上が好ましく、０．３以上がより好ましく、０．３５以上が更に好ましい。上限は特に制限はないが、好ましくは０．８０以下である。電子求引性基の具体例としては、シアノ基（σｐ値＝０．６６）、カルボキシ基（－ＣＯＯＨ：σｐ値＝０．４５）、アルコキシカルボニル基（－ＣＯＯＭｅ：σｐ値＝０．４５）、アリールオキシカルボニル基（例えば、－ＣＯＯＰｈ：σｐ値＝０．４４）、カルバモイル基（例えば－ＣＯＮＨ２：σｐ値＝０．３６）、アルキルカルボニル基（例えば－ＣＯＭｅ：σｐ値＝０．５０）、アリールカルボニル基（例えば－ＣＯＰｈ：σｐ値＝０．４３）、アルキルスルホニル基（例えば－ＳＯ２Ｍｅ：σｐ値＝０．７２）、アリールスルホニル基（例えば、－ＳＯ２Ｐｈ：σｐ値＝０．６８）などが挙げられる。ここで、Ｍｅはメチル基を、Ｐｈはフェニル基を表す。なお、ハメットの置換基定数σ値については、例えば、特開２０１１－６８７３１号公報の段落番号００１７～００１８を参酌でき、この内容は本明細書に組み込まれる。 At least one of R 2 and R 3 is preferably an electron withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-attracting group. Here, the substituent constant obtained by Hammett's rule includes a σp value and a σm value. These values can be found in many common books. In the present invention, substituents having Hammett's substituent constant σ value of 0.2 or more can be exemplified as electron-attracting groups. The σ 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. Specific examples of the electron withdrawing group include a cyano group (σp value = 0.66), a carboxy group (—COOH: σp value = 0.45), an alkoxycarbonyl group (—COOMe: σp value = 0.45). An aryloxycarbonyl group (for example, —COOPh: σp value = 0.44), a carbamoyl group (for example, —CONH 2 : σp value = 0.36), an alkylcarbonyl group (for example, —COMe: σp value = 0.50) An arylcarbonyl group (for example, —COPh: σp value = 0.43), an alkylsulfonyl group (for example, —SO 2 Me: σp value = 0.72), an arylsulfonyl group (for example, —SO 2 Ph: σp value = 0) .68). Here, Me represents a methyl group, and Ph represents a phenyl group. As for Hammett's substituent constant σ 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.
　Ｒ２およびＲ３が互いに結合して環を形成する場合は、５～７員環（好ましくは５または６員環）を形成することが好ましい。形成される環としては通常メロシアニン色素で酸性核として用いられるものが好ましく、その具体例としては、例えば特開２０１１－６８７３１号公報の段落００１９～００２１を参酌でき、この内容は本明細書に組み込まれる。 When 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.
　Ｒ２は電子求引性基（好ましくはシアノ基）を表し、Ｒ３はヘテロアリール基を表すことが好ましい。ヘテロアリール基は、５員環または６員環が好ましい。また、ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。ヘテロアリール基を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。ヘテロ原子としては、例えば、窒素原子、酸素原子、硫黄原子が例示される。ヘテロアリール基は、窒素原子を１個以上有することが好ましい。 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.
　Ｒ４が、アルキル基、アリール基またはヘテロアリール基を表す場合、アルキル基、アリール基およびヘテロアリール基としては、Ｒ１ａ、Ｒ１ｂで説明した基と同様であり、好ましい範囲も同様である。 When 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.
　Ｒ４が、－ＢＲ４ＡＲ４Ｂを表す場合、Ｒ４Ａ、Ｒ４Ｂは、各々独立に、置換基を表す。Ｒ４ＡおよびＲ４Ｂが表す置換基としては、上述した置換基Ｔが挙げられ、ハロゲン原子、アルキル基、アルコキシ基、アリール基、または、ヘテロアリール基が好ましく、アルキル基、アリール基、または、ヘテロアリール基がより好ましく、アリール基が特に好ましい。－ＢＲ４ＡＲ４Ｂで表される基の具体例としては、ジフルオロホウ素基、ジフェニルホウ素基、ジブチルホウ素基、ジナフチルホウ素基、カテコールホウ素基が挙げられる。中でもジフェニルホウ素基が特に好ましい。 When R 4 represents —BR 4A R 4B , R 4A and R 4B each independently represent a substituent. Examples of the 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. 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.
　Ｒ４が金属原子を表す場合、金属原子としては、マグネシウム、アルミニウム、カルシウム、バリウム、亜鉛、スズ、バナジウム、鉄、コバルト、ニッケル、銅、パラジウム、イリジウム、白金が挙げられ、アルミニウム、亜鉛、バナジウム、鉄、銅、パラジウム、イリジウム、白金が特に好ましい。 When 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.
　Ｒ４は、Ｒ１ａ、Ｒ１ｂおよびＲ３の少なくとも１種と共有結合もしくは配位結合していてもよく、特にＲ４がＲ３と配位結合していることが好ましい。Ｒ４は、水素原子または－ＢＲ４ＡＲ４Ｂで表される基（特にジフェニルホウ素基）であることが好ましい。 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).
　式（ＰＰ）で表される化合物の具体例としては、下記化合物が挙げられる。以下の構造式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。
Figure JPOXMLDOC01-appb-C000002
 Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group.
Figure JPOXMLDOC01-appb-C000002
　上述の特性を有する近赤外線吸収有機顔料は、例えば、近赤外線吸収有機顔料の粉砕条件を調整するなどの方法で製造することができる。例えば、近赤外線吸収有機顔料を水溶性有機溶剤および水溶性無機塩の存在下にて混練研磨して製造する方法が挙げられる。好ましくは、近赤外線吸収有機顔料の平均一次粒子径が１０～１００ｎｍの範囲となるように混練研磨し、更に好ましくは、近赤外線吸収有機顔料の平均一次粒子径が２０～４５ｎｍの範囲となるように混練研磨する。 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. For example, the method of kneading | polishing and manufacturing a near-infrared absorption organic pigment in presence of a water-soluble organic solvent and water-soluble inorganic salt is mentioned. Preferably, 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.
　水溶性無機塩は、摩砕剤の役目をし、近赤外線吸収有機顔料と共に混練されることにより近赤外線吸収有機顔料の微細化を進める。水溶性無機塩としては、塩化ナトリウム、塩化カリウム、塩化カルシウム、硫酸ナトリウム、硫酸アルミニウム、炭酸水素ナトリウム等が挙げられ、好ましくは塩化ナトリウムおよび硫酸ナトリウムである。これらの水溶性無機塩は、その粉砕物を用いることができる。また、これらの水溶性無機塩は、１種類単独でも使用できるし、２種類以上の混合物でも使用することができる。 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. Examples of 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.
　水溶性無機塩の平均粒子径Ｄ５０は、１５μｍ以上であることが好ましく、１８μｍ以上であることが更に好ましい。上限は、５０μｍ以下であることが好ましく、３０μｍ以下であることが更に好ましい。近赤外線吸収有機顔料は、有彩色系の有機顔料や、無機顔料と比較して硬度が低く、粒子径の小さい水溶性無機塩を用いて混練研磨を行うと、混練研磨時に近赤外線吸収有機顔料の構造にゆがみが生じたり、近赤外線吸収有機顔料の結晶構造などが変化して可視透明性などが低下することがあるが、粒子径が適度に大きい水溶性無機塩（好ましくは平均粒子径が１５μｍ以上の水溶性無機塩）を用いることで、近赤外線吸収有機顔料の結晶構造の歪みなどを抑制しつつ、結晶性（結晶化度）を適度に調整できる。更には、近赤外線吸収有機顔料を微細化できる（例えば、平均一次粒子径が１０～１００ｎｍ）。このため、粉末Ｘ線回折スペクトルにおいて上述の特性を有し、平均一次粒子径が１０～１００ｎｍの範囲である近赤外線吸収有機顔料を製造しやすい。更には、近赤外線吸収有機顔料の可視透明性および耐熱性をより向上することもできる。 The average particle diameter D50 of the water-soluble inorganic salt is preferably 15 μm or more, and more preferably 18 μm or more. The upper limit is preferably 50 μm or less, and more preferably 30 μm 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. May be distorted, or 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 μm or more, crystallinity (crystallinity) can be appropriately adjusted while suppressing distortion of the crystal structure of the near-infrared absorbing organic pigment. Furthermore, the near-infrared absorbing organic pigment can be refined (for example, the average primary particle size is 10 to 100 nm). Therefore, it is easy to produce a near-infrared absorbing organic pigment having the above-described characteristics in the powder X-ray diffraction spectrum and having an average primary particle diameter in the range of 10 to 100 nm. Furthermore, the visible transparency and heat resistance of the near infrared absorbing organic pigment can be further improved.
　水溶性無機塩の量は、近赤外線吸収有機顔料の質量に対して２．５～２０倍が好ましく、４～１８倍がより好ましく、７～１８倍が更に好ましい。下限は、８倍以上が特に好ましく、１０倍以上が最も好ましい。上限は１７倍以下が特に好ましく、１６倍以下が最も好ましい。水溶性無機塩の量が上述した範囲であれば、近赤外線吸収有機顔料の結晶構造の歪みなどを抑制しつつ、結晶性（結晶化度）を適度に調整できる。更には、近赤外線吸収有機顔料を微細化できる（例えば、平均一次粒子径が１０～１００ｎｍ）。このため、粉末Ｘ線回折スペクトルにおいて上述の特性を有し、平均一次粒子径が１０～１００ｎｍの範囲である近赤外線吸収有機顔料を製造しやすい。更には、近赤外線吸収有機顔料の可視透明性および耐熱性をより向上することもできる。 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. When the amount of the water-soluble inorganic salt is in the above-described range, the crystallinity (crystallinity) can be adjusted appropriately while suppressing the distortion of the crystal structure of the near-infrared absorbing organic pigment. Furthermore, the near-infrared absorbing organic pigment can be refined (for example, the average primary particle size is 10 to 100 nm). Therefore, it is easy to produce a near-infrared absorbing organic pigment having the above-described characteristics in the powder X-ray diffraction spectrum and having an average primary particle diameter in the range of 10 to 100 nm. Furthermore, the visible transparency and heat resistance of the near infrared absorbing organic pigment can be further improved.
　水溶性有機溶剤は、近赤外線吸収有機顔料および水溶性無機塩に対し粘結剤の役目をし、近赤外線吸収有機顔料、水溶性無機塩および水溶性有機溶剤を含む混合物に固さ、粘り気を与えると共に、近赤外線吸収有機顔料の結晶成長や結晶転移を抑制し得る。水溶性有機溶剤は、２３℃の水１００ｇに対する溶解度が２０ｇ以上であることが好ましく、５０ｇ以上であることがより好ましく、１００ｇ以上であることが更に好ましい。この態様によれば、水溶性無機塩を効率よく水洗できる。
　水溶性有機溶剤の具体例としては、エチレングリコール、プロピレングリコール等のアルキレングリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリエチレン－プロピレングリコール等のアルキレングリコールの縮合物、メトキシエタノール、ポリエチレングリコールモノメチルエーテル等の（ポリ）アルキレングリコールのアルキルエーテル、グリセリン等が挙げられ、近赤外線吸収有機顔料、水溶性無機塩および水溶性有機溶剤を含む混合物に適度な固さ、粘り気を与えるという理由から、エチレングリコール、ジエチレングリコール、ポリエチレングリコール等の粘性の高い水溶性有機溶剤が好ましい。水溶性有機溶剤は、１種類単独でも使用できるし、２種類以上の混合物でも使用することができる。水溶性有機溶剤の量は、近赤外線吸収有機顔料の量、水溶性無機塩の量、混練条件（温度、混練速度など）、用いる混練機の特性等により最適量は変わるが、近赤外線吸収有機顔料と水溶性無機塩の合計質量に対して０．１０～０．３５倍が好ましく、０．１２～０．３０倍がより好ましく、０．１５～０．２５倍がさらに好ましい。水溶性有機溶剤の量が上記範囲であれば、近赤外線吸収有機顔料、水溶性無機塩および水溶性有機溶剤を含む混合物に適度な固さ、粘り気を与えることができる。 The water-soluble organic solvent acts as a binder for the near-infrared absorbing organic pigment and the water-soluble inorganic salt. In addition, 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.
Specific examples of 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. 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.
　混練機としては、上記の混合物を混練しうる能力があればよく、双腕型ニーダー、フラッシャー、プラネタリーミキサー等を用いることができる。微細化に対しては剪断力の強い双腕型ニーダーがより好ましい。 As 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. For miniaturization, a double-arm kneader having a strong shearing force is more preferable.
　混練時の温度（ミリング温度）は、近赤外線吸収有機顔料の結晶成長速度の温度依存性や結晶転移性に応じて設定される。一般に低温な程、結晶成長速度は小さい。一方、水溶性有機溶剤の顔料表面への濡れやすさ、顔料塊への水溶性有機溶剤の浸透速度は、高温な程早い。近赤外線吸収有機顔料の整粒は、微細化と結晶成長の両方のバランスによって進展する。例えば、０℃以上が好ましく、１０℃以上がより好ましく、２０℃以上が更に好ましく、３０℃以上がより一層好ましく、４０℃以上が更に一層好ましい。なかでも、平均一次粒子径を１０～１００ｎｍの範囲に調整しつつ、可視透明性および耐熱性に優れた近赤外線吸収有機顔料を製造しやすいという理由から５０℃以上が特に好ましい。上限は、１２０℃以下が好ましく、１００℃以下がより好ましい。 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. Among these, 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.
　近赤外線吸収有機顔料の混練研磨時において、近赤外線吸収有機顔料の微細化、整粒化の進展に応じて、水溶性無機塩や水溶性有機溶剤を追加することができる。また、顔料混練物の排出、再混練は１回に限らず、複数回行っても良い。  At the time of kneading and polishing the near-infrared absorbing organic pigment, 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.
　近赤外線吸収有機顔料の混練研磨時において、近赤外線吸収有機顔料の微細化と共に結晶転移を行わせることもできる。また近赤外線吸収有機顔料の微細化や結晶型制御などのために、顔料誘導体や表面処理剤を添加することもできる。
　混練研磨後の混練物は、水、酸、アルカリなどによる洗浄等、公知の精製法によって精製することで、微細化された近赤外線吸収有機顔料が単離される。環境負荷低減という理由から水洗処理を行って単離することが好ましい。水洗処理後は水を含んだ状態の近赤外線吸収有機顔料をそのまま使用してもよく、乾燥処理を行って、水分を低減させたものを用いてもよい。乾燥処理方法は特に限定はないが、生産性向上という理由から熱風乾燥で行うことが好ましい。また、乾燥処理を行う場合、近赤外線吸収有機顔料の含水率を５％以下とすることが好ましく、２％以下とすることがより好ましい。 At the time of kneading and polishing the near-infrared absorbing organic pigment, crystal transition can be performed together with the miniaturization of the near-infrared absorbing organic pigment. In addition, 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. After the water washing treatment, 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. Moreover, when performing a drying process, it is preferable to make the moisture content of a near-infrared absorption organic pigment into 5% or less, and it is more preferable to set it as 2% or less.
＜顔料分散液＞
　次に、本発明の顔料分散液について説明する。本発明の顔料分散液は、上述した近赤外線吸収有機顔料と、樹脂と、溶剤とを含む。 <Pigment dispersion>
Next, the pigment dispersion of the present invention will be described. The pigment dispersion of the present invention contains the above-described near-infrared absorbing organic pigment, a resin, and a solvent.
　本発明の顔料分散液の粘度（２３℃）は、２～３０ｍＰａ・ｓであることが好ましい。下限は、３ｍＰａ・ｓ以上が好ましく、４ｍＰａ・ｓ以上がより好ましい。上限は、２０ｍＰａ・ｓ以下が好ましく、１５ｍＰａ・ｓ以下が更に好ましい。 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.
　本発明の顔料分散液のチキソトロピー性は、低いことが好ましい。チキソトロピー性とはＴｉ値の指標で表すことができる。例えばＥ型粘度計（東機産業製ＲＥ８５Ｌ）を用いて測定される粘度において、回転数が２０ｒｐｍと５０ｒｐｍの粘度をそれぞれη（２０ｒｐｍ）、η（５０ｒｐｍ）とする時のη（２０ｒｐｍ）／η（５０ｒｐｍ）の値をＴｉ値とする。Ｔｉ値が１に近いほどチキソトロピー性が低いことを意味する。このような測定方法で得られたＴｉ値に関して、２３℃におけるＴｉ値は、０．８～１．４であることが好ましく、０．９～１．２であることがより好ましく、０．９～１．１であることが更に好ましい。 It is preferable that 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. 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, η (20 rpm) and η (50 rpm), η (20 rpm) / η Let the value of (50 rpm) be Ti value. The closer the Ti value is to 1, the lower the thixotropic property. Regarding the Ti value obtained by such a measuring method, 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.
　本発明の顔料分散液は、波長７００～１０００ｎｍの範囲に極大吸収波長を有することが好ましい。また、波長５５０ｎｍにおける吸光度Ａ５５０と極大吸収波長における吸光度Ａｍａｘとの比である吸光度Ａ５５０／吸光度Ａｍａｘは、０．００２～０．０４０であることが好ましく、０．００３～０．０３０であることがより好ましく、０．００４～０．０２０であることが更に好ましい。また、波長４００ｎｍにおける吸光度Ａ４００と極大吸収波長における吸光度Ａｍａｘとの比である吸光度Ａ４００／吸光度Ａｍａｘは０．００５～０．１５０であることが好ましく、０．０２０～０．１００であることがより好ましく、０．０５０～０．０７０であることが更に好ましい。本発明の顔料分散液における極大吸収波長は、７２０～９８０ｎｍの範囲に有することがより好ましく、７４０～９６０ｎｍの範囲に有することがさらに好ましい。 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.
＜＜近赤外線吸収有機顔料＞＞
　本発明の顔料分散液は、上述した近赤外線吸収有機顔料を含有する。近赤外線吸収有機顔料の含有量は、顔料分散液の全固形分に対して３０～９９質量％であることが好ましく、５０～９９質量％であることがより好ましく、６０～９９質量％であることが更に好ましい。 << Near-infrared absorbing organic pigment >>
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.
＜＜溶剤＞＞
　本発明の分散液は、溶剤を含む。溶剤としては、有機溶剤が挙げられる。有機溶剤の例としては、例えば、以下の有機溶剤が挙げられる。エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸シクロヘキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が挙げられる。エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が挙げられる。ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン等が挙げられる。芳香族炭化水素類として、例えば、トルエン、キシレン等が挙げられる。ただし溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << Solvent >>
The dispersion of the present invention contains a solvent. Examples of the solvent include organic solvents. Examples of the organic solvent include the following organic solvents. Examples of 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, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Til, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of 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. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of 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).
　有機溶剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。有機溶剤を２種以上組み合わせて用いる場合、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、及びプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液が好ましい。 Organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone 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.
　本発明において、金属含有量の少ない溶剤を用いることが好ましく、溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 In the present invention, 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).
　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０ｎｍ以下が好ましく、５ｎｍ以下がより好ましく、３ｎｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 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.
　溶剤は、異性体（同じ原子数で異なる構造の化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 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.
　本発明において、有機溶剤は、過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
　溶剤の含有量は、顔料分散液の全量に対し、６０～９２質量％であることが好ましく、７０～９０質量％であることがより好ましく、７５～８９質量％であることが更に好ましい。溶剤は１種類のみでもよく、２種類以上でもよい。溶剤を２種類以上含む場合は、合計量が上記範囲となることが好ましい。 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.
＜＜樹脂＞＞
　本発明の顔料分散液は、樹脂を含む。樹脂は、顔料などを分散させる用途で配合される。なお、主に顔料などを分散させるために用いる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。 << Resin >>
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. However, such use of the resin is an example, and the resin can be used for purposes other than such use.
　樹脂の重量平均分子量（Ｍｗ）は、２,０００～２,０００,０００が好ましい。上限は、１,０００,０００以下が好ましく、５００,０００以下がより好ましい。下限は、３,０００以上が好ましく、５,０００以上がより好ましい。 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.
　分散剤として用いる樹脂としては、酸性樹脂、塩基性樹脂および両性樹脂から選ばれる１種以上が好ましく、酸性樹脂および両性樹脂から選ばれる１種以上がより好ましい。
　本発明において、酸性樹脂とは、酸基を有する樹脂であって、酸価が５ｍｇＫＯＨ／ｇ以上、アミン価が５ｍｇＫＯＨ／ｇ未満の樹脂を意味する。酸性樹脂は、塩基性基を有さないことが好ましい。酸性樹脂が有する酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。酸性樹脂の酸価は、５～２００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１００ｍｇＫＯＨ／ｇ以下がより好ましく、６０ｍｇＫＯＨ／ｇ以下がさらに好ましい。また、酸性樹脂のアミン価は、２ｍｇＫＯＨ／ｇ以下が好ましく、１ｍｇＫＯＨ／ｇ以下がより好ましい。
　本発明において、塩基性樹脂とは、塩基性基を有する樹脂であって、アミン価が５ｍｇＫＯＨ／ｇ以上、酸価が５ｍｇＫＯＨ／ｇ未満の樹脂を意味する。塩基性樹脂は、酸基を有さないことが好ましい。塩基性樹脂が有する塩基性基としては、アミノ基が好ましい。塩基性樹脂のアミン価は、５～２００ｍｇＫＯＨ／ｇが好ましく、５～１５０ｍｇＫＯＨ／ｇがより好ましく、５～１００ｍｇＫＯＨ／ｇがさらに好ましい。
　本発明において、両性樹脂とは、酸基と塩基性基を有する樹脂であって、酸価が５ｍｇＫＯＨ／ｇ以上で、アミン価が５ｍｇＫＯＨ／ｇ以上である樹脂を意味する。酸基としては、前述したものが挙げられ、カルボキシル基が好ましい。塩基性基としては、アミノ基が好ましい。両性樹脂は、酸価が５ｍｇＫＯＨ／ｇ以上で、アミン価が５ｍｇＫＯＨ／ｇ以上であることが好ましい。酸価は、５～２００ｍｇＫＯＨ／ｇがより好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。また、アミン価は、５～２００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。両性樹脂の酸価とアミン価の比率は、酸価：アミン価＝１：４～４：１が好ましく、１：３～３：１がより好ましい。 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.
In the present invention, 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. Further, the amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less.
In the present invention, 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. As a basic group which basic resin has, 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.
In the present invention, 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. Examples of the acid group include those described above, and a carboxyl group is preferable. As the basic group, 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 ratio between the acid value and the amine value of the amphoteric resin is preferably acid value: amine value = 1: 4 to 4: 1, more preferably 1: 3 to 3: 1.
　樹脂は、酸基を有する繰り返し単位を含むことが好ましい。酸基を有する繰り返し単位を含む樹脂を用いるにより、フォトリソグラフィによりパターンを形成する際、画素の下地に発生する残渣をより減少させることができる。 The resin preferably contains a repeating unit having an acid group. By using a resin including a repeating unit having an acid group, residue generated on the base of the pixel can be further reduced when a pattern is formed by photolithography.
　樹脂は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。末端変性型高分子としては、例えば、特開平３－１１２９９２号公報、特表２００３－５３３４５５号公報等に記載の末端にリン酸基を有する高分子、特開２００２－２７３１９１号公報等に記載の末端にスルホ基を有する高分子、特開平９－７７９９４号公報等に記載の有機色素の部分骨格や複素環を有する高分子などが挙げられる。また、特開２００７－２７７５１４号公報に記載の高分子末端に２個以上の顔料表面へのアンカー部位（酸基、塩基性基、有機色素の部分骨格やヘテロ環等）を導入した高分子も分散安定性に優れ好ましい。グラフト型高分子としては、例えば、特開昭５４－３７０８２号公報、特表平８－５０７９６０号公報、特開２００９－２５８６６８公報等に記載のポリ（低級アルキレンイミン）とポリエステルの反応生成物、特開平９－１６９８２１号公報等に記載のポリアリルアミンとポリエステルの反応生成物、特開平１０－３３９９４９号公報、特開２００４－３７９８６号公報等に記載のマクロモノマーと、窒素原子を有するモノマーとの共重合体、特開２００３－２３８８３７号公報、特開２００８－９４２６号公報、特開２００８－８１７３２号公報等に記載の有機色素の部分骨格や複素環を有するグラフト型高分子、特開２０１０－１０６２６８号公報等に記載のマクロモノマーと酸基含有モノマーの共重合体などが挙げられる。ブロック型高分子としては、特開２００３－４９１１０号公報、特開２００９－５２０１０号公報等に記載のブロック型高分子が好ましい。 Resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. Examples of 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. In addition, 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. Examples of 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. Reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, macromonomers described in JP-A-10-339949, JP-A-2004-37986, and the like, and a monomer having a nitrogen atom Copolymers, graft-type polymers having a partial skeleton of organic dye or a heterocyclic ring described in JP-A No. 2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc., JP-A 2010- Examples thereof include a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-106268. As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
　本発明において、樹脂は、下記式（１１）～式（１４）のいずれかで表される繰り返し単位を含むグラフト共重合体を用いることもできる。 In the present invention, as the resin, a graft copolymer containing a repeating unit represented by any of the following formulas (11) to (14) can also be used.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（１１）～式（１４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４はそれぞれ独立に酸素原子、または、ＮＨを表し、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５はそれぞれ独立に水素原子又は１価の基を表し、Ｙ１、Ｙ２、Ｙ３、及びＹ４はそれぞれ独立に２価の連結基を表し、Ｚ１、Ｚ２、Ｚ３、及びＺ４はそれぞれ独立に１価の基を表し、Ｒ３はアルキレン基を表し、Ｒ４は水素原子又は１価の基を表し、ｎ、ｍ、ｐ、及びｑはそれぞれ独立に１～５００の整数を表し、ｊ及びｋはそれぞれ独立に２～８の整数を表す。式（１３）において、ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよく、式（１４）において、ｑが２～５００のとき、複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。 In the formulas (11) to (14), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, and X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent group; Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group; and Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent group, R 3 represents an alkylene group, R 4 represents a hydrogen atom or a monovalent group, and 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. In the formula (13), 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.
　上記グラフト共重合体については、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、本明細書には上記内容が組み込まれる。上記グラフト共重合体の具体例としては、例えば、以下の樹脂が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号００７２～００９４に記載の樹脂が挙げられ、この内容は本明細書に組み込まれる。 Regarding the 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.
　また、樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むオリゴイミン系分散剤を用いることもできる。オリゴイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する繰り返し単位と、原子数４０～１０，０００の側鎖Ｙを含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子は、塩基性を呈する窒素原子であれば特に制限はない。
　オリゴイミン系分散剤は、例えば、下記式（Ｉ－１）で表される繰り返し単位と、式（Ｉ－２）で表される繰り返し単位、および／または、式（Ｉ－２ａ）で表される繰り返し単位を含む樹脂などが挙げられる。 In addition, as the resin, 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.
Figure JPOXMLDOC01-appb-C000004
 　Ｒ１及びＲ２は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１～６が好ましい）を表す。ａは、各々独立に、１～５の整数を表す。＊は繰り返し単位間の連結部を表す。Ｒ８及びＲ９はＲ１と同義の基である。Ｌは単結合、アルキレン基（炭素数１～６が好ましい）、アルケニレン基（炭素数２～６が好ましい）、アリーレン基（炭素数６～２４が好ましい）、ヘテロアリーレン基（炭素数１～６が好ましい）、イミノ基（炭素数０～６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは－ＣＲ５Ｒ６－ＮＲ７－（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ５、Ｒ６は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１～６が好ましい）を表す。Ｒ７は水素原子または炭素数１～６のアルキル基である。
　ＬａはＣＲ８ＣＲ９とＮとともに環構造を形成する構造部位であり、ＣＲ８ＣＲ９の炭素原子と合わせて炭素数３～７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくは、ＣＲ８ＣＲ９の炭素原子及びＮ（窒素原子）を合わせて５～７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。
　ＸはｐＫａ１４以下の官能基を有する基を表す。
　Ｙは原子数４０～１０，０００の側鎖を表す。
　オリゴイミン系分散剤は、さらに式（Ｉ－３）、式（Ｉ－４）、および、式（Ｉ－５）で表される繰り返し単位から選ばれる１種以上を共重合成分として含有していてもよい。オリゴイミン系分散剤が、このような繰り返し単位を含むことで、分散性能を更に向上させることができる。
Figure JPOXMLDOC01-appb-C000004
 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). Are preferred), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a combination group thereof. Among these, a single bond or —CR 5 R 6 —NR 7 — (imino group is X or Y) is preferable. Here, 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.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　Ｒ１、Ｒ２、Ｒ８、Ｒ９、Ｌ、Ｌａ、ａ及び＊は式（Ｉ－１）、（Ｉ－２）、（Ｉ－２ａ）における規定と同義である。Ｙａはアニオン基を有する原子数４０～１０，０００の側鎖を表す。式（Ｉ－３）で表される繰り返し単位は、主鎖部に一級又は二級アミノ基を有する樹脂に、アミンと反応して塩を形成する基を有するオリゴマー又はポリマーを添加して反応させることで形成することが可能である。 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.
　オリゴイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、本明細書には上記内容が組み込まれる。オリゴイミン系分散剤の具体例としては、例えば、以下が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号０１６８～０１７４に記載の樹脂を用いることができる。
Figure JPOXMLDOC01-appb-C000006
 Regarding the 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.
Figure JPOXMLDOC01-appb-C000006
　樹脂は、市販品としても入手可能であり、そのような具体例としては、Ｄｉｓｐｅｒｂｙｋ－１１１（ＢＹＫＣｈｅｍｉｅ社製）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。また、樹脂は、後述する硬化性組成物で説明するアルカリ可溶性樹脂などを用いることもできる。 The resin is also available as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie). In addition, 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. Moreover, alkali-soluble resin etc. which are demonstrated by curable composition mentioned later can also be used for resin.
　本発明の顔料分散液における樹脂の含有量は、顔料１００質量部に対して、０．１～１００質量部が好ましい。上限は、８０質量部以下がより好ましく、６０質量部以下がさらに好ましく、４０質量部以下が一層好ましい。下限は、０．５質量部以上がより好ましく、１質量部以上がさらに好ましい。樹脂の含有量が上記範囲であれば、顔料の分散性が良好である。 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. When the resin content is in the above range, the dispersibility of the pigment is good.
＜＜顔料誘導体＞＞
　本発明の顔料分散液は、更に顔料誘導体を含有することが好ましい。顔料誘導体としては、顔料の一部を、酸性基、塩基性基、塩構造を有する基又はフタルイミドメチル基で置換した構造を有する化合物が挙げられ、式（Ｂ１）で表される顔料誘導体が好ましい。 << Pigment derivative >>
The pigment dispersion of the present invention preferably further contains a pigment derivative. Examples of 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. .
Figure JPOXMLDOC01-appb-C000007
 　式（Ｂ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸性基、塩基性基、塩構造を有する基またはフタルイミドメチル基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。
Figure JPOXMLDOC01-appb-C000007
 In formula (B1), 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, and m is an integer of 1 or more. N represents an integer of 1 or more. When m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.
　式（Ｂ１）中、Ｐは、色素構造を表し、ピロロピロール色素構造、ジケトピロロピロール色素構造、キナクリドン色素構造、アントラキノン色素構造、ジアントラキノン色素構造、ベンゾイソインドール色素構造、チアジンインジゴ色素構造、アゾ色素構造、キノフタロン色素構造、フタロシアニン色素構造、ナフタロシアニン色素構造、ジオキサジン色素構造、ペリレン色素構造、ペリノン色素構造、ベンゾイミダゾロン色素構造、ベンゾチアゾール色素構造、ベンゾイミダゾール色素構造およびベンゾオキサゾール色素構造から選ばれる少なくとも１種が好ましく、ピロロピロール色素構造、ジケトピロロピロール色素構造、キナクリドン色素構造およびベンゾイミダゾロン色素構造から選ばれる少なくとも１種が更に好ましく、ピロロピロール色素構造が特に好ましい。 In formula (B1), 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.
　式（Ｂ１）中、Ｌは単結合または連結基を表す。連結基としては、１～１００個の炭素原子、０～１０個の窒素原子、０～５０個の酸素原子、１～２００個の水素原子、および０～２０個の硫黄原子から成り立つ基が好ましく、無置換でもよく、置換基を更に有していてもよい。具体的には、アルキレン基、アリーレン基、含窒素複素環基、－Ｏ－、－Ｓ－、－ＮＲ’－、－ＣＯ－、－ＳＯ２－もしくはこれらの組み合わせからなる基が挙げられる。Ｒ’は、水素原子、アルキル基またはアリール基を表す。 In formula (B1), 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.
　式（Ｂ１）中、Ｘは、酸性基、塩基性基、塩構造を有する基またはフタルイミドメチル基を表す。酸性基としては、カルボキシル基、スルホ基等が挙げられる。塩基性基としてはアミノ基が好ましく、特に三級アミノ基が好ましい。塩構造を有する基としては、上述した酸性基の塩、塩基性基の塩が挙げられる。塩を構成する原子または原子団としては、金属原子、テトラブチルアンモニウムなどが挙げられる。金属原子としては、アルカリ金属原子またはアルカリ土類金属原子が好ましい。アルカリ金属原子としては、リチウム、ナトリウム、カリウム等が挙げられる。アルカリ土類金属原子としては、カルシウム、マグネシウム等が挙げられる。 In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimidomethyl group. Examples of the acidic group include a carboxyl group and a sulfo group. As the basic group, an amino group is preferable, and a tertiary amino group is particularly preferable. Examples of the group having a salt structure include the above-mentioned acidic group salts and basic group salts. Examples of the atoms or atomic groups constituting the salt include metal atoms and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is preferable. Examples of the alkali metal atom include lithium, sodium, potassium and the like. Examples of alkaline earth metal atoms include calcium and magnesium.
　顔料誘導体の具体例としては、下記化合物が挙げられる。また、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平１－２１７０７７号公報、特開平３－９９６１号公報、特開平３－２６７６７号公報、特開平３－１５３７８０号公報、特開平３－４５６６２号公報、特開平４－２８５６６９号公報、特開平６－１４５５４６号公報、特開平６－２１２０８８号公報、特開平６－２４０１５８号公報、特開平１０－３００６３号公報、特開平１０－１９５３２６号公報、国際公開ＷＯ２０１１／０２４８９６号公報の段落番号００８６～００９８、国際公開ＷＯ２０１２／１０２３９９号公報の段落番号００６３～００９４等に記載の化合物、国際公開ＷＯ２０１６／０３５６９５号公報の段落番号００５３に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。顔料誘導体としては、下記の化合物（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－６）、（Ｂ－１５）、（Ｂ－１６）、（Ｂ－１８）、（Ｂ－３０）、（Ｂ－６１）、および（Ｂ－６２）が特に好ましい。 Specific examples of the pigment derivative 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. Examples of 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.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明の顔料分散液が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料１００質量部に対し、１～５０質量部が好ましい。下限値は、３質量部以上が好ましく、５質量部以上がより好ましい。上限値は、４０質量部以下が好ましく、３０質量部以下がより好ましい。顔料誘導体の含有量が上記範囲であれば、顔料の分散性を高めて、顔料の凝集を効率よく抑制できる。顔料誘導体は１種類のみでも、２種類以上でもよく、２種類以上の場合は、合計量が上記範囲となることが好ましい。 When the pigment dispersion of the present invention contains a pigment derivative, 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.
＜顔料分散液の調製＞
　本発明の顔料分散液は、前述の成分を混合して調製できる。顔料分散液の調製に際しては、各成分を一括配合してもよいし、各成分を溶剤に溶解または分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解または分散して顔料分散液を調製してもよい。 <Preparation of pigment dispersion>
The pigment dispersion of the present invention can be prepared by mixing the aforementioned components. In preparing the pigment dispersion, the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, a pigment dispersion may be prepared by simultaneously dissolving or dispersing all components in a solvent.
　顔料分散液の調製において、顔料を分散させるプロセスを含むことが好ましい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。 The preparation of the pigment dispersion preferably includes a process for dispersing the pigment. In the process of 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. Processes and dispersers that disperse pigments are described in “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)”. In fact, a comprehensive document collection, published by the Management Development Center Publishing Department, October 10, 1978 ”, paragraph No. 0022 of JP-A-2015-157893 can be suitably used.
　顔料分散液の調製にあたり、異物の除去や欠陥の低減などの目的で、顔料分散液をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。
　フィルタの孔径は、０．０１～７．０μｍ程度が適しており、好ましくは０．０１～３．０μｍ程度であり、更に好ましくは０．０５～０．５μｍ程度である。フィルタの孔径が上記範囲であれば、微細な異物を確実に除去できる。また、ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。具体的には、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）のフィルタカートリッジが挙げられる。 In preparing the pigment dispersion, it is preferable to filter the pigment dispersion with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration. For example, 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) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. 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. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Specifically, 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.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。
　また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社（ＤＦＡ４２０１ＮＸＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
　第２のフィルタは、第１のフィルタと同様の素材等で形成されたものを使用することができる。 When using the filters, different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
Moreover, you may combine the filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As 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.
As the second filter, a filter formed of the same material as the first filter can be used.
＜硬化性組成物＞
　次に、本発明の硬化性組成物について説明する。本発明の硬化性組成物は、上述した近赤外線吸収有機顔料と、樹脂と、硬化性化合物と、溶剤とを含む。本発明の硬化性組成物は、上述した顔料分散液と、硬化性化合物とを含む組成物であることも好ましい。本発明の硬化性組成物は、光硬化性組成物であってもよく、熱硬化性組成物であってもよい。光硬化性組成物の場合、重合性化合物（好ましくはラジカル重合性化合物）と光重合開始剤（好ましくは光ラジカル重合開始剤）とを含む組成物であることが好ましい。 <Curable composition>
Next, the curable composition of this invention is demonstrated. The curable composition of this invention contains the near-infrared absorption organic pigment mentioned above, resin, a sclerosing | hardenable compound, and a solvent. 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).
＜＜近赤外線吸収有機顔料＞＞
　本発明の硬化性組成物は、上述した近赤外線吸収有機顔料を含有する。近赤外線吸収有機顔料の含有量は、硬化性組成物の全固形分に対して、０．１～６０質量％が好ましい。下限は、１質量％以上が好ましく、５質量％以上がより好ましい。上限は、５０質量％以下が好ましく、４０質量％以下がより好ましい。 << Near-infrared absorbing organic pigment >>
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.
＜＜他の近赤外線吸収化合物＞＞
　本発明の組成物は、上述した近赤外線吸収有機顔料以外の近赤外線吸収化合物（他の近赤外線吸収化合物ともいう）をさらに含んでもよい。他の近赤外線吸収化合物としては、染料が挙げられる。化合物種としては、例えば、フタロシアニン化合物、ナフタロシアニン化合物、リレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、ジイミニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物及びジベンゾフラノン化合物などが挙げられる。フタロシアニン化合物、ナフタロシアニン化合物、ジイミニウム化合物およびクロコニウム化合物としては、特開２０１０－１１１７５０号公報の段落番号００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。また、ＩＲＡ８６８（Ｅｘｉｔｏｎ社製）、ＩＲＧ－０６８（日本化薬（株）製）などを用いることもできる。 << Other near-infrared absorbing compounds >>
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. Examples of other near infrared absorbing compounds include dyes. Examples of 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. As the 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.), and the like can also be used.
　また、他の近赤外線吸収化合物として、無機粒子を用いることもできる。無機粒子は、赤外線遮蔽性がより優れる点で、金属酸化物粒子または金属粒子が好ましい。金属酸化物粒子としては、例えば、酸化インジウムスズ（ＩＴＯ）粒子、酸化アンチモンスズ（ＡＴＯ）粒子、酸化亜鉛（ＺｎＯ）粒子、Ａｌドープ酸化亜鉛（ＡｌドープＺｎＯ）粒子、フッ素ドープ二酸化スズ（ＦドープＳｎＯ２）粒子、ニオブドープ二酸化チタン（ＮｂドープＴｉＯ２）粒子などが挙げられる。金属粒子としては、例えば、銀（Ａｇ）粒子、金（Ａｕ）粒子、銅（Ｃｕ）粒子、ニッケル（Ｎｉ）粒子など挙げられる。また、無機微粒子としては酸化タングステン系化合物が使用できる。酸化タングステン系化合物は、セシウム酸化タングステンであることが好ましい。酸化タングステン系化合物の詳細については、特開２０１６－００６４７６号公報の段落番号００８０を参酌でき、この内容は本明細書に組み込まれる。無機粒子の形状は特に制限されず、球状、非球状を問わず、シート状、ワイヤー状、チューブ状であってもよい。 Moreover, 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. Examples of 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). SnO 2 ) particles, niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. Moreover, a tungsten oxide compound can be used as the inorganic fine particles. The tungsten oxide compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, 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.
　無機粒子の平均粒子径は、８００ｎｍ以下が好ましく、４００ｎｍ以下がより好ましく、２００ｎｍ以下が更に好ましい。無機粒子の平均粒子径がこのような範囲であることによって、可視透明性が良好である。光散乱を回避する観点からは、平均粒子径は小さいほど好ましいが、製造時における取り扱い容易性などの理由から、無機粒子の平均粒子径は、通常、１ｎｍ以上である。 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. When the average particle diameter of the inorganic particles is within such a range, the visible transparency is good. From the viewpoint of avoiding light scattering, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the inorganic particles is usually 1 nm or more.
　本発明の硬化性組成物が他の近赤外線吸収化合物を含有する場合、他の近赤外線吸収化合物の含有量は、近赤外線吸収有機顔料の１００質量部に対し０．１～８０質量部が好ましく、５～６０質量部がより好ましく、１０～４０質量部がさらに好ましい。 When the curable composition of the present invention contains other near infrared absorbing compound, 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.
＜＜有彩色着色剤＞＞
　本発明の硬化性組成物は、有彩色着色剤を含有することができる。本発明において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、波長４００ｎｍ以上６５０ｎｍ未満の範囲に吸収を有する着色剤が好ましい。 << Chromatic colorant >>
The curable composition of the present invention can contain a chromatic colorant. In the present invention, 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.
　本発明において、有彩色着色剤は、顔料であってもよく、染料であってもよい。顔料は、有機顔料であることが好ましい。有機顔料としては、以下が挙げることができる。
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等（以上、青色顔料）、
　これら有機顔料は、単独若しくは種々組合せて用いることができる。 In the present invention, the chromatic colorant may be a pigment or a dye. The pigment is preferably an organic pigment. The following can be mentioned as an organic pigment.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange 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, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.
　染料としては特に制限はなく、公知の染料が使用できる。化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が使用できる。また、これらの染料の多量体を用いてもよい。また、特開２０１５－０２８１４４号公報、特開２０１５－３４９６６号公報に記載の染料を用いることもできる。 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.
　本発明の硬化性組成物が、有彩色着色剤を含有する場合、有彩色着色剤の含有量は、本発明の硬化性組成物の全固形分に対して０．１～７０質量％が好ましい。下限は、０．５質量％以上が好ましく、１．０質量％以上がより好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましい。
　有彩色着色剤の含有量は、近赤外線吸収有機顔料の１００質量部に対し、１０～１０００質量部が好ましく、５０～８００質量部がより好ましい。
　また、有彩色着色剤と近赤外線吸収有機顔料との合計量は、本発明の硬化性組成物の全固形分に対して１～８０質量％とすることが好ましい。下限は、５質量％以上が好ましく、１０質量％以上がより好ましい。上限は、７０質量％以下が好ましく、６０質量％以下がより好ましい。
　本発明の硬化性組成物が、有彩色着色剤を２種以上含む場合、その合計量が上記範囲内であることが好ましい。 When the curable composition of the present invention contains a chromatic colorant, 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.
When the curable composition of this invention contains 2 or more types of chromatic colorants, it is preferable that the total amount is in the said range.
＜＜赤外線を透過させて可視光を遮光する色材＞＞
　本発明の硬化性組成物は、赤外線を透過させて可視光を遮光する色材（以下、可視光を遮光する色材ともいう）を含有することもできる。
　本発明において、可視光を遮光する色材は、紫色から赤色の波長領域の光を吸収する色材であることが好ましい。また、本発明において、可視光を遮光する色材は、波長４５０～６５０ｎｍの波長領域の光を遮光する色材であることが好ましい。また、可視光を遮光する色材は、波長９００～１３００ｎｍの光を透過する色材であることが好ましい。
　本発明において、可視光を遮光する色材は、以下の（１）および（２）の少なくとも一方の要件を満たすことが好ましい。
（１）：２種類以上の有彩色着色剤を含み、２種以上の有彩色着色剤の組み合わせで黒色を形成している。
（２）：有機系黒色着色剤を含む。（２）の態様において、更に有彩色着色剤を含有することも好ましい。 << Coloring material that transmits infrared rays and blocks visible light >>
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).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the wavelength range from purple to red. In the present invention, 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.
In the present invention, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2).
(1): Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants.
(2): Contains an organic black colorant. In the aspect (2), it is also preferable to further contain a chromatic colorant.
　また、本発明において、可視光を遮光する色材としての有機系黒色着色剤は、可視光を吸収するが、赤外線の少なくとも一部は透過する材料である。したがって、本発明において、可視光を遮光する色材としての有機系黒色着色剤は、可視光および赤外線の両方を吸収する黒色着色剤、例えば、カーボンブラックやチタンブラックは含まない。 In the present invention, 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.
　有彩色着色剤としては、上述したものが挙げられる。有機系黒色着色剤としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ系化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。アゾメチン化合物としては、特開平１－１７０６０１号公報、特開平２－３４６６４号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。 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.
　本発明において、可視光を遮光する色材は、例えば、波長４５０～６５０ｎｍの範囲における吸光度の最小値Ａと、波長９００～１３００ｎｍの範囲における吸光度の最小値Ｂとの比であるＡ／Ｂが４．５以上であることが好ましい。
　上記の特性は、１種類の素材で満たしていてもよく、複数の素材の組み合わせで満たしていてもよい。例えば、上記（１）の態様の場合、複数の有彩色着色剤を組み合わせて上記分光特性を満たしていることが好ましい。また、上記（２）の態様の場合、有機系黒色着色剤が上記分光特性を満たしていてもよい。また、有機系黒色着色剤と有彩色着色剤との組み合わせで上記の分光特性を満たしていてもよい。 In the present invention, 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. For example, in the case of the above aspect (1), it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral characteristics. In the case of the above (2), the organic black colorant may satisfy the above spectral characteristics. Further, the above-described spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
　２種以上の有彩色着色剤の組み合わせで黒色を形成する場合の、有彩色着色剤の組み合わせとしては、例えば以下が挙げられる。
（１）黄色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（２）黄色着色剤、青色着色剤および赤色着色剤を含有する態様。
（３）黄色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（４）黄色着色剤および紫色着色剤を含有する態様。
（５）緑色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（６）紫色着色剤およびオレンジ色着色剤を含有する態様。
（７）緑色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（８）緑色着色剤および赤色着色剤を含有する態様。 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.
　各着色剤の比率(質量比)としては例えば以下が挙げられる。
Figure JPOXMLDOC01-appb-T000010
 Examples of the ratio (mass ratio) of each colorant include the following.
Figure JPOXMLDOC01-appb-T000010
　本発明の硬化性組成物が、可視光を遮光する色材を含有する場合、可視光を遮光する色材の含有量は、硬化性組成物の全固形分に対して３０質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下が更に好ましい。下限は、例えば、０．０１質量％以上とすることができ、０．５質量％以上とすることもできる。
　また、本発明の硬化性組成物は、可視光を遮光する色材を実質的に含有しない態様とすることもできる。可視光を遮光する色材を実質的に含有しないとは、可視光を遮光する色材の含有量が、本発明の硬化性組成物の全固形分中、０．００５質量％以下が好ましく、０．００１質量％以下が更に好ましく、可視光を遮光する色材を含有しないことが一層好ましい。 When the curable composition of the present invention contains a color material that blocks visible light, 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. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, 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.
＜＜顔料誘導体＞＞
　本発明の硬化性組成物は、顔料誘導体を含有することが好ましい。顔料誘導体としては、上述した顔料分散液で説明した顔料誘導体が挙げられる。 << Pigment derivative >>
The curable composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include the pigment derivatives described in the above-described pigment dispersion.
　本発明の硬化性組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料１００質量部に対し、１～５０質量部が好ましい。下限値は、３質量部以上が好ましく、５質量部以上がより好ましい。上限値は、４０質量部以下が好ましく、３０質量部以下がより好ましい。顔料誘導体は１種類のみでも、２種類以上でもよく、２種類以上の場合は、合計量が上記範囲となることが好ましい。 When the curable composition of the present invention contains a pigment derivative, 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.
＜＜樹脂＞＞
　本発明の硬化性組成物は、樹脂を含有する。樹脂は、例えば、顔料などを硬化性組成物中で分散させる用途、バインダーの用途で配合される。なお、主に顔料などを分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的で樹脂を使用することもできる。
　樹脂としては、 << Resin >>
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. However, such use of the resin is an example, and the resin can be used for purposes other than such use.
As resin,
　樹脂の重量平均分子量（Ｍｗ）は、２,０００～２,０００,０００が好ましい。上限は、１,０００,０００以下が好ましく、５００,０００以下がより好ましい。下限は、３,０００以上が好ましく、５,０００以上がより好ましい。 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.
　樹脂としては、上述した顔料分散液で説明した樹脂が挙げられる。また、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルフォスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などの樹脂を用いることも好ましい。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。 Examples of the resin 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.
　本発明で用いる樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシル基などが挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂として用いることもできる。また、分散剤として用いることもできる。 The resin used in the present invention may have an acid group. Examples of 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.
　アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）は、５０００～１００，０００が好ましい。また、アルカリ可溶性樹脂の数平均分子量（Ｍｎ）は、１０００～２０，０００が好ましい。アルカリ可溶性樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上が更に好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下が更に好ましく、１５０ｍｇＫＯＨ／ｇ以下が特に好ましく、１２０ｍｇＫＯＨ／ｇ以下が最も好ましい。 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.
　アルカリ可溶性樹脂としては、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。また、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。 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.
　アルカリ可溶性樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。具体例としては、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシル基を有するポリマーに酸無水物を付加させた樹脂が挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等、ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。また他のモノマーは、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマー、例えば、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等を用いることもできる。なお、これらの（メタ）アクリル酸と共重合可能な他のモノマーは１種のみであってもよいし、２種以上であってもよい。 As the 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. 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. In particular, 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. As 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, Examples of 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, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used. In addition, 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.
　アルカリ可溶性樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体なども好ましく用いることができる。 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. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.
　アルカリ可溶性樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分を重合してなるポリマーを含むことも好ましい。 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.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（ＥＤ１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000012
 　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), 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.
Figure JPOXMLDOC01-appb-C000012
 In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP 2010-168539 A can be referred to.
　式（ＥＤ１）中、Ｒ１およびＲ２で表される置換基を有していてもよい炭素数１～２５の炭化水素基としては、特に制限はないが、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｔｅｒｔ－アミル、ステアリル、ラウリル、２－エチルヘキシル等の直鎖状または分岐状のアルキル基；フェニル等のアリール基；シクロヘキシル、ｔｅｒｔ－ブチルシクロヘキシル、ジシクロペンタジエニル、トリシクロデカニル、イソボルニル、アダマンチル、２－メチル－２－アダマンチル等の脂環式基；１－メトキシエチル、１－エトキシエチル等のアルコキシで置換されたアルキル基；ベンジル等のアリール基で置換されたアルキル基；等が挙げられる。これらの中でも特に、メチル、エチル、シクロヘキシル、ベンジル等のような酸や熱で脱離しにくい１級または２級炭素の置換基が耐熱性の点で好ましい。 In the formula (ED1), 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 Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.
　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 As a specific example of the 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.
　酸基を有する樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000013
 　式（Ｘ）において、Ｒ１は、水素原子またはメチル基を表し、Ｒ２は炭素数２～１０のアルキレン基を表し、Ｒ３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000013
 In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
　アルカリ可溶性樹脂としては、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Examples of the alkali-soluble resin 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.
　アルカリ可溶性樹脂としては、重合性基を有するアルカリ可溶性樹脂を使用してもよい。重合性基としては、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。重合性基を有するアルカリ可溶性樹脂は、重合性基を側鎖に有するアルカリ可溶性樹脂が好ましい。重合性基を有するアルカリ可溶性樹脂としては、ダイヤナールＮＲシリーズ（三菱レイヨン株式会社製）、Ｐｈｏｔｏｍｅｒ６１７３（ＣＯＯＨ含有　ｐｏｌｙｕｒｅｔｈａｎｅ　ａｃｒｙｌｉｃ　ｏｌｉｇｏｍｅｒ．Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業株式会社製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれも（株）ダイセル製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー株式会社製）、アクリキュアーＲＤ－Ｆ８（日本触媒（株）製）などが挙げられる。 As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. Examples of 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. Examples of 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). All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corp.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 ( Nippon Shokubai Co., Ltd.).
　本発明の硬化性組成物において、樹脂の含有量は、本発明の硬化性組成物の全固形分に対し、１４～７０質量％が好ましい。下限は、１７質量％以上が好ましく、２０質量％以上がより好ましい。上限は、５６質量％以下が好ましく、４２質量％以下がより好ましい。また、酸基を有する樹脂の含有量は、本発明の硬化性組成物の全固形分に対し、１４～７０質量％が好ましい。下限は、１７質量％以上が好ましく、２０質量％以上がより好ましい。上限は、５６質量％以下が好ましく、４２質量％以下がより好ましい。また、アルカリ可溶性樹脂の含有量は、本発明の硬化性組成物の全固形分に対し、１４～７０質量％が好ましい。下限は、１７質量％以上が好ましく、２０質量％以上がより好ましい。上限は、５６質量％以下が好ましく、４２質量％以下がより好ましい。 In the curable composition of the present invention, 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.
＜＜溶剤＞＞
　本発明の硬化性組成物は、溶剤を含有する。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や硬化性組成物の塗布性を満足すれば基本的には特に制限はないが、硬化性組成物の塗布性、安全性を考慮して選ばれることが好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類などが挙げられる。これらの詳細については、上述した顔料分散液で説明した有機溶剤を用いることができる。有機溶剤としては、例えば、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテートが好ましい。 << Solvent >>
The curable composition of the present invention contains a solvent. Examples of 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. Examples of 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. Examples of the organic solvent 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.
　溶剤の含有量は、硬化性組成物の全量に対し、１０～９０質量％であることが好ましく、２０～８０質量％であることがより好ましく、２５～７５質量％であることが更に好ましい。本発明の硬化性組成物は、溶剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。溶剤を２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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.
＜＜硬化性化合物＞＞
　本発明の硬化性組成物は、硬化性化合物を含有する。硬化性化合物としては、ラジカル、酸、熱により架橋可能な公知の化合物を用いることができる。硬化性化合物としては、例えば、重合性化合物、エポキシ基を有する化合物などが挙げられる。重合性化合物としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などのエチレン性不飽和結合基を有する化合物が挙げられる。重合性化合物は、ラジカル重合性化合物であることが好ましい。 << Curable compound >>
The curable composition of the present invention contains a curable compound. As the curable compound, known compounds that can be cross-linked by radicals, acids, and heat can be used. Examples of the curable compound include a polymerizable compound and a compound having an epoxy group. Examples of 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.
　本発明の硬化性組成物において、硬化性化合物の含有量は、硬化性組成物の全固形分に対し、０．１～５０質量％が好ましい。下限は、例えば０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、例えば、４５質量％以下がより好ましく、４０質量％以下が更に好ましい。硬化性化合物は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲となることが好ましい。 In the curable composition of the present invention, 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. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, 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.
（重合性化合物）
　重合性化合物は、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～３０００が好ましい。上限は、２０００以下がより好ましく、１５００以下が更に好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。
　重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。これらの具体的な化合物としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 (Polymerizable compound)
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. 0095 to 0108 in JP-A-2009-288705, paragraph 0227 in JP-A-2013-29760, and paragraph numbers 0254 to 0257 in JP-A-2008-292970. Compounds, the contents of which are incorporated herein.
　重合性化合物は、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。これらのオリゴマータイプも使用できる。
　また、重合性化合物として、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることも好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 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 from the company) Is preferred. These oligomer types can also be used.
In addition, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use 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.
　重合性化合物として、酸基を有する重合性化合物を用いることもできる。酸基を有する重合性化合物を用いることで、現像時に未露光部の重合性化合物が除去されやすく、現像残渣の発生を抑制できる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性化合物の市販品としては、アロニックスＭ－５１０、Ｍ－５２０（東亞合成（株）製）等が挙げられる。 A polymerizable compound having an acid group can also be used as the polymerizable compound. 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. Examples of 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.).
　酸基を有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。さらには、硬化性に優れる。 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.
　重合性化合物として、カプロラクトン構造を有する重合性化合物を用いることもできる。また、重合性化合物として、アルキレンオキシ基を有する重合性化合物を用いることもできる。アルキレンオキシ基を有する重合性化合物は、エチレンオキシ基および／またはプロピレンオキシ基を有する重合性化合物が好ましく、エチレンオキシ基を有する重合性化合物がより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物がさらに好ましい。アルキレンオキシ基を有する重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 A polymerizable compound having a caprolactone structure can also be used as the polymerizable compound. Moreover, 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.
　重合性化合物として、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載されているエチレンオキサイド系骨格を有するウレタン化合物類も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類を用いることも好ましい。
　市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ社製）、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬社製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）などが挙げられる。 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. Further, 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.
Commercially available products include 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.
　本発明の硬化性組成物が重合性化合物を含有する場合、重合性化合物の含有量は、硬化性組成物の全固形分に対して、０．１～４０質量％が好ましい。下限は、例えば０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、例えば、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。重合性化合物は１種単独であってもよいし、２種以上を併用してもよい。重合性化合物を２種以上併用する場合は、合計量が上記範囲となることが好ましい。 When the curable composition of the present invention contains a polymerizable compound, 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. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, 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.
（エポキシ基を有する化合物）
　本発明の硬化性組成物は、硬化性化合物としてエポキシ基を有する化合物を含有することができる。エポキシ基を有する化合物としては、１分子内にエポキシ基を２つ以上有する化合物が好ましい。エポキシ基を有する化合物は、エポキシ基を２～１００個有する化合物であることが好ましい。エポキシ基の上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。 (Compound having an epoxy group)
The curable composition of this invention can contain the compound which has an epoxy group as a sclerosing | hardenable compound. As the compound having an epoxy group, 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.
　エポキシ基を有する化合物は、エポキシ当量（＝エポキシ基を有する化合物の分子量／エポキシ基の数）が５００ｇ／当量以下であることが好ましく、１００～４００ｇ／当量であることがより好ましく、１００～３００ｇ／当量であることがさらに好ましい。 The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. / Equivalent is more preferable.
　エポキシ基を有する化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。 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.
　エポキシ基を有する化合物は、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。また、エポキシ基を有する化合物（エポキシ樹脂）は、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（日油（株）製、エポキシ基含有ポリマー）を使用することも好ましい。 Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. Further, compounds having an epoxy group (epoxy resin) are Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100. G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer) is also preferably used.
　本発明の硬化性組成物がエポキシ基を有する化合物を含有する場合、エポキシ基を有する化合物の含有量は、硬化性組成物の全固形分に対し、０．１～４０質量％が好ましい。下限は、例えば０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、例えば、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。エポキシ基を有する化合物は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲となることが好ましい。
　また、重合性化合物と、エポキシ基を有する化合物との質量比は、重合性化合物の質量：エポキシ基を有する化合物の質量＝１００：１～１００：４００が好ましく、１００：１～１００：１００がより好ましく、１００：１～１００：５０がさらに好ましい。 When the curable composition of the present invention contains a compound having an epoxy group, 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. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, 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 mass ratio of the polymerizable compound to the compound having an epoxy group is preferably the mass of the polymerizable compound: the mass of the compound having an epoxy group = 100: 1 to 100: 400, preferably 100: 1 to 100: 100. More preferably, 100: 1 to 100: 50 is even more preferable.
＜＜光重合開始剤＞＞
　本発明の硬化性組成物は、光重合開始剤を含有することができる。特に、本発明の硬化性組成物が、重合性化合物を含む場合、光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 << photopolymerization initiator >>
The curable composition of the present invention can contain a photopolymerization initiator. In particular, when the curable composition of the present invention contains a polymerizable compound, it preferably contains a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, 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.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノンなどが挙げられる。トリアジン骨格を有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報に記載の化合物、独国特許３３３７０２４号明細書に記載の化合物、Ｆ．Ｃ．ＳｃｈａｅｆｅｒなどによるＪ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報に記載の化合物、特開平５－２８１７２８号公報に記載の化合物、特開平５－３４９２０号公報に記載の化合物、米国特許第４２１２９７６号明細書に記載の化合物などが挙げられる。 Examples of the photopolymerization initiator 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. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US patents And the compounds described in the specification of No. 42122976.
　光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。 Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-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.
　光重合開始剤としては、α－ヒドロキシケトン化合物、α－アミノケトン化合物、及び、アシルホスフィン化合物も好適に用いることができる。例えば、特開平１０－２９１９６９号公報に記載のα－アミノケトン化合物、特許第４２２５８９８号公報に記載のアシルホスフィン化合物も用いることができる。α－ヒドロキシケトン化合物としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（以上、ＢＡＳＦ社製）を用いることができる。α－アミノケトン化合物としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９、及び、ＩＲＧＡＣＵＲＥ－３７９ＥＧ（以上、ＢＡＳＦ社製）を用いることができる。α－アミノケトン化合物は、特開２００９－１９１１７９号公報に記載の化合物を用いることができる。アシルホスフィン化合物としては、市販品であるＩＲＧＡＣＵＲＥ－８１９やＤＡＲＯＣＵＲ－ＴＰＯ（以上、ＢＡＳＦ社製）を用いることができる。 As the photopolymerization initiator, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds can also be suitably used. For example, α-aminoketone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898 can also be used. As the α-hydroxyketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF) can be used. As an α-aminoketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF) can be used. As the α-aminoketone compound, compounds described in JP2009-191179A can be used. As the acylphosphine compound, commercially available products such as IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF) can be used.
　光重合開始剤は、オキシム化合物を用いることが好ましい。オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１６－２１０１２号公報に記載などが挙げられる。本発明において好適に用いることができるオキシム化合物としては、例えば、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）、特開２０００－６６３８５号公報、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報に記載の化合物等も挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）、アデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光重合開始剤２）も用いることができる。 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. In addition, J.H. C. S. Perkin II (1979, pp. 1653-1660), J. MoI. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000-66385 A, JP 2000-80068 A, and Special Table 2004 Examples thereof include compounds described in JP-A-534797 and JP-A-2006-342166.
As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF) are also preferably used. Also, 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) can also be used.
　また上記記載以外のオキシム化合物として、カルバゾール環のＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報及び米国特許公開２００９－２９２０３９号公報に記載の化合物、国際公開ＷＯ２００９／１３１１８９号公報に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物などを用いてもよい。 Further, as 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 Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton In the same molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and the like. Also good.
　オキシム化合物は、下記式（ＯＸ－１）で表される化合物を好ましく用いることができる。オキシム化合物は、オキシムのＮ－Ｏ結合が（Ｅ）体のオキシム化合物であってもよく、オキシムのＮ－Ｏ結合が（Ｚ）体のオキシム化合物であってもよく、（Ｅ）体と（Ｚ）体との混合物であってもよい。 As 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.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（ＯＸ－１）中、ＲおよびＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。式（ＯＸ－１）の詳細については、特開２０１３－０２９７６０号公報の段落番号０２７６～０３０４の記載を参酌でき、この内容は本明細書に組み込まれる。 In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. As for the details of the formula (OX-1), 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.
　本発明は、光重合開始剤として、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。この内容は本明細書に組み込まれる。 In the present invention, 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.
　本発明は、光重合開始剤として、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。この内容は本明細書に組み込まれる。 In the present invention, 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.
　本発明は、光重合開始剤として、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 In the present invention, 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).
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　オキシム化合物は、３５０ｎｍ～５００ｎｍの波長領域に吸収極大を有する化合物が好ましく、３６０ｎｍ～４８０ｎｍの波長領域に吸収極大を有する化合物がより好ましい。また、オキシム化合物は、３６５ｎｍ及び４０５ｎｍの吸光度が高い化合物が好ましい。
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１,０００～３００，０００であることが好ましく、２,０００～３００，０００であることがより好ましく、５,０００～２００，０００であることが特に好ましい。
　化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 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.
　光重合開始剤は、オキシム化合物とα－アミノケトン化合物とを含むことも好ましい。両者を併用することで、現像性が向上し、矩形性に優れたパターンを形成しやすい。オキシム化合物とα－アミノケトン化合物とを併用する場合、オキシム化合物１００質量部に対して、α－アミノケトン化合物が５０～６００質量部が好ましく、１５０～４００質量部がより好ましい。 The photopolymerization initiator preferably contains an oxime compound and an α-aminoketone compound. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed. When the oxime compound and the α-aminoketone compound are used in combination, the α-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.
　光重合開始剤の含有量は、硬化性組成物の全固形分に対し０．１～５０質量％が好ましく、０．５～３０質量％がより好ましく、１～２０質量％が更に好ましい。光重合開始剤の含有量が上記範囲であれば、より良好な感度とパターン形成性が得られる。本発明の硬化性組成物は、光重合開始剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。光重合開始剤を２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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.
＜＜連鎖移動剤＞＞
　本発明の硬化性組成物は、連鎖移動剤を含有することができる。この態様によれば、露光によって膜表面（パターン表面）の硬化を促進できる。このため、露光時の膜厚の減少などを抑制でき、より矩形性に優れたパターンを形成しやすい。 << Chain transfer agent >>
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.
　連鎖移動剤としては、Ｎ，Ｎ-ジアルキルアミノ安息香酸アルキルエステルや、チオール化合物などが挙げられ、チオール化合物が好ましい。チオール化合物は、分子内に２個以上（好ましくは２～８個、より好ましくは３～６個）のチオール基を有する化合物が好ましい。チオール化合物の具体例としては、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、Ｎ－フェニルメルカプトベンゾイミダゾール、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンなどの複素環を有するチオール化合物、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタンなどの脂肪族系のチオール化合物などが挙げられる。また、下記化合物を用いることも好ましい。また、連鎖移動剤の市販品としては、ＰＥＭＰ（長瀬産業（株）製、チオール化合物）、サンセラー　Ｍ（三新化学工業（株）製、チオール化合物）、カレンズＭＴ　ＢＤ１（昭和電工社（株）製、チオール化合物）などが挙げられる。
Figure JPOXMLDOC01-appb-C000017
 Examples of 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. Specific examples of the thiol compound 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. Commercially available 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).
Figure JPOXMLDOC01-appb-C000017
　連鎖移動剤の含有量は、硬化性組成物の全固形分に対して０．２～５．０質量％が好ましく、０．４～３．０質量％がより好ましい。また、連鎖移動剤の含有量は、重合性化合物の１００質量部に対し、１～４０質量部が好ましく、２～２０質量部がより好ましい。 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. In addition, 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.
＜＜重合禁止剤＞＞
　本発明の硬化性組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。重合禁止剤の含有量は、硬化性組成物の全固形分に対して、０．０１～５質量％が好ましい。また、重合禁止剤の含有量は、重合性化合物の１００質量部に対し、０．００１～１質量部であることが好ましい。上限は、０．５質量部以下が好ましく、０．２質量部以下がより好ましい。下限は、０．０１質量部以上が好ましく、０．０３質量部以上がより好ましい。本発明の硬化性組成物は、重合禁止剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。重合禁止剤を２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 << Polymerization inhibitor >>
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.
＜＜紫外線吸収剤＞＞
　本発明の硬化性組成物は、紫外線吸収剤を含有することが好ましい。
　紫外線吸収剤は、共役ジエン系化合物およびジケトン化合物が挙げられる。共役ジエン系化合物としては式（ＵＶ－１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000018
 << UV absorber >>
It is preferable that the curable composition of this invention contains a ultraviolet absorber.
Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds. Examples of the conjugated diene compound include a compound represented by the formula (UV-1).
Figure JPOXMLDOC01-appb-C000018
　式（ＵＶ－１）において、Ｒ１及びＲ２は、各々独立に、水素原子、炭素原子数１～２０のアルキル基、又は炭素原子数６～２０のアリール基を表し、Ｒ１とＲ２とは互いに同一でも異なっていてもよいが、同時に水素原子を表すことはない。 In 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.
　式（ＵＶ－１）で示される化合物の置換基の説明は、国際公開ＷＯ２００９／１２３１０９号公報の段落番号００２４～００３３の記載を参酌でき、この内容は本明細書に組み込まれる。式（ＵＶ－１）で表される化合物の具体例としては、国際公開ＷＯ２００９／１２３１０９号公報の段落番号００３４～００３７の例示化合物（１）～（１４）が挙げられ、この内容は本明細書に組み込まれる。式（ＵＶ－１）で示される紫外線吸収剤の市販品としては、例えば、ＵＶ５０３（大東化学（株）製）などが挙げられる。 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.).
　ジケトン化合物としては、下記式（ＵＶ－２）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000019
 　式（ＵＶ－２）において、Ｒ１０１及びＲ１０２は、各々独立に、置換基を表し、ｍ１およびｍ２は、それぞれ独立して０～４を表す。置換基は、アルキル基、アルケニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロアリールオキシカルボニル基、アシルオキシ基、アミノ基、アシルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、ヘテロアリールオキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アルキルスルホニル基、アリールスルホニル基、ヘテロアリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、ヘテロアリールスルフィニル基、ウレイド基、リン酸アミド基、メルカプト基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、シリル基、ヒドロキシル基、ハロゲン原子、シアノ基などが挙げられ、アルキル基およびアルコキシ基が好ましい。
　アルキル基の炭素数は、１～２０が好ましい。アルキル基は、直鎖、分岐、環状が挙げられ、直鎖または分岐が好ましく、分岐がより好ましい。
　アルコキシ基の炭素数は、１～２０が好ましい。アルコキシ基は、直鎖、分岐、環状が挙げられ、直鎖または分岐が好ましく、分岐がより好ましい。
　Ｒ１０１及びＲ１０２の一方がアルキル基で、他方がアルコキシ基である組み合わせが好ましい。
　ｍ１およびｍ２は、それぞれ独立して０～４を表す。ｍ１およびｍ２は、それぞれ独立して０～２が好ましく、０～１がより好ましく、１が特に好ましい。 Examples of the diketone compound include compounds represented by the following formula (UV-2).
Figure JPOXMLDOC01-appb-C000019
 In the formula (UV-2), R 101 and R 102 each independently represent a substituent, and 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, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl, ureido, phosphate amide, mercapto, E group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, or a cyano group, an alkyl group and alkoxy group are preferred.
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.
　式（ＵＶ－２）で表される化合物としては、下記化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000020
 Examples of the compound represented by the formula (UV-2) include the following compounds.
Figure JPOXMLDOC01-appb-C000020
　紫外線吸収剤は、ユビナールＡ（ＢＡＳＦ社製）を用いることもできる。また、紫外線吸収剤は、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、トリアジン化合物等の紫外線吸収剤を用いることができ、具体例としては特開２０１３－６８８１４号に記載の化合物が挙げられる。ベンゾトリアゾール化合物としてはミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）を用いてもよい。 As the UV absorber, Yubinal A (manufactured by BASF) can be used. As the ultraviolet absorber, 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. As the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil and Fat may be used.
　紫外線吸収剤の含有量は、本発明の硬化性組成物の全固形分に対して、０．０１～１０質量％が好ましく、０．０１～５質量％がより好ましい。また、紫外線吸収剤の含有量は、重合性化合物の１００質量部に対し、５～１００質量部であることが好ましい。上限は、８０質量部以下が好ましく、６０質量部以下がより好ましい。下限は、１０質量部以上が好ましく、２０質量部以上がより好ましい。 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.
＜＜シランカップリング剤＞＞
　本発明の硬化性組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基は、樹脂との間で相互作用もしくは結合を形成して親和性を示す基が好ましい。例えば、ビニル基、スチリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基などが挙げられ、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤として、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２２９～０２３６に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 << Silane coupling agent >>
The curable composition of the present invention can contain a silane coupling agent. In the present invention, 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. As 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. In addition, 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. As the 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.
　シランカップリング剤の含有量は、硬化性組成物の全固形分に対して、０．１～３０質量％が好ましく、０．５～２０質量％がより好ましく、１～１０質量％が特に好ましい。本発明の硬化性組成物は、シランカップリング剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。シランカップリング剤を２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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.
＜＜界面活性剤＞＞
　本発明の硬化性組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。界面活性剤は、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。 << Surfactant >>
The curable composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. As for the surfactant, paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
　本発明の硬化性組成物にフッ素系界面活性剤を含有させることで、塗布液として調製したときの液特性（特に、流動性）がより向上し、塗布厚の均一性や省液性をより改善することができる。フッ素系界面活性剤を含有する硬化性組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力が低下して、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、厚みムラの小さい均一厚の膜形成をより好適に行うことができる。 By including a fluorosurfactant in the curable composition of the present invention, 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. Can be improved. In the case of forming a film using a coating liquid to which a curable composition containing a fluorosurfactant is applied, 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 | paintability to a to-be-coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 The fluorine content in the fluorosurfactant is preferably 3 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.
　フッ素系界面活性剤として具体的には、特開２０１４－４１３１８号公報の段落番号００６０～００６４（対応する国際公開２０１４／１７６６９号公報の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 Specific examples of the fluorosurfactant 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. Commercially available 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.
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造で、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられ、これらを用いることができる。 In addition, 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. Can be used. Examples of such 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.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000021
 　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％は質量％である。 As the fluorosurfactant, 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.
Figure JPOXMLDOC01-appb-C000021
 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%.
　また、フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 Further, as the fluorosurfactant, 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. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 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 Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
　界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
　界面活性剤の含有量は、硬化性組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。 Only one type of surfactant may be used, or two or more types may be combined.
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.
＜＜その他成分＞＞
　本発明の硬化性組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、熱重合禁止剤、可塑剤、密着促進剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分は、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、この内容は本明細書に組み込まれる。また、酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。酸化防止剤としては、分子量５００以上のフェノール化合物、分子量５００以上の亜リン酸エステル化合物又は分子量５００以上のチオエーテル化合物がより好ましい。これらは２種以上を混合して使用してもよい。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。特に、フェノール性水酸基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましく、メチル基、エチル基、プロピオニル基、イソプロピオニル基、ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、イソペンチル基、ｔ－ペンチル基、ヘキシル基、オクチル基、イソオクチル基、２－エチルへキシル基がより好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、および亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）からなる群から選ばれる少なくとも１種の化合物が挙げられる。これらは、市販品として入手できる。例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（（株）ＡＤＥＫＡ）などが挙げられる。酸化防止剤の含有量は、組成物の全固形分に対して、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 << Other ingredients >>
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. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the antioxidant, 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. As 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. As the above-mentioned substituent, 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. Moreover, phosphorus antioxidant can also be used suitably for antioxidant. As the 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. For example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330 (stock) ADEKA) and the like. 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.
　本発明の硬化性組成物の粘度（２３℃）は、例えば、塗布により膜を形成する場合、１～３０００ｍＰａ・ｓの範囲にあることが好ましい。下限は、３ｍＰａ・ｓ以上が好ましく、５ｍＰａ・ｓ以上がより好ましい。上限は、２０００ｍＰａ・ｓ以下が好ましく、１０００ｍＰａ・ｓ以下がより好ましい。 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.
　本発明の硬化性組成物の２３℃におけるＴｉ値は、０．８～１．４であることが好ましく、０．９～１．２であることがより好ましく、０．９～１．１であることが更に好ましい。硬化性組成物のＴｉ値は、上述した顔料分散液の欄で説明した方法で測定することができる。 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.
　本発明の硬化性組成物は、近赤外線カットフィルタや赤外線透過フィルタなどの形成に好ましく用いることができる。 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.
＜硬化性組成物の調製方法＞
　本発明の硬化性組成物は、上述した各成分を混合することによって調製することができる。また、異物の除去や欠陥の低減などの目的で、フィルタでろ過することが好ましい。フィルタの種類、ろ過方法については、顔料分散液の調製の欄で説明したものが挙げられ、好ましい範囲も同様である。 <Method for preparing curable composition>
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.
＜膜、近赤外線カットフィルタ＞
　次に、本発明の膜について説明する。本発明の膜は、上述した本発明の硬化性組成物を用いてなるものである。本発明の膜は、近赤外線カットフィルタや赤外線透過フィルタなどの光学フィルタとして好ましく用いることができる。また、光学フィルタは、本発明の膜を用いた画素と、赤、緑、青、マゼンタ、黄、シアン、黒および無色から選ばれる画素とを有する態様も好ましい態様である。また、本発明の膜は、熱線遮蔽フィルタとして用いることもできる。本発明の膜は、パターンを有していてもよく、パターンを有さない膜（平坦膜）であってもよい。また、本発明の膜は、支持体上に積層して用いてもよく、本発明の膜を支持体から剥離して用いてもよい。また、本発明の膜を赤外線透過フィルタとして用いる場合、赤外線透過フィルタは、例えば、可視光を遮光し、波長９００ｎｍ以上の波長の光を透過するフィルタが挙げられる。本発明の膜を、赤外線透過フィルタとして用いる場合、近赤外線吸収有機顔料と可視光を遮光する色材（好ましくは、２種以上の有彩色着色剤を含有する色材、または、有機系黒色着色剤を少なくとも含有する色材）とを含む硬化性組成物を用いたフィルタであるか、近赤外線吸収有機顔料を含む層の他に、可視光を遮光する色材の層が別途存在するフィルタであることが好ましい。本発明の膜を赤外線透過フィルタとして用いる場合、近赤外線吸収有機顔料は、透過する光（近赤外線）をより長波長側に限定する役割を有している。 <Membrane, near-infrared cut filter>
Next, the film of the present invention will be described. 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. In addition, 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. When the film of the present invention is used as an infrared transmission filter, examples of the infrared transmission filter include a filter that blocks visible light and transmits light having a wavelength of 900 nm or more. 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. When the film of the present invention is used as an infrared transmission filter, the near-infrared absorbing organic pigment has a role of limiting transmitted light (near-infrared light) to a longer wavelength side.
　本発明の膜の膜厚は、目的に応じて適宜調整できる。膜厚は、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上が更に好ましい。 The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.
　本発明の膜は、有彩色着色剤を含むカラーフィルタと組み合わせて用いることもできる。カラーフィルタは、有彩色着色剤を含む着色組成物を用いて製造できる。有彩色着色剤としては、本発明の硬化性組成物で説明した有彩色着色剤が挙げられる。着色組成物は、樹脂、硬化性化合物、光重合開始剤、界面活性剤、溶剤、重合禁止剤、紫外線吸収剤などをさらに含有することができる。これらの詳細については、本発明の硬化性組成物で説明した材料が挙げられ、これらを用いることができる。また、本発明の膜に有彩色着色剤を含有させて、近赤外線カットフィルタとカラーフィルタとしての機能を備えたフィルタとしてもよい。 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. Examples of 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.
　なお、本発明において、近赤外線カットフィルタとは、可視領域の波長の光（可視光）を透過させ、近赤外領域の波長の光（近赤外線）の少なくとも一部を遮光するフィルタを意味する。近赤外線カットフィルタは、可視領域の波長の光をすべて透過するものであってもよく、可視領域の波長の光のうち、特定の波長領域の光を通過させ、特定の波長領域の光を遮光するものであってもよい。また、本発明において、カラーフィルタとは、可視領域の波長の光のうち、特定の波長領域の光を通過させ、特定の波長領域の光を遮光するフィルタを意味する。また、赤外線透過フィルタとは、可視領域の波長の光を遮光し、近赤外領域の波長の光（近赤外線）の少なくとも一部を透過させるフィルタを意味する。 In the present invention, 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. In the present invention, 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).
　本発明の膜を近赤外線カットフィルタとして用いる場合、本発明の膜は、７００～１０００ｎｍの範囲に極大吸収波長を有することが好ましい。また、波長５５０ｎｍにおける吸光度Ａ５５０と極大吸収波長における吸光度Ａｍａｘとの比である吸光度Ａ５５０／吸光度Ａｍａｘは０．００２～０．０４０であることが好ましく、０．００３～０．０３０であることがより好ましく、０．００４～０．０２０であることが更に好ましい。また、波長４００ｎｍにおける吸光度Ａ４００と極大吸収波長における吸光度Ａｍａｘとの比である吸光度Ａ４００／吸光度Ａｍａｘは０．００５～０．１５０であることが好ましく、０．０２０～０．１００であることがより好ましく、０．０５０～０．０７０であることが更に好ましい。また、膜の極大吸収波長は、７２０～９８０ｎｍの範囲に有することがより好ましく、７４０～９６０ｎｍの範囲に有することがさらに好ましい。 When the film of the present invention is used as a near infrared cut filter, 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.
　本発明の近赤外線カットフィルタは、光の透過率について以下の（１）～（４）のうちの少なくとも１つの条件を満たすことが好ましく、（１）～（４）のすべての条件を満たすことがさらに好ましい。
（１）波長４００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、８５％以上がさらに好ましく、９０％以上が特に好ましい。
（２）波長５００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。
（３）波長６００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。
（４）波長６５０ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。 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.
(1) 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.
(2) 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.
(3) 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.
(4) 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.
　本発明において、近赤外線カットフィルタは、膜厚２０μｍ以下で、波長４００～６５０ｎｍの全ての範囲での透過率が７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。また、波長７００～１０００ｎｍの範囲の少なくとも１点での透過率が２０％以下であることが好ましい。 In the present invention, the near-infrared cut filter preferably has a film thickness of 20 μm 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.
　本発明の近赤外線カットフィルタは、本発明の膜の他に、更に、銅を含有する層、誘電体多層膜、紫外線吸収層などを有していてもよい。近赤外線カットフィルタが、更に、銅を含有する層および／または誘電体多層膜を有することで、視野角が広く、赤外線遮蔽性に優れた近赤外線カットフィルタが得られ易い。また、近赤外線カットフィルタが、更に、紫外線吸収層を有することで、紫外線遮蔽性に優れた近赤外線カットフィルタとすることができる。紫外線吸収層としては、例えば、国際公開ＷＯ２０１５／０９９０６０号公報の段落番号００４０～００７０、０１１９～０１４５に記載の吸収層を参酌でき、この内容は本明細書に組み込まれる。誘電体多層膜としては、特開２０１４－４１３１８号公報の段落番号０２５５～０２５９の記載を参酌でき、この内容は本明細書に組み込まれる。銅を含有する層としては、銅を含有するガラスで構成されたガラス基板（銅含有ガラス基板）や、銅錯体を含む層（銅錯体含有層）を用いることもできる。銅含有ガラス基板としては、銅を含有する燐酸塩ガラス、銅を含有する弗燐酸塩ガラスなどが挙げられる。銅含有ガラスの市販品としては、ＮＦ－５０（ＡＧＣテクノグラス（株）製）、ＢＧ－６０、ＢＧ－６１（ショット社製）、ＣＤ５０００（ＨＯＹＡ（株）製）等が挙げられる。銅錯体含有層としては、銅錯体を含む組成物を用いて形成してなる層が挙げられる。銅錯体は、７００～１２００ｎｍの波長領域に極大吸収波長を有する化合物が好ましい。銅錯体の極大吸収波長は、７２０～１２００ｎｍの波長領域に有することがより好ましく、８００～１１００ｎｍの波長領域に有することがさらに好ましい。 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. When the near-infrared cut filter further has a copper-containing layer and / or a dielectric multilayer film, a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained. Moreover, 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. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraph Nos. 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 099060 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification. As a layer containing copper, 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. Examples of 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. As 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.
　本発明の膜および近赤外線カットフィルタは、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や、赤外線センサ、画像表示装置などの各種装置に用いることができる。 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.
＜積層体＞
　本発明の積層体は、本発明の膜と、有彩色着色剤を含むカラーフィルタとを有する。本発明の積層体は、本発明の膜とカラーフィルタとが厚み方向で隣接していてもよく、隣接していなくてもよい。本発明の膜と、カラーフィルタとが厚み方向で隣接していない場合は、カラーフィルタが形成された支持体とは別の支持体上に本発明の膜が形成されていてもよく、本発明の膜とカラーフィルタとの間に、固体撮像素子を構成する他の部材（例えば、マイクロレンズ、平坦化層など）が介在していてもよい。 <Laminated body>
The laminate of the present invention has the film of the present invention and a color filter containing a chromatic colorant. In the laminate of the present invention, the film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the film of the present invention and the color filter are not 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. Between the film and the color filter, other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state imaging device may be interposed.
＜パターン形成方法＞
　次に、本発明の硬化性組成物を用いたパターン形成方法について説明する。パターン形成方法は、本発明の硬化性組成物を用いて支持体上に組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、組成物層に対してパターンを形成する工程と、を含むことが好ましい。 <Pattern formation method>
Next, the pattern formation method using the curable composition of this invention is demonstrated. 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.
　フォトリソグラフィ法でのパターン形成方法は、硬化性組成物を用いて支持体上に組成物層を形成する工程と、組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程と、を含むことが好ましい。必要に応じて、組成物層をベークする工程（プリベーク工程）、および、現像されたパターンをベークする工程（ポストベーク工程）を設けてもよい。ドライエッチング法でのパターン形成方法は、硬化性組成物を用いて支持体上に組成物層を形成し、硬化して硬化物層を形成する工程と、硬化物層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして硬化物層をドライエッチングしてパターンを形成する工程とを含むことが好ましい。以下、各工程について説明する。 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. It is preferable to include 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. Hereinafter, each step will be described.
＜＜組成物層を形成する工程＞＞
　組成物層を形成する工程では、硬化性組成物を用いて、支持体上に組成物層を形成する。 << 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.
　支持体としては、例えば、基板（例えば、シリコン基板）上にＣＣＤやＣＭＯＳ等の固体撮像素子（受光素子）が設けられた固体撮像素子用基板を用いることができる。パターンは、固体撮像素子用基板の固体撮像素子形成面側（おもて面）に形成してもよいし、固体撮像素子非形成面側（裏面）に形成してもよい。支持体上には、必要により、上部の層との密着改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。 As the support, for example, 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). If necessary, 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.
　支持体への硬化性組成物の適用方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された特許公報に記載の方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。 As a method for applying the curable composition to the support, a known method can be used. For example, a dropping method (drop casting); a slit coating method; 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. Various printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. The application method in the ink jet is not particularly limited. For example, the method described in the patent publication shown in “Expanding and usable ink jet: unlimited possibilities seen in patents, issued in February 2005, Sumibe Techno Research”. (Especially pages 115 to 133), JP2003-262716A, JP2003-185831A, JP2003-261627A, JP2012-126830A, JP2006-169325A, etc. The method of description is mentioned.
　支持体上に形成した組成物層は、乾燥（プリベーク）してもよい。低温プロセスによりパターンを形成する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク温度を１５０℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。プリベーク時間は、１０秒～３００秒が好ましく、４０～２５０秒がより好ましく、８０～２２０秒がさらに好ましい。プリベークは、ホットプレート、オーブン等を用いて行うことができる。 The composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When performing prebaking, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. By performing the pre-baking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be more effectively maintained. 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.
（フォトリソグラフィ法でパターン形成する場合）
＜＜露光工程＞＞
　次に、組成物層を、パターン状に露光する（露光工程）。例えば、組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等の紫外線が好ましく、ｉ線がより好ましい。照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましく、０．０８～０．５Ｊ／ｃｍ２が最も好ましい。
　露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ２～１０００００Ｗ／ｍ２（例えば、５０００Ｗ／ｍ２、１５０００Ｗ／ｍ２、３５０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 (When forming a pattern by photolithography)
<< Exposure process >>
Next, the composition layer is exposed in a pattern (exposure process). For example, 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. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% by volume. Further, 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.
＜＜現像工程＞＞
　次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。
　現像液としては、下地の固体撮像素子や回路などにダメージを起さない、アルカリ現像液が望ましい。
　現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返してもよい。 << Development process >>
Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains on a support body.
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.
　現像液に用いるアルカリ剤としては、例えば、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。現像液は、これらのアルカリ剤を純水で希釈したアルカリ性水溶液が好ましく使用される。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、上述した硬化性組成物で説明した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、現像後純水で洗浄（リンス）することが好ましい。 Examples of the alkaline agent used in the developer 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. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The 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. Further, 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. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.
　現像後、乾燥を施した後に加熱処理（ポストベーク）を行うこともできる。ポストベークは、膜の硬化を完全なものとするための現像後の加熱処理である。ポストベークを行う場合、ポストベーク温度は、例えば１００～２４０℃が好ましい。膜硬化の観点から、２００～２３０℃がより好ましい。また、発光光源として有機エレクトロルミネッセンス（有機ＥＬ）素子を用いた場合や、イメージセンサの光電変換膜を有機素材で構成した場合は、ポストベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１００℃以下が更に好ましく、９０℃以下が特に好ましい。下限は、例えば、５０℃以上とすることができる。ポストベークは、現像後の膜に対して、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。 Developed, dried and then heat-treated (post-baked). Post-baking is a heat treatment after development for complete film curing. In the case of performing post-baking, 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. In addition, when an organic electroluminescence (organic EL) element is used as the light source, or when the photoelectric conversion film of the image sensor is made of an organic material, 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.
　また、本発明のパターン形成方法は、未露光部を現像除去した後（現像後）、更に、露光する工程（以下、現像後の露光を後露光ともいう）を有していてもよい。光重合開始剤として、オキシム化合物とα－アミノケトン化合物とを含む硬化性組成物を用いた場合においては、後露光を行うことが好ましい。パターン形成の前後の２段階で組成物層を露光することにより、最初の露光（パターンを形成する前の露光）で組成物を適度に硬化させることができ、次の露光（パターンを形成した後の露光）で組成物全体をほぼ硬化させることができる。結果として、ポストベーク温度が１８０℃以下であっても、硬化性組成物を効果的に硬化させることができる。露光を２段階で行う場合においても、後露光の後に、更に、ポストベークを行ってもよい。ポストベーク温度は、例えば１００～２４０℃が好ましい。 In addition, 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). When a curable composition containing an oxime compound and an α-aminoketone compound is used as a photopolymerization initiator, post-exposure is preferably performed. By exposing 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). As a result, even if the post-bake temperature is 180 ° C. or lower, the curable composition can be effectively cured. Even when the exposure is performed in two stages, post-baking may be further performed after the post-exposure. The post-bake temperature is preferably 100 to 240 ° C., for example.
（ドライエッチング法でパターン形成する場合）
　ドライエッチング法でのパターン形成は、支持体上に形成した組成物層を硬化して硬化物層を形成し、次いで、得られた硬化物層に対して、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 (When pattern is formed by dry etching method)
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. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in this specification.
＜固体撮像素子＞
　本発明の固体撮像素子は、上述した本発明の膜を有する。本発明の固体撮像素子の構成としては、本発明の膜を有する構成であり、固体撮像素子として機能する構成であれば特に限定はない。例えば、以下のような構成が挙げられる。 <Solid-state imaging device>
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.
　支持体上に、固体撮像素子の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、本発明の膜を有する構成である。さらに、デバイス保護膜上であって、本発明の膜の下（支持体に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、本発明の膜上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。 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. Furthermore, it is on the device protective film and 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. In addition, 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.
＜画像表示装置＞
　本発明の膜は、液晶表示装置や有機エレクトロルミネッセンス（有機ＥＬ）表示装置などの画像表示装置に用いることもできる。例えば、本発明の膜を、画像表示装置のバックライト（例えば白色発光ダイオード（白色ＬＥＤ））に含まれる赤外光を遮断する目的、周辺機器の誤作動を防止する目的、各着色画素に加えて赤外の画素を形成する目的で用いることができる。 <Image display device>
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. For example, 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. Can be used for the purpose of forming infrared pixels.
　画像表示装置の定義や詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 For the definition and details of 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”.
　画像表示装置は、白色有機ＥＬ素子を有するものであってもよい。白色有機ＥＬ素子としては、タンデム構造であることが好ましい。有機ＥＬ素子のタンデム構造については、特開２００３－４５６７６号公報、三上明義監修、「有機ＥＬ技術開発の最前線－高輝度・高精度・長寿命化・ノウハウ集－」、技術情報協会、３２６－３２８ページ、２００８年などに記載されている。有機ＥＬ素子が発光する白色光のスペクトルは、青色領域（４３０ｎｍ－４８５ｎｍ）、緑色領域（５３０ｎｍ－５８０ｎｍ）及び黄色領域（５８０ｎｍ－６２０ｎｍ）に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域（６５０ｎｍ－７００ｎｍ）に極大発光ピークを有するものがより好ましい。 The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, 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.
＜赤外線センサ＞
　本発明の赤外線センサは、上述した本発明の膜を有する。本発明の赤外線センサの構成としては、本発明の膜を有する構成であり、赤外線センサとして機能する構成であれば特に限定はない。 <Infrared sensor>
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.
　以下、本発明の赤外線センサの一実施形態について、図面を用いて説明する。
　図１において、符号１１０は、固体撮像素子である。固体撮像素子１１０上に設けられている撮像領域は、近赤外線カットフィルタ１１１と、赤外線透過フィルタ１１４とを有する。また、近赤外線カットフィルタ１１１上には、カラーフィルタ１１２が積層している。カラーフィルタ１１２および赤外線透過フィルタ１１４の入射光ｈν側には、マイクロレンズ１１５が配置されている。マイクロレンズ１１５を覆うように平坦化層１１６が形成されている。近赤外線カットフィルタ１１１は、本発明の組成物を用いて形成することができる。 Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.
In FIG. 1, 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 hν 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.
　カラーフィルタ１１２は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、特に限定はなく、従来公知の画素形成用のカラーフィルタを用いることができる。例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタなどが用いられる。例えば、特開２０１４－０４３５５６号公報の段落番号０２１４～０２６３の記載を参酌することができ、この内容は本明細書に組み込まれる。 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. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description of 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.
　赤外線透過フィルタ１１４は、使用する赤外ＬＥＤの発光波長によりその特性は選択される。例えば、赤外ＬＥＤの発光波長が８５０ｎｍである場合、赤外線透過フィルタ１１４は、膜の厚み方向における光透過率の、波長４００～６５０ｎｍの範囲における最大値が３０％以下であることが好ましく、２０％以下であることがより好ましく、１０％以下であることがさらに好ましく、０．１％以下であることが特に好ましい。この透過率は、波長４００～６５０ｎｍの範囲の全域で上記の条件を満たすことが好ましい。波長４００～６５０ｎｍの範囲における最大値は、通常、０．１％以上である。 The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, 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.
　赤外線透過フィルタ１１４は、膜の厚み方向における光透過率の、波長８００ｎｍ以上（好ましくは８００～１３００ｎｍ）の範囲における最小値が７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることがさらに好ましい。この透過率は、波長８００ｎｍ以上の範囲の一部で上記の条件を満たすことが好ましく、赤外ＬＥＤの発光波長に対応する波長で上記の条件を満たすことが好ましい。波長９００～１３００ｎｍの範囲における光透過率の最小値は、通常、９９．９％以下である。 In the infrared transmission filter 114, the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 nm or more (preferably 800 to 1300 nm) 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.
　赤外線透過フィルタ１１４の膜厚は、１００μｍ以下が好ましく、１５μｍ以下がより好ましく、５μｍ以下がさらに好ましく、１μｍ以下が特に好ましい。下限値は、０．１μｍが好ましい。膜厚が上記範囲であれば、上述した分光特性を満たす膜とすることができる。
　赤外線透過フィルタ１１４の分光特性、膜厚等の測定方法を以下に示す。
　膜厚は、膜を有する乾燥後の基板を、触針式表面形状測定器（ＵＬＶＡＣ社製　ＤＥＫＴＡＫ１５０）を用いて測定した。
　膜の分光特性は、紫外可視近赤外分光光度計（日立ハイテクノロジーズ社製　Ｕ－４１００）を用いて、波長３００～１３００ｎｍの範囲において透過率を測定した値である。 The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. When the film thickness is in the above range, a film satisfying the above-described spectral characteristics can be obtained.
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).
　また、例えば、赤外ＬＥＤの発光波長が９４０ｎｍである場合、赤外線透過フィルタ１１４は、膜の厚み方向における光の透過率の、波長４５０～６５０ｎｍの範囲における最大値が２０％以下であり、膜の厚み方向における、波長８３５ｎｍの光の透過率が２０％以下であり、膜の厚み方向における光の透過率の、波長１０００～１３００ｎｍの範囲における最小値が７０％以上であることが好ましい。 For example, when the emission wavelength of the infrared LED is 940 nm, 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. In the thickness direction, the transmittance of light having a wavelength of 835 nm is preferably 20% or less, and 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.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「％」および「部」は質量基準である。以下の構造式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group.
＜近赤外線吸収有機顔料の製造＞
　下記の表に記載の顔料、摩砕剤および粘結剤をラボプラストミル（（株）東洋精機製作所製）に添加し、装置中の混練物の温度が下記表に記載の温度（ミリング温度）になるように温度コントロールして、下記表に記載のミリング時間にて混練した。
　混練研磨後の混練物を、２４℃の水１０Ｌで水洗処理して摩砕剤および粘結剤を取り除き、加熱オーブンで８０℃２４時間の処理を行って、近赤外線吸収有機顔料を得た。得られた近赤外線吸収有機顔料の平均一次粒子径、一次粒子径の変動係数、平均長短辺比、長短辺比の変動係数および粉末Ｘ線回折スペクトルを測定した。また、粉末Ｘ線回折スペクトルに基づき、回折角度２θが５～１２°の領域での回折強度が最も大きいピークの半値全幅、結晶化度の値を求めた。 <Manufacture of near-infrared absorbing organic pigment>
The pigment, milling agent and binder described in the following table are added to Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the temperature of the kneaded material in the apparatus is the temperature described in the following table (milling temperature). The mixture was kneaded at the milling time described in the following table under temperature control.
The kneaded product after kneading and polishing was washed with 10 L of water at 24 ° C. to remove the milling agent and the binder, and treated in a heating oven at 80 ° C. for 24 hours to obtain a near infrared absorbing organic pigment. 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 2θ is 5 to 12 ° were obtained.
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
　上記表に記載の材料は以下の通りである。
（顔料）
　顔料２：下記構造の化合物（近赤外線吸収有機顔料である）
Figure JPOXMLDOC01-appb-C000023
 　顔料４：下記構造の化合物（近赤外線吸収有機顔料である）
Figure JPOXMLDOC01-appb-C000024
 （摩砕剤）
　摩砕剤１：中性無水芒硝Ｅ（硫酸ナトリウム、平均粒子径（体積基準の５０％径（Ｄ５０））＝２０μｍ、三田尻化学製）
　摩砕剤２：ナクルＵＭ（塩化ナトリウム、平均粒子径（体積基準の５０％径（Ｄ５０））＝５０μｍ、ナイカイ塩業製）
　摩砕剤３：オシオミクロンＴ－０（塩化ナトリウム、平均粒子径（体積基準の５０％径（Ｄ５０））＝１０μｍ、赤穂化成製）
（粘結剤）
　ＤＥＧ：ジエチレングリコール The materials described in the above table are as follows.
(Pigment)
Pigment 2: Compound having the following structure (near infrared absorbing organic pigment)
Figure JPOXMLDOC01-appb-C000023
 Pigment 4: Compound having the following structure (near-infrared absorbing organic pigment)
Figure JPOXMLDOC01-appb-C000024
 (Abrasive)
Milling agent 1: neutral anhydrous sodium sulfate E (sodium sulfate, average particle size (50% diameter (D50) based on volume) = 20 μm, manufactured by Mitajiri Chemical)
Milling agent 2: Nakuru UM (sodium chloride, average particle diameter (50% diameter (D50) based on volume) = 50 μm, manufactured by Naikai salt industry)
Milling agent 3: Osiomicron T-0 (sodium chloride, average particle diameter (50% diameter on a volume basis (D50)) = 10 μm, manufactured by Ako Kasei)
(Binder)
DEG: Diethylene glycol
＜評価＞
（近赤外線吸収有機顔料の平均一次粒子径、一次粒子径の変動係数の測定）
　近赤外線吸収有機顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めた。具体的には、近赤外線吸収有機顔料の一次粒子の投影面積を求め、それに対応する円相当径を近赤外線吸収有機顔料の一次粒子径とした。４００個の近赤外線吸収有機顔料の一次粒子についての一次粒子径の算術平均値を平均一次粒子径とした。また、下記式に基づき、一次粒子径の変動係数を求めた。
　近赤外線吸収有機顔料の一次粒子径の変動係数＝（近赤外線吸収有機顔料の一次粒子径の標準偏差／近赤外線吸収有機顔料の一次粒子径の算術平均値）×１００ <Evaluation>
(Measurement of average primary particle diameter and coefficient of variation of primary particle diameter of near-infrared absorbing organic pigment)
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 projected area of the primary particles of the near-infrared absorbing organic pigment was determined, and the corresponding equivalent circle diameter was defined as the primary particle size of the near-infrared absorbing organic pigment. The arithmetic average value of the primary particle diameters for the primary particles of 400 near-infrared absorbing organic pigments was defined as the average primary particle diameter. Further, the coefficient of variation of the primary particle size was determined based on 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
　（近赤外線吸収有機顔料の平均長短辺比、長短辺比の変動係数の測定）
　近赤外線吸収有機顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めた。具体的には、投影された写真から、近赤外線吸収有機顔料の一次粒子の短辺と長辺との比（短辺／長辺）を求めて、長短辺比を算出した。また、下記式に基づき、長短辺比の変動係数を求めた。
　近赤外線吸収有機顔料の長短辺比の変動係数＝（近赤外線吸収有機顔料の長短辺比の標準偏差／近赤外線吸収有機顔料の長短辺比の算術平均値）×１００ (Measurement of variation coefficient of average long-short side ratio, long-short side ratio of near-infrared absorbing organic pigment)
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
（近赤外線吸収有機顔料の粉末Ｘ線回折スペクトルの測定）
　測定装置として、リガク製　試料水平型強力Ｘ線回折装置　ＲＩＮＴ－ＴＴＲ　ＩＩＩを使用し、回折角度２θ＝５°～５５°、電圧５０ｋＶ、電流３００ｍＡ、スキャンスピード４°／ｍｉｎ、ステップ間隔０．１、スリット（散乱０．０５ｍｍ、発散１０ｍｍ、受光０．１５ｍｍ）の条件で、近赤外線吸収有機顔料の粉末Ｘ線回折スペクトルを測定した。 (Measurement of powder X-ray diffraction spectrum of near-infrared absorbing organic pigment)
As a measuring device, a Rigaku sample horizontal type strong X-ray diffractometer RINT-TTR III is used, diffraction angle 2θ = 5 ° to 55 °, voltage 50 kV, current 300 mA, scan speed 4 ° / min, step interval 0.1. The powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment was measured under the conditions of slit (scattering 0.05 mm, divergence 10 mm, light receiving 0.15 mm).
（半値全幅の測定）
　得られた粉末Ｘ線回折スペクトルにおいて、回折角度２θが５～１２°の回折強度が最も大きいピークを、ローレンツ関数［ｙ＝Ａ／（１＋（（ｘ－ｘ０）／ｗ）２）＋ｈ］にフィッティングして、同ピークの半値全幅を求めた。ここで、ｙは強度、Ａはピーク高さ、ｘは２θ、ｘ０はピーク位置、ｗはピーク幅（半値半幅）、ｈはベースラインである。 (Measurement of full width at half maximum)
In the obtained powder X-ray diffraction spectrum, the peak having the highest diffraction intensity at a diffraction angle 2θ of 5 to 12 ° is represented by the Lorentz function [y = A / (1 + ((x−x0) / w) 2 ) + h]. Fitting was performed to determine the full width at half maximum of the same peak. Here, y is the intensity, A is the peak height, x is 2θ, x0 is the peak position, w is the peak width (half width at half maximum), and h is the baseline.
（結晶化度の測定）
　粉末Ｘ線回折スペクトルにおいて、回折角度２θが５～１５°の領域で最も低い点と、２５～３５°の領域で最も低い点を結んだ直線をベースラインとし、粉末Ｘ線回折スペクトルの実測値からベースラインの値を引いたスペクトル補正値を用いて、下記式を用いて結晶化度を測定した。
　結晶化度＝［Ｉｃ／（Ｉａ＋Ｉｃ）］
　式中、Ｉｃは、回折角度２θが１５°以上の領域であって、粉末Ｘ線回折スペクトルにおける結晶に由来するピークの回折強度の最大値であり、Ｉａは、粉末Ｘ線回折スペクトルにおけるアモルファスに由来するピークの回折強度の最大値である。
　なお、半値全幅が１°以下のピークを結晶に由来するピークとする。また半値全幅が３°を超えるピークをアモルファスに由来するピークとする。 (Measurement of crystallinity)
In the powder X-ray diffraction spectrum, 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 2θ is 5 to 15 ° and the lowest point in the region of 25 to 35 °. Using the spectrum correction value obtained by subtracting the baseline value from the value, the crystallinity was measured using the following formula.
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is a region where the diffraction angle 2θ 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, and 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.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
＜分散液の調製＞
　実施例１～９、比較例１～３の近赤外線吸収有機顔料の３．１３質量部と、顔料誘導体１を０．６３質量部と、分散剤１を２．２５質量部と、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を４４質量部と、直径０．５ｍｍ径のジルコニアビーズを６６質量部とをペイントシェーカーで１２０分間分散処理を行った後、ジルコニアビーズをデカンテーションで分離して、分散液を調製した。 <Preparation of dispersion>
3.13 parts by mass of the near-infrared absorbing organic pigments of Examples 1 to 9 and Comparative Examples 1 to 3, 0.63 parts by mass of pigment derivative 1, 2.25 parts by mass of dispersant 1, and propylene glycol monomethyl After 44 parts by mass of ether acetate (PGMEA) and 66 parts by mass of zirconia beads having a diameter of 0.5 mm were dispersed in a paint shaker for 120 minutes, the zirconia beads were separated by decantation, and the dispersion was Prepared.
　顔料誘導体１：下記化合物
Figure JPOXMLDOC01-appb-C000026
 　分散剤１：下記構造の樹脂（重量平均分子量＝２１０００）。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。
Figure JPOXMLDOC01-appb-C000027
 Pigment derivative 1:
Figure JPOXMLDOC01-appb-C000026
 Dispersant 1: Resin having the following structure (weight average molecular weight = 21000). 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.
Figure JPOXMLDOC01-appb-C000027
＜分光特性、耐熱性の評価＞
　上記で得られた実施例および比較例の近赤外線吸収有機顔料を用いた分散液１０質量部と、樹脂１の１０質量部とを混合した試料溶液を用いて、分光特性及び耐熱性を評価した。
樹脂１：（株）ダイセル製サイクロマーＰ　（ＡＣＡ）２３０ＡＡ <Evaluation of spectral characteristics and heat resistance>
Spectral characteristics and heat resistance were evaluated using a sample solution in which 10 parts by mass of the dispersion using the near-infrared absorbing organic pigments of Examples and Comparative Examples obtained above and 10 parts by mass of Resin 1 were mixed. .
Resin 1: Cyclomer P (ACA) 230AA manufactured by Daicel Corporation
（分光特性）
　試料溶液を、塗布後の膜厚が０．３μｍになるように、ガラスウェハ上にスピンコート法で塗布し、その後ホットプレートを用いて、１００℃で２分間加熱した。次にｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い１０００ｍＪ／ｃｍ２で露光した。さらに、ホットプレートを用いて２２０℃で５分間加熱し、膜を形成した。膜が形成された基板に対して、分光光度計Ｕ－４１００（日立ハイテクノロジーズ（株）製）を用いて、極大吸収波長、極大吸収波長における吸光度Ａｍａｘ、波長５５０ｎｍにおける吸光度Ａ５５０、波長４００ｎｍにおける吸光度Ａ４００を求め、波長５５０ｎｍにおける吸光度Ａ５５０と極大吸収波長における吸光度Ａｍａｘとの比（吸光度Ａ５５０／吸光度Ａｍａｘ）、波長４００ｎｍにおける吸光度Ａ４００と極大吸収波長における吸光度Ａｍａｘとの比（吸光度Ａ４００／吸光度Ａｍａｘ）を算出した。 (Spectral characteristics)
The sample solution was applied onto a glass wafer by spin coating so that the film thickness after application was 0.3 μm, 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 | membrane. Using the spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), 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.
（耐熱性）
　上記分光特性で評価した基板を、さらにホットプレートを用いて２２０℃６０分間加熱し、分光硬度計Ｕ－４１００（日立ハイテクノロジーズ（株）製）を用いて透過率を測定した。波長４００～１０００ｎｍの範囲における透過率のうち、加熱前後で透過率の変化が最も大きい波長における透過率の変化（最大透過率変動）を下記式より求めた。最大透過率変動がゼロに近いほうが耐熱性に優れていることを示す。
　最大透過率変動＝加熱前の透過率－加熱後の透過率
Figure JPOXMLDOC01-appb-T000028
 (Heat-resistant)
The substrate evaluated by the above spectral characteristics was further heated at 220 ° C. for 60 minutes using a hot plate, and the transmittance was measured using a spectral hardness meter U-4100 (manufactured by Hitachi High-Technologies Corporation). Of the transmittances in the wavelength range of 400 to 1000 nm, the transmittance change (maximum transmittance fluctuation) at the wavelength where the transmittance change was largest before and after heating was determined from the following equation. It shows that the one where the maximum transmittance fluctuation is close to zero is excellent in heat resistance.
Maximum transmittance fluctuation = transmittance before heating-transmittance after heating
Figure JPOXMLDOC01-appb-T000028
　上記表に示す通り、実施例は、吸光度Ａ４００および吸光度Ａ５５０が低く、可視透明性に優れていた。また、耐熱性も良好であった。 As shown in the above table, the Examples had low absorbance A400 and absorbance A550, and were excellent in visible transparency. Moreover, heat resistance was also favorable.
　実施例において、分散剤として本明細書に記載の分散剤に置き換えても同様の効果が得られる。 In the examples, the same effect can be obtained by replacing the dispersant described in this specification as the dispersant.
　また、近赤外線吸収有機顔料としてスクアリリウム化合物やシアニン化合物を用いた場合であっても、以下の特性を満たすことで、実施例と同様の効果が得られる。
　近赤外線吸収有機顔料における粉末Ｘ線回折スペクトルにおいて回折角度２θが５～１２°の領域に回折強度のピークを有し、この領域での回折強度が最も大きいピークの半値全幅が０．３～０．６°である。 Even when a squarylium compound or a cyanine compound is used as the near-infrared absorbing organic pigment, the same effects as in the examples can be obtained by satisfying the following characteristics.
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 2θ 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：固体撮像素子、１１１：近赤外線カットフィルタ、１１２：カラーフィルタ、１１４：赤外線透過フィルタ、１１５：マイクロレンズ、１１６：平坦化層 110: Solid-state imaging device, 111: Near-infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Micro lens, 116: Flattening layer

Claims (18)

  1. 　粉末Ｘ線回折スペクトルにおいて回折角度２θが５～１２°の領域に回折強度のピークを有し、前記領域での回折強度が最も大きいピークの半値全幅が０．３～０．６°である、近赤外線吸収有機顔料。 The powder X-ray diffraction spectrum has a diffraction intensity peak in a region where the diffraction angle 2θ is 5 to 12 °, and the full width at half maximum of the peak having the highest diffraction intensity in the region is 0.3 to 0.6 °. Near-infrared absorbing organic pigment.
  2. 　前記半値全幅が０．３～０．４５°である、請求項１に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to claim 1, wherein the full width at half maximum is 0.3 to 0.45 °.
  3. 　前記近赤外線吸収有機顔料の平均一次粒子径が１０～１００ｎｍである、請求項１または２に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to claim 1 or 2, wherein the near-infrared absorbing organic pigment has an average primary particle diameter of 10 to 100 nm.
  4. 　前記近赤外線吸収有機顔料の平均一次粒子径が２０～４５ｎｍである、請求項１または２に記載の近赤外線吸収有機顔料。 3. The near-infrared absorbing organic pigment according to claim 1 or 2, wherein the near-infrared absorbing organic pigment has an average primary particle size of 20 to 45 nm.
  5. 　前記近赤外線吸収有機顔料の一次粒子径の変動係数が２０～３５％である、請求項１～４のいずれか１項に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to any one of claims 1 to 4, wherein a variation coefficient of a primary particle diameter of the near-infrared absorbing organic pigment is 20 to 35%.
  6. 　前記近赤外線吸収有機顔料の平均長短辺比が０．５～０．９である、請求項１～５のいずれか１項に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to any one of claims 1 to 5, wherein the near-infrared absorbing organic pigment has an average long-short side ratio of 0.5 to 0.9.
  7. 　前記近赤外線吸収有機顔料の長短辺比の変動係数が１０～３０％である、請求項１～６のいずれか１項に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to any one of claims 1 to 6, wherein the near-infrared absorbing organic pigment has a coefficient of variation in the long-short side ratio of 10 to 30%.
  8. 　前記近赤外線吸収有機顔料の下記式で表される結晶化度の値が０．９～０．９９である、請求項１～７のいずれか１項に記載の近赤外線吸収有機顔料；
    　結晶化度＝［Ｉｃ／（Ｉａ＋Ｉｃ）］
    　式中、Ｉｃは、回折角度２θが１５°以上の領域であって、粉末Ｘ線回折スペクトルにおける結晶に由来するピークの回折強度の最大値であり、
    　Ｉａは、粉末Ｘ線回折スペクトルにおけるアモルファスに由来するピークの回折強度の最大値である。     The near-infrared absorbing organic pigment according to any one of claims 1 to 7, wherein the near-infrared absorbing organic pigment has a crystallinity value represented by the following formula of 0.9 to 0.99;
    Crystallinity = [Ic / (Ia + Ic)]
    In the formula, Ic is a region where the diffraction angle 2θ 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.
  9. 　前記近赤外線吸収有機顔料が、ピロロピロール化合物およびスクアリリウム化合物から選ばれる少なくとも１種である、請求項１～８のいずれか１項に記載の近赤外線吸収有機顔料。 The near-infrared absorbing organic pigment according to any one of claims 1 to 8, wherein the near-infrared absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squarylium compound.
  10. 　請求項１～９のいずれか１項に記載の近赤外線吸収有機顔料と、樹脂と、溶剤とを含む顔料分散液。 A pigment dispersion containing the near-infrared absorbing organic pigment according to any one of claims 1 to 9, a resin, and a solvent.
  11. 　更に顔料誘導体を含む、請求項１０に記載の顔料分散液。 The pigment dispersion according to claim 10, further comprising a pigment derivative.
  12. 　請求項１～９のいずれか１項に記載の近赤外線吸収有機顔料と、樹脂と、硬化性化合物と、溶剤とを含む硬化性組成物。 A curable composition comprising the near-infrared absorbing organic pigment according to any one of claims 1 to 9, a resin, a curable compound, and a solvent.
  13. 　請求項１２に記載の硬化性組成物を用いた膜。 A film using the curable composition according to claim 12.
  14. 　請求項１３に記載の膜を有する近赤外線カットフィルタ。 A near-infrared cut filter having the film according to claim 13.
  15. 　請求項１３に記載の膜と、有彩色着色剤を含むカラーフィルタとを有する積層体。 A laminate comprising the film according to claim 13 and a color filter containing a chromatic colorant.
  16. 　請求項１３に記載の膜を有する固体撮像素子。 A solid-state imaging device having the film according to claim 13.
  17. 　請求項１３に記載の膜を有する画像表示装置。 An image display device having the film according to claim 13.
  18. 　請求項１３に記載の膜を有する赤外線センサ。 An infrared sensor having the film according to claim 13.
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