WO2017038252A1 - Matériau, composition, composition durcissable, film durci, filtre optique, élément d'imagerie solide, capteur de rayon infrarouge, module de caméra et procédé de production dudit matériau - Google Patents

Matériau, composition, composition durcissable, film durci, filtre optique, élément d'imagerie solide, capteur de rayon infrarouge, module de caméra et procédé de production dudit matériau Download PDF

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WO2017038252A1
WO2017038252A1 PCT/JP2016/070210 JP2016070210W WO2017038252A1 WO 2017038252 A1 WO2017038252 A1 WO 2017038252A1 JP 2016070210 W JP2016070210 W JP 2016070210W WO 2017038252 A1 WO2017038252 A1 WO 2017038252A1
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group
compound
ring
mass
pigment
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PCT/JP2016/070210
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English (en)
Japanese (ja)
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拓也 鶴田
恭平 荒山
全弘 森
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富士フイルム株式会社
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Priority to JP2017537627A priority Critical patent/JP6625130B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/10—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths
    • H04N23/12—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths with one sensor only

Definitions

  • the present invention relates to a material containing a pigment and a compound having a structure having an adsorptivity to a resin. Moreover, it is related with the manufacturing method of a composition, a curable composition, a cured film, an optical filter, a solid-state image sensor, an infrared sensor, a camera module, and material.
  • Patent Document 1 discloses a diketopyrrolopyrrole pigment (A), a dye derivative (B), a water-soluble inorganic salt (C), and a water-soluble organic solvent (D) that does not substantially dissolve the water-soluble inorganic salt (C). It is described that after kneading a mixture containing a water-soluble inorganic salt (C) and a water-soluble organic solvent (D), a pigment for a color filter is produced. In Patent Document 1, a color filter is manufactured using a coloring composition obtained by dispersing this pigment in a transparent resin.
  • the pigment may be used by being dispersed in a resin, a solvent, or the like, but if the pigment itself has low adsorptivity to the resin, the dispersibility of the pigment in the composition tends to decrease.
  • the color filter pigment obtained by the method described in Patent Document 1 is produced by mixing a diketopyrrolopyrrole pigment and a dye derivative.
  • the pigment for use was found to have poor adhesion between the diketopyrrolopyrrole pigment and the dye derivative, and the dye derivative was easily peeled off from the diketopyrrolopyrrole pigment.
  • the color filter pigment described in Patent Document 1 has a low adsorptivity with a resin and insufficient dispersibility of the pigment in the composition.
  • an object of the present invention is to provide a material containing a pigment and having excellent dispersibility of the pigment in the composition. Moreover, it is providing the manufacturing method of the composition excellent in the dispersibility of a pigment, a curable composition, a cured film, an optical filter, a solid-state image sensor, an infrared sensor, a camera module, and material.
  • the present inventors have synthesized a pigment by reacting a pigment raw material compound in the presence of a compound having a structure having an adsorptive property to a resin. It was found that a material in which the compound B having a structure having the above structure was firmly adsorbed was obtained. Although the detailed mechanism for obtaining a material in which compound B is firmly attached to pigment A is unknown, pigment A is synthesized by reacting the raw material compound of pigment A in the presence of compound B to produce pigment A. Since the compound B is taken into the particles, it is presumed that a material having the compound B physically and firmly attached to the pigment A was obtained.
  • the present invention provides the following.
  • ⁇ 2> The material according to ⁇ 1>, wherein the pigment A has absorption in the near infrared region.
  • Pigment A is one or more selected from phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complex compounds, naphthoquinone compounds, iminium compounds, azo compounds, and squarylium compounds.
  • pyrrolopyrrole compound is a compound represented by the following formula (1);
  • 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 They 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 bonded or coordinated, and R 4A and R 4B each independently represents a substituent.
  • Dye structure is 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 At least one selected from a structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure
  • the compound B has at least one selected from an acidic group, a basic group, a hydrogen bonding group, a dipole interacting group, and a ⁇ - ⁇ interacting group, from ⁇ 1> to ⁇ 8>
  • the material according to any one ⁇ 10> A composition comprising the material according to any one of ⁇ 1> to ⁇ 9>.
  • the composition according to ⁇ 10> further comprising at least one selected from an organic solvent, a resin, and a pigment derivative.
  • a curable composition comprising the composition according to ⁇ 10> or ⁇ 11> and a curable compound.
  • ⁇ 13> A cured film using the curable composition according to ⁇ 12>.
  • ⁇ 14> An optical filter having the cured film according to ⁇ 13>.
  • the optical filter according to ⁇ 14> which is at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter.
  • ⁇ 16> A pixel of the cured film according to ⁇ 13>, The optical filter according to ⁇ 14> or ⁇ 15>, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
  • ⁇ 17> A solid-state imaging device having the cured film according to ⁇ 13>.
  • ⁇ 18> An infrared sensor having the cured film according to ⁇ 13>.
  • a method for producing a material comprising a pigment A and a compound B having a structure having an adsorptivity to a resin, A method for producing a material, wherein the pigment A is synthesized by reacting the raw material compound of the pigment A in the presence of the compound B having a structure having an adsorptivity to the resin when the pigment A is synthesized.
  • the present invention it is possible to provide a material containing a pigment and having excellent dispersibility of the pigment in the composition.
  • a composition, a curable composition, a cured film, an infrared cut filter, a solid-state imaging device, an infrared sensor, a camera module, and a material manufacturing method excellent in pigment dispersibility it has become possible to provide a composition, a curable composition, a cured film, an infrared cut filter, a solid-state imaging device, an infrared sensor, a camera module, and a material manufacturing method excellent in pigment dispersibility.
  • 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).
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the near-infrared region refers to a range where the wavelength region is 700 to 2500 nm.
  • Near-infrared light refers to light (electromagnetic wave) having a wavelength region of 700 to 2500 nm.
  • the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • solid content means solid content in 25 degreeC.
  • a weight average molecular weight is defined as a polystyrene conversion value by 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.
  • the pigment means an insoluble compound that is difficult to dissolve in a specific solvent. Typically, it means a compound that exists in a dispersed state as particles in the composition.
  • the solvent illustrated in the column of the solvent mentioned later for example is mentioned.
  • the pigment used in the present invention preferably has a solubility in propylene glycol monomethyl ether acetate at 25 ° C. of 0.02% by mass or less.
  • the material of the present invention is a material containing the pigment A and the compound B having a structure having an adsorptivity to a resin, and X 1 represented by the following formula (I) is 0.99 or more.
  • X 1 (X 2 / X 3 ) ⁇ 100
  • X 2 is a solvent having a solubility of Pigment A of 0.02% by mass or less and a solubility of Compound B of 0.2% by mass or more at 25 ° C., and the mass of Compound B in the material after dipping the material
  • X 3 is the mass of the solid content of the material after being immersed in the solvent.
  • the compound B described above is firmly attached to the pigment A, and the adsorptivity of the pigment A to the resin is excellent. For this reason, the dispersibility of the pigment in a composition can be made favorable.
  • the pigment A and the compound B exist as separate compounds.
  • Pigment A and Compound B are present as separate compounds means that Pigment A is present outside the molecule of Compound B, and the two are not covalently bonded. To do. That is, the material of the present invention is different from a compound (for example, a dye derivative) obtained by introducing a group having adsorptivity to a resin into a part of pigment molecules.
  • the content of the pigment A in the material of the present invention is preferably 30 to 99% by mass.
  • the lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more.
  • the upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the content of Compound B in the material of the present invention is preferably 0.99% by mass or more and less than 70% by mass.
  • the lower limit is more preferably 2.91% by mass or more, and particularly preferably 4.76% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the compound B is preferably contained in an amount of 1 to 150 parts by mass with respect to 100 parts by mass of the pigment A.
  • 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 100 parts by mass or less, and more preferably 70 parts by mass or less.
  • the content of Compound B in the material is determined by measuring the amount of Compound B contained in the filtrate discharged during the production of the material by high performance liquid chromatography (HPLC), thereby determining the amount of Compound B remaining in the material. It can be calculated. It can also be quantified and calculated by a method such as infrared spectroscopy (IR).
  • IR infrared spectroscopy
  • X 1 represented by the above formula (I) (content ratio of compound B in the material after immersion in the solvent) is 0.99 or more, preferably 3 or more, and particularly preferably 5 or more. .
  • the upper limit can be, for example, 70 or less, 60 or less, or 50 or less.
  • X 1 is equal to or more than 0.99, compound B has firmly adhered to the pigment A, excellent in adsorptivity to the resin of the pigment. For this reason, the dispersibility of the pigment in a composition can be made favorable.
  • X 1 is calculated using, for example, X 2 and X 3 measured as follows.
  • the mass X 3 of the solid content of the material after immersion in the solvent can be obtained by measuring the mass after removing the solvent adhering to the material from the material after immersion in the solvent by a method such as drying. .
  • the mass at the time when the weight reduction rate of the material after immersion in the solvent is saturated (the mass when the weight reduction rate becomes almost constant) can be obtained by thermal analysis TGA (differential thermal analysis).
  • the measuring device include a thermogravimetric measuring device Q500 type ((TE Instruments Japan Co., Ltd.)).
  • X 2 which is the mass of the compound B in the material after the solvent immersion is obtained by measuring the amount of the compound B contained in the filtrate discharged after washing the material with the solvent by high performance liquid chromatography (HPLC). It can be calculated as the amount of compound B remaining therein.
  • the material before and after immersion in the solvent can be quantified and calculated by a method such as infrared spectroscopy (IR).
  • the solvent is not particularly limited as long as it satisfies the requirement that the solubility of the pigment A is 0.02% by mass or less and the solubility of the compound B is 0.2% by mass or more at 25 ° C. .
  • the organic solvent etc. which the composition mentioned later may contain are mentioned. Specific examples include methanol, ethanol, tetrahydrofuran, acetone and the like.
  • the dipping method include a method of adding 16.6 mL of a solvent to 1 g of a sample, heating and refluxing for 30 minutes, and then performing a filtration treatment.
  • the material of the present invention will be described.
  • the material of the present invention contains pigment A.
  • the type of the pigment A is not particularly limited. It may be a pigment having absorption in the visible region (hereinafter also referred to as a chromatic pigment), or may be a pigment having absorption in the near infrared region (hereinafter also referred to as near infrared absorbing dye).
  • the chromatic pigment is not particularly limited, and examples thereof include compounds having absorption in the visible region (preferably in the wavelength range of 400 to 700 nm, more preferably in the range of 400 to 650 nm). Examples include diketopyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, azo compounds, isoindoline compounds, quinophthalone compounds, benzimidazolone compounds, and perinone compounds. Specific examples of the chromatic pigment include the following.
  • the near-infrared absorbing dye a compound having a maximum absorption wavelength in the range of 700 to 1200 nm is preferable, and a compound having a maximum absorption wavelength in the range of 700 to 1000 nm is more preferable.
  • the pigment A is preferably a near infrared absorbing dye. Many near-infrared absorbing dyes tend to have low dispersibility in the composition, and further improvement in dispersibility is desired, and the effects of the present invention are particularly easily obtained.
  • Examples of near-infrared absorbing dyes include phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complex compounds, naphthoquinone compounds, iminium compounds, azo compounds, and squarylium compounds.
  • a naphthalocyanine compound, a pyrrolopyrrole compound, a cyanine compound and a squarylium compound are preferred, and a pyrrolopyrrole compound is more preferred.
  • the pyrrolopyrrole compound is preferably a pyrrolopyrrole boron compound.
  • a pyrrolopyrrole compound is excellent in near-infrared absorptivity and invisibility, it is easy to obtain a cured film such as an infrared cut filter excellent in near-infrared shielding and visible transmission. Further, the pyrrolopyrrole compound is a pigment having low dispersibility in the composition, but according to the present invention, the dispersibility of the pigment in the composition can be improved, and the effects of the present invention can be more easily obtained. . Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614.
  • phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound
  • the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated.
  • the cyanine compound for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .
  • the pyrrolopyrrole compound is preferably a compound represented by the formula (1). This compound is excellent in near-infrared absorptivity and invisibility.
  • 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 They 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 from 1 to 30, and more preferably from 1 to 12.
  • hetero atom which comprises a heteroaryl group
  • a nitrogen atom, an oxygen atom, and a sulfur atom can be 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, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further 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.
  • the substituent examples include the groups exemplified 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.
  • R 1a and R 1b in formula (1) may be the same as or different from each other.
  • R 2 and R 3 each independently represents a hydrogen atom or a substituent.
  • R 2 and R 3 may combine 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.
  • the following substituent T can be mentioned as an example of a substituent.
  • Substituent T An alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably 2 to 30 carbon atoms).
  • Substituted or unsubstituted alkynyl group an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), an amino group (preferably a substituted or unsubstituted amino group having 0 to 30 carbon atoms), An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably carbon A substituted or unsubstituted heteroaryloxy group having 1 to 30 carbon atoms, an acyl group (preferably a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms).
  • Unsubstituted acyl group alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms) Group), an acyloxy group (preferably a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably A substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably having a carbon
  • Substituted phosphate amide group hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heteroaryl group (preferably carbon number) 1-30).
  • the carboxy group may be dissociated from a hydrogen atom or may be in a salt state.
  • the sulfo group may be dissociated from a hydrogen atom or in a salt state.
  • these groups are further substitutable groups, they may further have a substituent. Examples of the substituent include the groups described above for the substituent T.
  • At least one of R 2 and R 3 is preferably an electron-withdrawing group.
  • a substituent having a positive Hammett ⁇ p value acts as an electron-withdrawing group.
  • a substituent having a Hammett ⁇ p value of 0.2 or more can be exemplified as an electron-withdrawing group.
  • the ⁇ p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.
  • the upper limit is not particularly limited, but is preferably 0.80.
  • cyano group (0.66), carboxy group (—COOH: 0.45), alkoxycarbonyl group (—COOMe: 0.45), aryloxycarbonyl group (—COOPh: 0.44), carbamoyl.
  • a group (—CONH 2 : 0.36), an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO 2 Me: 0.72), or And arylsulfonyl group (—SO 2 Ph: 0.68).
  • a cyano group is particularly preferred.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the Hammett's substituent constant ⁇ value for example, paragraphs 0017 to 0018 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated herein.
  • 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 3 is particularly preferably 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 further 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.
  • the number of carbon atoms constituting the heteroaryl group is preferably 1 to 30, and more preferably 1 to 12.
  • Specific examples of the heteroaryl group include imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, quinoxalyl group, isoquinolyl group, indolenyl group, furyl group, thienyl group, benzoxazolyl group.
  • the heteroaryl group may have a substituent or may be unsubstituted.
  • substituents include the groups described above for the substituent T.
  • an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned.
  • Two R 2 in the formula (1) may be the same as or different from each other, and two R 3 may be the same as or different from each other.
  • R 4 represents an alkyl group, an aryl group, or a heteroaryl group
  • the alkyl group, aryl group, and heteroaryl group have the same meanings 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.
  • Specific examples of the group represented by —BR 4A R 4B include difluoroboron, diphenylboron, dibutylboron, dinaphthylboron, and catecholboron. Of these, diphenylboron 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 diphenylboron). Two R 4 in the formula (1) may be the same or different.
  • the dye represented by the formula (1) is more preferably a dye represented by the following formula (1A).
  • each R 10 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 14A R 14B or a metal atom.
  • R 10 may be covalently bonded or coordinated to R 12 .
  • R 11 and R 12 each independently represent a hydrogen atom or a substituent, at least one of which is a cyano group, and R 11 and R 12 may combine to form a ring.
  • R 13 each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms.
  • R 10 has the same meaning as R 4 described in the above formula (1), and the preferred range is also the same.
  • a hydrogen atom or a group represented by —BR 14A R 14B (particularly diphenylboron) is preferred, and a group represented by —BR 14A R 14B is particularly preferred.
  • R 11 and R 12 have the same meanings as R 2 and R 3 described in (1) above, and preferred ranges are also the same. More preferably, one of R 11 and R 12 is a cyano group and the other is a heteroaryl group.
  • R 14A and R 14B have the same meanings as R 4A and R 4B described in (1) above, and preferred ranges are also the same.
  • R 13 each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms in the branched alkyl group is more preferably 3-20.
  • Ar-1 to Ar-4 and R-1 to R-7 in the above table are as follows.
  • “*” is a bond.
  • the squarylium compound is preferably a compound represented by the formula (11). This compound is excellent in near-infrared absorptivity and invisibility.
  • a 1 and A 2 each independently represent an aryl group, a heteroaryl group or a group represented by the following formula (12);
  • Z 1 represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle
  • R 2 represents an alkyl group, an alkenyl group, or an aralkyl group
  • d represents 0 or 1
  • a wavy line represents This represents a connecting hand with the formula (11).
  • a 1 and A 2 in Formula (11) each independently represent an aryl group, a heteroaryl group, or a group represented by Formula (12), and a group represented by Formula (12) is preferable.
  • the number of carbon atoms of the aryl group represented by A 1 and A 2 is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. Specific examples include a phenyl group and a naphthyl group. When the aryl group has a substituent, the carbon number of the aryl group means the number excluding the carbon number of the substituent.
  • the heteroaryl group represented by A 1 and A 2 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, still more preferably a single ring or a condensed ring having 2 to 4 condensations, a single ring or A condensed ring having a condensation number of 2 or 3 is particularly preferred.
  • a hetero atom which comprises a heteroaryl group a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
  • aryl group and heteroaryl group may have a substituent.
  • substituents include the substituent T described in the above-described pyrrolopyrrole compound.
  • the substituent that the aryl group and heteroaryl group may have is preferably a halogen atom, an alkyl group, a hydroxy group, an amino group, or an acylamino group.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5, and most preferably 1 to 4.
  • the alkyl group is preferably linear or branched.
  • the amino group is preferably a group represented by —NR 100 R 101 .
  • R 100 and R 101 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group is preferably linear or branched, and more preferably linear.
  • the acylamino group is preferably a group represented by —NR 102 —C ( ⁇ O) —R 103 .
  • R102 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
  • R 103 represents an alkyl group.
  • the number of carbon atoms of the alkyl group represented by R 102 and R 103 is preferably 1-20, more preferably 1-10, still more preferably 1-5, and particularly preferably 1-4.
  • the plurality of substituents may be the same or different.
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group
  • Alkyl groups are preferred.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms.
  • the alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
  • the aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms.
  • the nitrogen-containing heterocycle formed by Z 1 is preferably a 5-membered ring or a 6-membered ring.
  • the nitrogen-containing heterocycle is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations, Is particularly preferably a fused ring of 2 or 3.
  • the nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom.
  • the nitrogen-containing heterocycle may have a substituent. Examples of the substituent include the groups described above for the substituent T.
  • a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms.
  • the alkyl group is preferably linear or branched.
  • the group represented by the formula (12) is preferably a group represented by the following formula (13) or the formula (14).
  • R 11 represents an alkyl group, an alkenyl group or an aralkyl group
  • R 12 represents a substituent
  • m represents 2 or more, R 12 are linked to each other.
  • a ring may form
  • X represents a nitrogen atom or CR 13 R 14
  • R 13 and R 14 each independently represent a hydrogen atom or a substituent
  • m represents an integer of 0 to 4
  • the wavy line represents a connecting hand with the formula (11).
  • R 11 in formula (13) and formula (14) has the same meaning as R 2 in formula (12); The preferable range is also the same.
  • R 12 in Formula (13) and Formula (14) represents a substituent.
  • the substituent include the groups described above for the substituent T.
  • a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable.
  • the halogen atom is preferably a chlorine atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms.
  • the alkyl group is preferably linear or branched.
  • R 12 may be linked to form a ring.
  • the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, a heterocyclic ring, and the like.
  • the ring may be monocyclic or multicyclic.
  • the linking group is a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. They can be linked by a divalent linking group selected from the above.
  • R 12 are connected to each other to form a benzene ring.
  • X in Formula (13) represents a nitrogen atom or CR 13 R 14 , and R 13 and R 14 each independently represent a hydrogen atom or a substituent.
  • substituents include the groups described above for the substituent T.
  • an alkyl group etc. are mentioned.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1.
  • the alkyl group is preferably linear or branched, and particularly preferably linear.
  • m represents an integer of 0 to 4, preferably 0 to 2.
  • the squarylium compound is preferably a compound represented by the following formula (15).
  • Ring A and Ring B each independently represent an aromatic ring or a heteroaromatic ring
  • X A and X B each independently represent a substituent
  • G A and G B each independently represent a substituent
  • kA represents an integer of 0 to n A
  • kB represents an integer of 0 to n B
  • n A and n B each represent the largest integer that can be substituted for ring A or ring B
  • X A and G A, X B and G B may combine with each other to form a ring, if G A and G B are present in plural may be bonded to form a ring structure .
  • G A and G B each independently represent a substituent.
  • Substituents include halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, —OR 10 , —COR 11 , —COOR 12 , —OCOR 13 , — NR 14 R 15 , —NHCOR 16 , —CONR 17 R 18 , —NHCONR 19 R 20 , —NHCOOR 21 , —SR 22 , —SO 2 R 23 , —SO 2 OR 24 , —NHSO 2 R 25 or —SO 2 NR 26 R 27 may be mentioned.
  • R 10 to R 27 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group.
  • R 12 of —COOR 12 is hydrogen (ie, a carboxy group)
  • the hydrogen atom may be dissociated or may be in a salt state.
  • R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
  • the hydrogen atom may be dissociated or may be in a salt state.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkynyl group has preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 25 carbon atoms.
  • the alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkyl part of the aralkyl group is the same as the above alkyl group.
  • the aryl part of the aralkyl group is the same as the above aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
  • 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 further preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.
  • heteroaryl groups include pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring , Indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring.
  • alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted.
  • substituent include the groups described in the substituent group T described above.
  • X A and X B each independently represent a substituent.
  • the substituent is preferably a group having active hydrogen, —OH, —SH, —COOH, —SO 3 H, —NR X1 R X2 , —NHCOR X1 , —CONR X1 R X2 , —NHCONR X1 R X2 , —NHCOOR X 1 , —NHSO 2 R X1 , —B (OH) 2 and —PO (OH) 2 are more preferable, and —OH, —SH and —NR X1 R X2 are still more preferable.
  • R X1 and R X2 each independently represent a hydrogen atom or a substituent.
  • substituents examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group.
  • Alkyl groups are preferred.
  • the alkyl group is preferably linear or branched.
  • Alkyl group, an alkenyl group, an alkynyl group, an aryl group and that details of the heteroaryl group, is as defined and ranges described for the G A and G B.
  • Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring.
  • the aromatic ring and heteroaromatic ring may be a single ring or a condensed ring.
  • Specific examples of the aromatic ring and heteroaromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring , Chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazin
  • X A and G A, X B and G B may combine with each other to form a ring, if G A and G B are present in plural may be bonded to each other to form a ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring.
  • the ring may be monocyclic or multicyclic.
  • X A and G A, X B and G B, when forming a G A or between G B are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-,
  • a ring may be formed by bonding via a divalent linking group selected from the group consisting of —O—, —NH—, —BR— and combinations thereof.
  • X A and G A , X B and G B , G A or G B are preferably bonded via —BR— to form a ring.
  • R represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described in G A and G B. An alkyl group or an aryl group is preferred.
  • KA represents an integer of 0 to nA
  • kB represents an integer of 0 to nB
  • nA represents the largest integer that can be substituted for ring A
  • nB represents the largest integer that can be substituted for ring B.
  • kA and kB are each independently preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.
  • the cyanine compound is preferably a compound represented by the formula (A).
  • This compound is excellent in near-infrared absorptivity and invisibility.
  • Formula (A) In the formula (A), Z 1 and Z 2 are each independently a nonmetallic atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and R 1 and R 2 are Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, L 1 represents a methine chain having an odd number of methine groups, and a and b are each independently 0 or 1 Yes, When the site represented by Cy in the formula is a cation moiety, X 1 represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X 1 represents
  • Z 1 and Z 2 each independently represents a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed.
  • the nitrogen-containing heterocyclic ring may be condensed with other heterocyclic ring, aromatic ring or aliphatic ring.
  • the nitrogen-containing heterocycle is preferably a 5-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring.
  • nitrogen-containing heterocycle examples include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimi
  • the nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent.
  • substituents include the substituents described above for G A and G B in the formula (15). Specifically, halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, —OR 10 , —COR 11 , —COOR 12 , —OCOR 13 , — NR 14 R 15 , —NHCOR 16 , —CONR 17 R 18 , —NHCONR 19 R 20 , —NHCOOR 21 , —SR 22 , —SO 2 R 23 , —SO 2 OR 24 , —NHSO 2 R 25 or —SO 2 NR 26 R 27 may be mentioned.
  • R 10 to R 27 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group.
  • R 12 of —COOR 12 is hydrogen (ie, a carboxy group)
  • the hydrogen atom may be dissociated or may be in a salt state.
  • R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
  • the hydrogen atom may be dissociated or may be in a salt state.
  • the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted.
  • substituents include the groups described in the above-mentioned substituent group T, preferably a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, an amino group, and the like, more preferably a carboxy group and a sulfo group, and a sulfo group.
  • the group is particularly preferred.
  • the carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.
  • R 1 and R 2 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkynyl group has preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 25 carbon atoms.
  • the alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkyl part of the aralkyl group is the same as the above alkyl group.
  • the aryl part of the aralkyl group is the same as the above aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
  • the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group.
  • a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable.
  • the carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.
  • L 1 represents a methine chain having an odd number of methine groups.
  • L 1 is preferably a methine chain having 3, 5, or 7 methine groups, and more preferably a methine chain having 5 or 7 methine groups.
  • the methine group may have a substituent.
  • the methine group having a substituent is preferably a central (meso-position) methine group.
  • Specific examples of the substituent include a substituent which the nitrogen-containing heterocycle of Z 1 and Z 2 may have, and a group represented by the formula (a).
  • two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.
  • * represents a connecting part with a methine chain
  • a 1 represents an oxygen atom or a sulfur atom.
  • a and b are each independently 0 or 1. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. When a and b are both 0, the formula (A) is expressed as follows.
  • X 1 represents an anion
  • c represents a number necessary for balancing the charge.
  • anions include halide ions (Cl ⁇ , Br ⁇ , I ⁇ ), paratoluenesulfonate ions, ethyl sulfate ions, PF 6 ⁇ , BF 4 ⁇ or ClO 4 ⁇ , tris (halogenoalkylsulfonyl) methide anions (eg, , (CF 3 SO 2 ) 3 C ⁇ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF 3 SO 2 ) 2 N ⁇ ), tetracyanoborate anion, and the like.
  • X 1 represents a cation
  • c represents a number necessary for balancing the charge.
  • alkali metal ions Li + , Na + , K + etc.
  • alkaline earth metal ions Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+, etc.
  • transition metal ions Al 3+
  • Examples include ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium and the like.
  • the compound represented by the formula (A) is also preferably a compound represented by the following (A-1) or (A-2), and more preferably a compound represented by the following (A-2).
  • R 1A , R 2A , R 1B and R 2B each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group
  • L 1A and L 1B each independently represent a methine chain having an odd number of methines
  • Y 1 and Y 2 each independently represent —S—, —O—, —NR X1 — or —CR X2 R X3 —
  • R X1 , R X2 and R X3 each independently represent a hydrogen atom or an alkyl group
  • V 1A , V 2A , V 1B and V 2B are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, —OR 10 , — COR 11 , —COOR 12 , —OCOR 13
  • n1 and m2 each independently represents 0 to 4;
  • X 1 represents an anion
  • c represents a number necessary to balance the charge
  • X 1 represents a cation
  • c represents a number necessary for balancing the charge
  • the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.
  • R 1A , R 2A , R 1B and R 2B are synonymous with the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described for R 1 and R 2 in formula (A), and preferred ranges Is the same. These groups may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group. A carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable.
  • the carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.
  • R 1A , R 2A , R 1B and R 2B represent an alkyl group, it is more preferably a linear alkyl group.
  • Y 1 and Y 2 are each independently -S -, - O -, - NR X1 - or -CR X2 R X3 - represents, -NR X1 - is preferred.
  • R X1 , R X2 and R X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • the alkyl group is particularly preferably a methyl group or an ethyl group.
  • L 1A and L 1B have the same meaning as L 1 in formula (A), and the preferred range is also the same.
  • the groups represented by V 1A , V 2A , V 1B and V 2B are synonymous with the ranges described for the substituents that the nitrogen-containing heterocycles of Z 1 and Z 2 in formula (A) may have, and preferred ranges Is the same.
  • m1 and m2 each independently represents 0 to 4, preferably 0 to 2.
  • the anion and cation represented by X 1 have the same meaning as the range described for X 1 in formula (A), and the preferred range is also the
  • the compound represented by the formula (A) is preferably a compound represented by the following (A-11) to (A-16).
  • R 1a and R 2a each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group
  • X 1 and X 2 each independently represent —S—, —O—, —NR X1 — or —CR X2 R X3 —
  • R X1 , R X2 and R X3 each independently represent a hydrogen atom or an alkyl group
  • R 3a , R 4a , V 1a and V 2a are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, —OR 10 , — COR 11 , —COOR 12 , —OCOR 13 , —NR 14 R 15 , —NHCOR 16 , —CONR 17 R 18 , —NHCONR 19 R 20 ,
  • R 1a and R 2a has the same meaning as R 1 and R 2 in formula (A-1), and the preferred range is also the same.
  • R 1a and R 2a represent an alkyl group, it is more preferably a linear alkyl group.
  • X 1 and X 2 has the same meaning as X 1 and X 2 in the formula (A-1), and preferred ranges are also the same.
  • R ⁇ 3a> and R ⁇ 4a> are synonymous with the range demonstrated by the substituent which L ⁇ 1 > may have which was demonstrated in Formula (A), and its preferable range is also the same.
  • V 1a and V 2a are synonymous with the ranges described in the nitrogen-containing heterocycle described in the formula (A) and the substituents that the ring condensed thereto may have, and the preferred ranges are also the same. It is. m1 and m2 each independently represents 0 to 4, preferably 0 to 2.
  • examples of the diketopyrrolopyrrole compound include compounds represented by the following formula (DP).
  • Formula (DP) In the formula, R 1 and R 2 each independently represents an alkyl group, an aryl group, or a heteroaryl group. R 1 and R 2 are preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the number of carbon atoms constituting the heteroaryl group is preferably 1-30, and more preferably 1-12.
  • a kind of hetero atom which comprises a heteroaryl group a nitrogen atom, an oxygen atom, and a sulfur atom can be 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, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further 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. Examples of the substituent include the substituent T described above. For example, a halogen atom is preferable.
  • phthalocyanine compound compound having a phthalocyanine structure
  • examples of the phthalocyanine compound include compounds represented by the following formula (PC).
  • X 1 to X 16 each independently represents a hydrogen atom or a substituent, and M 1 represents a metal atom or a metal compound.
  • Examples of the substituent represented by X 1 to X 16 include the substituent T described above. Examples include a halogen atom, an alkoxy group, an arylalkoxy group, a heteroarylalkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group, and a halogen atom is preferable.
  • a compound (oxotitanyl phthalocyanine) in which M 1 is represented by Ti ⁇ O is excellent in near infrared absorption.
  • compounds in which M 1 is Zn or Cu and at least one of X 1 to X 16 is a halogen atom have excellent spectral characteristics in the visible region. It can be preferably used as a green pigment.
  • examples of the naphthalocyanine compound include compounds represented by the following formula (NPC).
  • X 1 to X 24 each independently represents a hydrogen atom or a substituent
  • M 1 represents a metal atom or a metal compound.
  • substituent represented by X 1 to X 24 include the substituent T described above. Examples include a halogen atom, an alkoxy group, an arylalkoxy group, a heteroarylalkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group, and an alkoxy group is preferable.
  • Specific examples of the compound represented by the formula (NPC) include the following compounds.
  • the material of the present invention contains Compound B having a structure having an adsorptivity to a resin.
  • Compound B is preferably a compound having substantially no molecular weight distribution. That is, the compound B is preferably a compound other than the polymer. According to this aspect, since the molecular weight is smaller than that of the polymer, the mobility in the solvent is high, and it can exist uniformly in the system. Therefore, the effect that it can be included efficiently at the time of pigment production can be expected.
  • the molecular weight of Compound B is preferably 50 to 2000, and more preferably 100 to 1500. In the present invention, the compound B has a solubility in a solvent at 25 ° C.
  • the solvent illustrated in the column of the solvent mentioned later is mentioned, One or more types chosen from methanol, ethanol, tetrahydrofuran, and acetone are preferable.
  • the structure of the compound B having an adsorptivity to the resin include an acidic group, a basic group, a hydrogen bonding group, a dipole interaction group, and a ⁇ - ⁇ interaction group.
  • the group having an acidic group, a basic group, or a salt structure include groups described in the dye derivatives described later.
  • the interaction between dipoles means that polarized molecules interact with other dipoles, and hydrogen bonds are one of them.
  • specific examples other than hydrogen bonds include nitrile groups, perfluoroalkyl groups, perfluoroaryl groups, and the like.
  • a hydrogen bond is a non-covalent bond formed by a hydrogen atom covalently bonded to an atom having a large electronegativity with a lone electron pair such as nitrogen, oxygen, sulfur, fluorine, or a ⁇ electron system located nearby. It is an attractive interaction of sex.
  • the hydrogen bonding group in the present invention is a substituent having at least one of the above hydrogen atom or lone electron pair, and examples thereof include an amide group, an alcohol group, a phenol group, and a carboxy group.
  • ⁇ - ⁇ interaction is a dispersion force acting between aromatic rings of organic compound molecules, and is also called stacking interaction.
  • aromatic compounds have a strong planar structure and abundant electrons delocalized by the ⁇ -electron system, so that the London dispersion force is particularly strong. Therefore, the force attracting each other increases as the number of ⁇ electrons increases.
  • ⁇ - ⁇ interacting groups include aromatic rings and heteroaromatic rings.
  • benzene ring naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, Isobenzofuran ring, quinolidine
  • Compound B preferably has at least one selected from a dye structure, a heterocyclic structure, and an acyclic heteroatom-containing group, and more preferably has at least a dye structure. Since compound B has these structures, compound B is easily included in the particles of pigment A, and a material in which pigment A and compound B are firmly attached is easily obtained.
  • 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
  • Preferred examples include a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzoimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure.
  • Heterocyclic structures include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, Preferred examples of pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzimidazole, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone As mentioned.
  • Examples of the acyclic heteroatom-containing group include a group having a nitrogen atom, and preferable examples include a urea group, an imide group, an amide group, and a sulfonamide group.
  • —NR 100 CONR 101 R 102 may be mentioned.
  • R 100 , R 101 , and R 102 each independently represents a hydrogen atom, an alkyl group, or an aryl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms.
  • R 100 and R 101 are preferably hydrogen atoms.
  • R 102 is preferably an alkyl group or an aryl group, and more preferably an aryl group.
  • compound B is preferably a pigment derivative.
  • the compound B is easily included in the particles of the pigment A, and a material in which the compound B is firmly attached to the pigment A is easily obtained.
  • the dye derivative a compound having a structure in which a part of the dye is substituted with an acidic group, a basic group or a phthalimidomethyl group is preferable, and a dye derivative represented by the formula (B1) is more preferable.
  • the dye derivative represented by the formula (B1) can improve the dispersibility of the pigment A in the composition because the dye structure P is easily adsorbed on the surface of the pigment A.
  • the terminal portion X of the dye derivative is adsorbed to the resin by interaction with the adsorption portion (polar group or the like) of the resin, so that the dispersibility of the pigment A can be further improved.
  • 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 phthalimide group
  • m represents 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. When the pigment derivative has these pigment structures, the dispersibility of the pigment A can be further
  • 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. These may be unsubstituted or may further have a substituent. Examples of the substituent include the substituent T described above, and an alkyl group, an aryl group, a hydroxy group, or a halogen atom is preferable.
  • the linking group is preferably an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, —NR′—, —SO 2 —, —S—, —O—, —CO— or a group consisting of these, an alkylene group, A nitrogen-containing heterocyclic group, —NR′—, —SO 2 —, or a combination thereof is more preferable.
  • R ′ represents a hydrogen atom, an alkyl group (preferably having 1 to 30 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms).
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkylene group may have a substituent.
  • the alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic.
  • the carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 10, and particularly preferably a phenylene group.
  • the nitrogen-containing heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the nitrogen-containing heterocyclic 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 further preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of nitrogen atoms constituting the nitrogen-containing heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.
  • the nitrogen-containing heterocyclic group may contain a hetero atom other than the nitrogen atom.
  • Examples of the hetero atom other than the nitrogen atom include an oxygen atom and a sulfur atom.
  • the number of heteroatoms other than nitrogen atoms is preferably 0-3, more preferably 0-1.
  • linking group examples include an alkylene group, an arylene group, —SO 2 —, and the above (L-1).
  • a group represented by the above (L-5) a group composed of a combination of -O- and an alkylene group, a group composed of a combination of -NR'- and an alkylene group, -NR'- and A group consisting of a combination with —CO— (—NR′—CO—, —NR′—CO—NR′—, etc.), a group consisting of a combination of —NR′—, —CO— and an alkylene group, —NR ′ A group comprising a combination of-, -CO-, an alkylene group and an arylene group, a group comprising a combination of -NR'-, -CO- and an arylene group, a combination of -NR'-, -SO 2 -and an alkylene group A group consisting of a combination of —NR′—, —SO 2 —, an
  • X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide group.
  • the acidic group include a carboxy group and a sulfo group.
  • the basic group include groups represented by formulas (X-3) to (X-9).
  • the group having a salt structure include the above-described acidic group salts, basic group salts, groups represented by the formula (X-1), and groups represented by (X-2).
  • 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 more preferable.
  • alkali metal atom examples include lithium, sodium, potassium and the like.
  • alkaline earth metal atoms include calcium and magnesium.
  • the phthalimide group may be unsubstituted or may have a substituent.
  • substituent examples include the acid groups, basic groups, and groups having a salt structure described above.
  • substituent T mentioned above may be sufficient.
  • the substituent T may be further substituted with another substituent. Examples of other substituents include a carboxy group and a sulfo group.
  • X is preferably at least one selected from a carboxy group, a sulfo group, a phthalimide group, and groups represented by the following formulas (X-1) to (X-9).
  • * represents a bond to L in the formula (B1)
  • R 100 to R 106 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl R 100 and R 101 may be connected to each other to form a ring
  • M represents an atom or an atomic group constituting a salt with an anion.
  • the alkyl group may be linear, branched or cyclic.
  • the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms.
  • the cyclic alkyl group may be monocyclic or polycyclic.
  • the carbon number of the cyclic alkyl group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
  • the alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • R 100 and R 101 may be connected to each other to form a ring.
  • the ring may be an aliphatic ring or an aromatic ring.
  • the ring may be monocyclic or multicyclic.
  • Examples of the linking group in the case where R 100 and R 101 are bonded to form a ring include —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. It can connect with the bivalent coupling group chosen from the group which consists of.
  • m represents an integer of 1 or more.
  • the upper limit of m represents the number of substituents that the dye structure P can take. For example, 10 or less is preferable and 5 or less is more preferable.
  • m is 2 or more, a plurality of L and X may be different from each other.
  • n represents an integer of 1 or more, preferably 1 to 3, and more preferably 1 to 2.
  • the plurality of Xs may be different from each other.
  • dye derivative represented by the formula (B1) include the following (B-1) to (B-62).
  • m, m1, m2, and m3 each independently represents an integer of 1 or more.
  • Ar-5, Ar-6, R-1 to R-7, Ra to R-1 in the above table are as follows.
  • “*” is a bond.
  • JP-A No. 56-118462 JP-A No. 63-264673, JP-A No. 1-217077, JP-A No. 3-9961 and JP-A No. 3-26767 are disclosed.
  • the method for producing a material of the present invention is a method for producing a material containing pigment A and compound B having a structure having an adsorptive property to resin, and has a structure having an adsorptive property to resin when the pigment A is synthesized.
  • Pigment A is synthesized by reacting the raw material compound of Pigment A in the presence of Compound B having NO. By thus synthesizing the pigment A, a material in which the compound B is firmly attached to the pigment A is obtained. Even if this material is washed with a solvent or the like, the compound B adheres firmly to the pigment A.
  • Pigment A is obtained by reacting the raw material compound of Pigment A in the presence of Compound B.
  • the compound B is taken into the particles of the pigment A, it is presumed that a material in which the compound B is firmly attached to the pigment A is obtained.
  • the adsorptivity of the compound B to the pigment A is low, and when the mixed material is washed with a solvent having solubility in the compound B, the pigment A Compound B is peeled off from the surface, and compound B hardly remains on the surface of pigment A. Therefore, the material obtained by the production method of the present invention has different characteristics from the material produced by the conventional method.
  • the material obtained by the production method of the present invention preferably has a pigment A content of 30 to 99% by mass.
  • the lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more.
  • the upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the content of Compound B is preferably 0.99 mass% or more and less than 70 mass%.
  • the lower limit is more preferably 2.91% by mass or more, and particularly preferably 4.76% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • X 1 represented by the following formula (I) is preferably 0.99 or more, more preferably 3 or more, and particularly preferably 5 or more.
  • the upper limit can be, for example, 70 or less, 60 or less, or 50 or less.
  • X 1 (X 2 / X 3 ) ⁇ 100
  • X 2 is a solvent having a solubility of Pigment A of 0.02% by mass or less and a solubility of Compound B of 0.2% by mass or more at 25 ° C., and the mass of Compound B in the material after dipping the material
  • X 3 is the mass of the solid content of the material after being immersed in the solvent.
  • the said solvent and the immersion method are synonymous with the content demonstrated with the material of this invention mentioned above.
  • the composition of the present invention includes the material of the present invention described above.
  • the content of the material in the composition of the present invention is preferably 1 to 80% by mass in the total solid content, and the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the composition of the present invention may further contain a chromatic colorant in addition to the above-described material of 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 a maximum absorption wavelength in the wavelength range of 400 to 650 nm.
  • the chromatic colorant may be a pigment or a dye. Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Examples of the organic pigment include the chromatic pigment described in the above-described material of the present invention. Examples of the dye include, for example, JP-A No. 64-90403, JP-A No.
  • pyrazole azo compounds When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
  • the content of the chromatic colorant is preferably 0.01 to 70% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 0.1% by mass or more, and more preferably 0.5% 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 a total of 100 parts by mass of the material of the present invention and the infrared absorber shown below.
  • the total amount of the material of the present invention, the infrared absorber, and the chromatic colorant is preferably 1 to 70% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the composition of the present invention may be an embodiment that does not substantially contain a chromatic colorant.
  • the term “substantially does not contain a chromatic colorant” means that the content of the chromatic colorant is the present invention.
  • the total solid content of the composition is preferably 0.005% by mass or less, more preferably 0.001% by mass or less, and even more preferably no chromatic colorant.
  • the composition of the present invention may further contain an infrared absorber in addition to the above-described material of the present invention.
  • the infrared absorber means a compound having absorption in the near infrared region (preferably, wavelength 700 to 1200 nm).
  • the maximum absorption wavelength of the infrared absorber is more preferably in the range of 700 to 1000 nm, and particularly preferably in the range of 800 to 1000 nm.
  • the infrared absorber may be a pigment or a dye.
  • infrared absorbers examples include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene compounds, dithiol metal complex compounds, croconium. Compounds, oxole compounds and the like.
  • the content of the infrared absorber is preferably 0.1 to 50 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the material of the composition of the present invention. 30 parts by mass is more preferable, and 1.0 to 15 parts by mass is even more preferable. Moreover, it can also be set as the composition which does not contain an infrared absorber substantially. In addition, it is preferable that content of an infrared absorber is 0.1 mass part or less with respect to 100 mass parts of materials, and 0.05 mass part or less is more, for example, that it does not contain an infrared absorber substantially. Preferably, 0.01 mass part or less is still more preferable, and it is still more preferable not to contain.
  • the composition of the present invention can also contain a colorant that blocks visible light.
  • This composition can be preferably used as, for example, a composition for forming an infrared transmission filter.
  • the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits light having a wavelength in the infrared region (infrared).
  • the color material that shields visible light preferably exhibits black, gray, or a color close to them by a combination of a plurality of color materials.
  • the colorant that blocks visible light is preferably a 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 range of 450 to 650 nm.
  • the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).
  • the organic black colorant as a colorant that shields visible light means a material that absorbs visible light but transmits at least part of infrared light. 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 the chromatic colorant 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 those 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 those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
  • 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.
  • the chromatic colorants are red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. It is preferable that it is a coloring agent chosen from these.
  • combinations of chromatic colorants in the case of forming a color material that shields visible light 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.
  • Embodiment containing yellow colorant, blue colorant and red colorant (3) Embodiment containing yellow colorant, purple colorant and red colorant (4) Embodiment containing yellow colorant and purple colorant (5) Embodiment containing green colorant, blue colorant, purple colorant and red colorant (6) Embodiment containing purple colorant and orange colorant (7) Green colorant, purple colorant and red coloration (8) A mode containing a green colorant and a red colorant
  • the content of the colorant that blocks visible light is 0.01 to 70% by mass in the total solid content of the composition of the present invention. It is preferable.
  • the lower limit is preferably 0.1% by mass or more, and more preferably 0.5% 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 colorant that blocks visible light is preferably 10 to 1000 parts by mass, and more preferably 50 to 800 parts by mass with respect to 100 parts by mass in total of the material of the present invention and the infrared absorber.
  • the total amount of the material of the present invention, the infrared absorber, and the colorant that blocks visible light is preferably 1 to 70% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the composition of the present invention preferably further contains a pigment derivative.
  • a pigment derivative By including the pigment derivative, the dispersibility of the pigment in the composition can be enhanced, and the aggregation of the pigment can be efficiently suppressed.
  • the dye derivative include the dye derivatives described in the compound B of the material of the present invention described above.
  • the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the composition.
  • 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 the content of the pigment derivative is in the above range, the dispersibility of the pigment can be increased and the aggregation of particles can be efficiently suppressed. Only one type of pigment derivative 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 composition of the present invention preferably further contains an organic solvent.
  • an organic solvent There is no restriction
  • alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like are preferable. These may be used alone or in combination of two or more. Specific examples of the alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph No. 0136 of JP 2012-194534 A, the contents of which are incorporated herein.
  • esters, ketones, and ethers include those described in JP 2012-208494 A, paragraph 0497 (corresponding to US Patent Application Publication No. 2012/0235099, ⁇ 0609>). It is done. Furthermore, acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like can be mentioned.
  • Organic solvents include cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, 2-butanol, ethanol, ethyl lactate and propylene glycol monomethyl ether (1-methoxy-2-propanol) At least one selected from the group consisting of
  • the organic solvent is preferably an organic solvent having a low metal content.
  • the metal content of the organic solvent is preferably 10 ppb or less, for example. If necessary, a ppt level solvent may be used, and such a high-purity solvent is provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter in filtration using a filter 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 a polytetrafluoroethylene, polyethylene, or nylon filter.
  • the organic 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 content of the organic solvent is preferably such that the total solid content of the composition of the present invention is 5 to 60% by mass, and more preferably 10 to 40% by mass. Only one type of organic solvent 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 composition of the present invention preferably further contains a resin.
  • the resin is blended, for example, as a dispersant for dispersing the pigment, the material of the present invention, and the like in the composition.
  • the resin acting as a dispersant is preferably an acid type resin and / or a basic type resin.
  • the acid type resin represents a resin having a larger amount of acid groups than that of basic groups.
  • the acid type resin preferably has an acid group content of 70 mol% or more when the total amount of acid groups and basic groups in the resin is 100 mol%. What consists only of group is more preferable.
  • the acid group possessed by the acidic resin is preferably a carboxy group.
  • the acid value of the acid type resin is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
  • the basic type resin represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • the basic type resin preferably occupies 50 mol% or more of the basic group when the total amount of the acid group and the basic group in the resin is 100 mol%.
  • the basic group possessed by the basic type resin is preferably an amine.
  • 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 end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191.
  • examples thereof include a polymer having a sulfonic acid 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.
  • Copolymers of polyallylamine and polyester reaction products described in JP-A-9-169821 and the like macromonomers described in JP-A-10-339949, JP-A-2004-37986, etc., and nitrogen atom monomers JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like, graft-type polymers having a partial skeleton or a heterocyclic ring of organic dyes, and JP-A-2010-106268 And the like, and the like.
  • macromonomer examples include macromonomer AA-6 (polymethyl methacrylate whose terminal group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S manufactured by Toagosei Co., Ltd. (A copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polybutyl acrylate whose terminal group is a methacryloyl group), Plaxel FM5 (2-hydroxy methacrylate) manufactured by Daicel Chemical Industries, Ltd.
  • AA-6 polymethyl methacrylate whose terminal group is a methacryloyl group
  • AS-6 polystyrene whose terminal group is a methacryloyl group
  • AN-6S manufactured by Toagosei Co., Ltd.
  • ⁇ -caprolactone 5 molar equivalent addition product of ethyl FA10L (10 molar equivalent addition product of ⁇ -caprolactone of 2-hydroxyethyl acrylate), polyester macromonomer described in JP-A-2-272009, and the like.
  • block polymer block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • a graft copolymer containing a structural unit represented by any one of the following formulas (1) to (4) can also be used.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, preferably an oxygen atom.
  • R 3 represents a branched or straight chain alkylene group (preferably having 1 to 10 carbon atoms, more preferably 2 or 3), and —CH 2 —CH (CH 3 ) from the viewpoint of dispersion stability.
  • a group represented by — or a group represented by —CH (CH 3 ) —CH 2 — is preferred.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group.
  • the description of paragraph numbers 0025 to 0069 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. Further, resins described in JP-A-2012-255128, paragraphs 0072 to 0094 can be used.
  • an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used.
  • the oligoimine resin includes a repeating unit having a group X containing a partial structure having a functional group of pKa 14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and side A resin having a basic nitrogen atom in at least one of the chains is preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • the oligoimine resin includes, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2a). Examples include resins containing units.
  • 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 R 6 each independently represents 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 ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . 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 is particularly preferably a structural part to form pyrrolidine. This structural part may further have a substituent such as an alkyl group.
  • X represents a group including a partial structure having a functional group of pKa14 or less.
  • Y represents a side chain having 40 to 10,000 atoms.
  • the resin oligoimine-based resin
  • the resin 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) You may do it.
  • the resin contains such a repeating unit, the dispersion performance of the pigment 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 resin 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 resin include the following.
  • resins described in JP-A-2012-255128, paragraph numbers 0168 to 0174 can be used.
  • a resin containing a structural unit represented by the formula (P1) can also be used.
  • the dispersibility of the pigment can be further improved by using the following resins.
  • R 1 represents hydrogen or a methyl group
  • R 2 represents an alkylene group
  • Z represents a nitrogen-containing heterocyclic structure.
  • the alkylene group represented by R 2 is not particularly limited.
  • methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, 2-hydroxypropylene group, methyleneoxy group, ethyleneoxy group, methyleneoxycarbonyl Group, a methylenethio group, etc. are mentioned suitably, A methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group is more preferable.
  • the nitrogen-containing heterocyclic structure represented by Z is, for example, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone Examples thereof include a ring, an anthraquinone ring, a benzimidazole structure, a benztriazole structure, a benzthiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure.
  • the nitrogen-containing heterocyclic structure represented by Z is preferably a structure represented by the following formula (P2) or formula (P3).
  • X is a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and —C ( ⁇ O )-.
  • R represents a hydrogen atom or an alkyl group.
  • R represents an alkyl group
  • examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples thereof include t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
  • X is preferably a single bond, a methylene group, —O— or —C ( ⁇ O) —, and particularly preferably —C ( ⁇ O) —.
  • ring A, ring B, and ring C each independently represent an aromatic ring.
  • the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, phenothiazine.
  • Ring, phenoxazine ring, acridone ring, anthraquinone ring, etc. among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.
  • the resin including the structural unit represented by the formula (P1) may further include a structural unit represented by any one of the above formulas (1) to (4). Further, it further includes a repeating unit represented by the formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2a). You may go out. Specific examples of the resin containing the structural unit represented by the formula (P1) include the following.
  • the resin is also available as a commercial product. Specific examples of such resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group) manufactured by BYK Chemie.
  • the resin may be an alkali-soluble resin.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable.
  • Resins and acrylic / acrylamide copolymer resins are preferred.
  • examples of the group that promotes alkali solubility include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group.
  • the group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable.
  • These acid groups may be used alone or in combination of two or more.
  • the alkali-soluble resin description in paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to ⁇ 0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Are incorporated herein.
  • the alkali-soluble resin is also preferably a resin containing a compound represented by the following formula (ED) as a copolymerization component.
  • ED a compound represented by the following formula (ED)
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • the hydrocarbon group having 1 to 25 carbon atoms represented by R 1 and R 2 is not particularly limited.
  • methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t -Linear or branched alkyl groups such as amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, And alicyclic groups such as 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like.
  • R 1 and R 2 may be the same type of substituent or different substituents.
  • the acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g.
  • the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
  • the upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000.
  • the lower limit is preferably 5,000 or more, and more preferably 7,000 or more.
  • the upper limit is preferably 30,000 or less, and more preferably 20,000 or less.
  • the content of the resin in the composition 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 preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less.
  • the lower limit is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more.
  • the composition of this invention can be prepared by mixing each component mentioned above.
  • the components constituting the composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in an organic solvent.
  • the mechanical force used for dispersing the material of the present invention includes compression, squeezing, impact, shearing, cavitation and the like.
  • a refinement process by a salt milling process may be performed.
  • materials, equipment, processing conditions, etc. used in the salt milling process for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.
  • the composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
  • a filter for the purpose of removing foreign substances or reducing defects.
  • Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • PP polypropylene
  • nylon 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, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.
  • filters When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or may be performed twice or more. Moreover, you may combine the 1st 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.
  • a commercially available filter for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
  • As the second filter a filter formed of the same material as the first filter described above can be used.
  • the curable composition of this invention contains the composition mentioned above and a curable compound.
  • the content of the material of the present invention can be adjusted as necessary.
  • the content is preferably 0.01 to 50% by mass in the total solid content of the curable composition.
  • the lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
  • the upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.
  • the curable composition of the present invention contains a curable compound.
  • a curable compound a compound that can be cross-linked by a radical, an acid, or heat can be used.
  • examples thereof include compounds having a radical polymerizable group, a cyclic ether (epoxy, oxetane) group, a methylol group, and the like.
  • the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • a polymerizable or non-polymerizable binder polymer can also be used as the curable compound.
  • the curable compound is preferably a polymerizable compound, and more preferably a radical photopolymerizable 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 a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof.
  • a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is preferably 2000 or less, and more preferably 1500 or less.
  • the lower limit is preferably 150 or more, and more 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 paragraph numbers [0095] to [0108] of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph number 0254 to JP-A-2008-292970.
  • the compounds described in 0257 can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A) -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, SR454, SR4
  • the polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group.
  • an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group.
  • Examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerizability is good and the curability is excellent.
  • the polymerizable compound is also preferably a polymerizable compound having a caprolactone structure.
  • the polymerizable compound having a caprolactone structure the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
  • Examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
  • a polymerizable compound having an alkyleneoxy group can also be used.
  • 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 acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, 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.
  • urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (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 polymerizable compound is also preferably isocyanuric acid ethyleneoxy-modified (meth) acrylate.
  • examples of commercially available products include Aronix M-315 and M-313 (manufactured by Toagosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR368 (manufactured by Sartomer), and the like.
  • the content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the 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 content of the polymerizable compound is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total mass of the curable compound.
  • a compound having an epoxy group can also be used as the curable compound.
  • a compound having two or more epoxy groups in one molecule is preferable.
  • the upper limit of the number of epoxy groups can be, for example, 100 or less, 10 or less, or 5 or less.
  • the compound having an epoxy group preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring.
  • the epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group.
  • the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • the epoxy group is preferably a compound formed by directly bonding (single bond) to the aliphatic ring.
  • the epoxy group is preferably a compound formed by bonding to an aromatic ring via a linking group.
  • the linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
  • the compound which has an epoxy group can also use the compound which has a structure which two or more aromatic rings connected with the hydrocarbon group.
  • the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.
  • the compound having an epoxy group may be either a low molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (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 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
  • Examples of the compound having an epoxy group include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and glycidyl. Ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group, and the like And copolymers with other polymerizable unsaturated compounds.
  • epoxy resin that is a glycidyl etherified product of a phenol compound
  • epoxy resins that are glycidyl etherification products of novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols.
  • novolak resins such as a novolak resin, a phenol novolak resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolak resin containing a fluorene skeleton.
  • Examples of the alicyclic epoxy resin include alicyclic skeletons having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.
  • An epoxy resin is mentioned.
  • Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
  • heterocyclic epoxy resin examples include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
  • examples of the glycidyl ester-based epoxy resin include epoxy resins composed of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
  • examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
  • epoxy resins obtained by glycidylation of halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A.
  • An epoxy resin obtained by glycidylation of halogenated phenols can be mentioned.
  • copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds commercially available products include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 and the like.
  • the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1,2-epoxide and the like.
  • Examples of the copolymer of other polymerizable unsaturated compounds include methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane and the like, and particularly methyl (meth) acrylate. , Benzyl (meth) acrylate, and styrene are preferable.
  • EPICLON 860 EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), and the like.
  • Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like.
  • phenol novolac type epoxy resins jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Is mentioned.
  • Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), OXT-221 (manufactured by Toagosei Co., Ltd.) and the like.
  • 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 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 content of the compound having an epoxy group is preferably 1 to 80% by mass and more preferably 1 to 50% by mass with respect to the total mass of the curable compound.
  • Polymerizable or non-polymerizable binder polymer in the present invention, a polymerizable or non-polymerizable binder polymer can also be used as the curable compound.
  • Polymerizable or non-polymerizable binder polymers include cyclic olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, polysulfone resin, poly Examples include ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, and fluorinated aromatic resin. Specific examples include polymers having the following repeating units.
  • the resin demonstrated with the composition mentioned above can also be used as a polymeric or nonpolymerizable binder polymer.
  • the content of the binder polymer 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.
  • the binder polymer may be used alone or in combination of two or more. 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 may contain a polymerization initiator.
  • the curable composition of the present invention contains a polymerizable compound as the curable compound, it preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light or heat, or both, and can be appropriately selected according to the purpose.
  • a photopolymerization initiator is preferred.
  • the photopolymerization initiator preferably has photosensitivity to light in the ultraviolet region to the visible region. Further, when the polymerization of the polymerizable compound is initiated by heat, a thermal polymerization initiator is preferable.
  • the thermal polymerization initiator is preferably one that decomposes at 150 to 250 ° C.
  • the polymerization initiator include acylphosphine compounds, acetophenone compounds, ⁇ -aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, Examples include organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, onium salt compounds such as metallocene compounds, organic boron salt compounds, disulfone compounds, and thiol compounds.
  • the polymerization initiator is preferably a compound having at least an aromatic group.
  • the description in paragraphs 0218 to 0251 of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated in the present specification.
  • compounds described in JP-A-2016-21012 can also be used.
  • the polymerization initiator is preferably an oxime compound, an acetophenone compound or an acylphosphine compound.
  • oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-930 ( ADEKA) and the like. It is also possible to use an oxime initiator having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph 0345 of JP 2014-500852 A, JP 2013 2013. Compound (C-3) described in paragraph 0101 of JP-A No. 164471.
  • oxime multimers described in JP-T-2010-527339 and International Publication WO2015 / 004565 can also be used. It is also possible to use an oxime initiator having a nitro group.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime initiator 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, Adeka Arkles NCI-831 (manufactured by ADEKA) can be mentioned.
  • Examples of commercially available acetophenone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF).
  • Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF).
  • the photopolymerization initiator is preferably a combination of an acetophenone compound and an oxime compound.
  • the content of the polymerization initiator is preferably 0.01 to 30% by mass with respect to the total solid content of the curable composition.
  • the lower limit is preferably 0.1% by mass or more.
  • the upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Only one type of polymerization initiator 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 curable composition of this invention contains the compound which has an epoxy group, it is preferable to further contain at least 1 sort (s) chosen from an acid anhydride and polyhydric carboxylic acid.
  • acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Is mentioned.
  • methyltetrahydrophthalic anhydride methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-diethylglutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2, 1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Etc. are preferable from the viewpoint of light resistance, transparency, and workability.
  • the polyvalent carboxylic acid is a compound having at least two carboxyl groups.
  • a geometric isomer or an optical isomer exists in the following compound, it is not particularly limited.
  • the polyvalent carboxylic acid is preferably a bi- to hexafunctional carboxylic acid, such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid.
  • Alkyltricarboxylic acids such as acid and citric acid; aliphatic cyclic polyvalents such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid Carboxylic acids; Multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof; linear alkyl diacids such as malic acid are preferred; hexanedioic acid, pentanedioic acid, heptane Diacid, octanedioic acid, nonanedioic acid and decanedioic acid are preferred. Sex, more preferable from the viewpoint of transparency of the cured product.
  • the content of the acid anhydride and polyvalent carboxylic acid is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound having an epoxy group. 6.0 parts by mass is more preferable.
  • the curable composition of the present invention may contain an alkali-soluble resin.
  • an alkali-soluble resin By containing an alkali-soluble resin, a desired pattern can be formed by alkali development.
  • alkali-soluble resin what was demonstrated by the composition is mentioned, A preferable range is also the same.
  • the content of the alkali-soluble resin is preferably 1% by mass or more, preferably 2% by mass or more in the total solid content of the curable composition of the present invention. It can also be 5 mass% or more, and can also be 10 mass% or more.
  • content of alkali-soluble resin can also be 80 mass% or less in the total solid of the curable composition of this invention, can also be 65 mass% or less, and shall be 60 mass% or less. It can also be made into 15 mass% or less.
  • content of alkali-soluble resin can also be 80 mass% or less in the total solid of the curable composition of this invention, can also be 65 mass% or less, and shall be 60 mass% or less. It can also be made into 15 mass% or less.
  • the curable composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined.
  • the content of the surfactant is preferably 0.0001 to 2% by mass with respect to the solid content of the curable composition of the present invention.
  • the lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more.
  • the upper limit is preferably 1.0% by mass or less, and more preferably 0.1% by mass or less.
  • 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.
  • the curable composition of the present invention preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. According to this, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability to the coated surface is improved. For this reason, the liquid characteristic (especially fluidity
  • the fluorine content of the fluorosurfactant is preferably 3 to 40% by mass.
  • the lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more.
  • the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.
  • the fluorosurfactant include the surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060-0064 of the corresponding international publication WO2014 / 17669 pamphlet), JP-A-2011 Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-1252503, the contents of which are incorporated herein.
  • fluorosurfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, R30, F-437, F-475, F-479, F-482, F-554, F-780 (above, manufactured by DIC Corporation) Fluorard FC430, FC431, FC171 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) Etc.
  • 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.
  • the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
  • Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, and RS-72K manufactured by DIC. Is mentioned.
  • the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • nonionic surfactants include nonionic surfactants described in paragraph No. 0553 of JP2012-208494A (corresponding to [0679] of US 2012/0235099). The contents of which are incorporated herein by reference.
  • Specific examples of the cationic surfactant include the cationic surfactant described in paragraph No. 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
  • silicone surfactant include silicone surfactants described in paragraph No. 0556 of JP 2012-208494 A (corresponding US Patent Application Publication No. 2012/0235099, [0682]). The contents of which are incorporated herein by reference.
  • the curable composition of the present invention can contain a substrate adhesion agent.
  • a substrate adhesion agent it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
  • silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltri Methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl
  • the content of the substrate adhesion 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 a small amount of a polymerization inhibitor in order to prevent unnecessary reaction of the curable compound during production or storage.
  • a polymerization inhibitor include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, Examples include cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, phosphorus compounds, lactone compounds, and transition metal compounds (FeCl 3 , CuCl 2, etc.).
  • these compounds may be composite compounds in which a plurality of structures that exhibit a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton are present in the same molecule.
  • a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton
  • the compounds described in JP-A-10-46035 are also preferably used.
  • the polymerization inhibitor examples include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol) 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like, and paramethoxyphenol 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 of the present invention.
  • the curable composition of the present invention may contain an ultraviolet absorber.
  • a well-known compound can be used for a ultraviolet absorber.
  • UV503 (Daito Chemical Co., Ltd.) etc. are mentioned, for example.
  • the ultraviolet absorber aminodiene-based, salicylate-based, benzophenone-based, benzotriazole-based, acrylonitrile-based, triazine-based ultraviolet absorbers, and the like can be used. Specific examples include the compounds described in JP2013-68814A.
  • 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.
  • the curable composition of the present invention may contain an organic solvent.
  • an organic solvent what was demonstrated by the said composition is mentioned, A preferable range is also the same.
  • the content of the organic solvent in the curable composition of the present invention is preferably such that the total solid content of the curable composition of the present invention is 5 to 90% by mass, more preferably 10 to 80% by mass. More preferred is an amount of 20 to 75% by mass.
  • the curable composition of this invention may select and use another component suitably according to the objective.
  • the curable composition of the present invention can contain one or more selected from a chromatic colorant, an infrared absorber, and a colorant that blocks visible light, in addition to the above-described material of the present invention.
  • a chromatic colorant demonstrated with the composition mentioned above, an infrared absorber, and the coloring material which shields visible light are mentioned. These can be appropriately selected depending on the use of the curable composition.
  • Examples of other components that can be used in combination include a sensitizer, a crosslinking agent (crosslinking agent aqueous solution), acetic anhydride, a silane compound, a curing accelerator, a filler, a plasticizer, and other auxiliary agents (for example, conductive Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
  • These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding ⁇ 0237> to ⁇ 0309> of US Patent Application Publication No. 2013/0034812) and JP2008-250074. Paragraph Nos.
  • 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. About the kind of filter and the filtration method, what was demonstrated by the composition is mentioned, A preferable range is also the same.
  • the curable composition of the present invention can be in a liquid state, for example, by applying the curable composition of the present invention to a substrate and drying it, a color filter, an infrared cut filter, an infrared transmission filter, etc. Can be easily produced.
  • a color filter, an infrared cut filter, an infrared transmission filter, etc. Can be easily produced.
  • the pigment A in the material of the present invention is a near infrared absorbing dye
  • an infrared cut filter can be produced by using a curable composition containing the material of the present invention.
  • the curable composition of the present invention further contains an infrared absorber in addition to the material of the present invention, a wider wavelength than can be cut with the pigment A contained in the material of the present invention.
  • an infrared cut filter capable of absorbing light in the near infrared region of the region.
  • an infrared transmission filter can be produced.
  • an infrared cut filter having a function as a color filter can be produced.
  • the pigment A in the material of the present invention is a chromatic pigment
  • a color filter can be produced by using a curable composition containing the material of the present invention.
  • the 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 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. It may be a thing.
  • the color filter means a filter that transmits a specific wavelength range of visible light and shields the specific wavelength range.
  • the viscosity of the curable composition of the present invention is preferably 1 to 3000 mPa ⁇ s when a cured film is formed by coating.
  • the lower limit is preferably 2 mPa ⁇ s or more, and more preferably 3 mPa ⁇ s or more.
  • the upper limit is preferably 100 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or less, still more preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • the total solid content of the curable composition of the present invention varies depending on the coating method, but is preferably 1 to 50% by mass, for example.
  • the lower limit is more preferably 10% by mass or more.
  • the upper limit is more preferably 30% by mass or less.
  • an infrared cut filter on the light receiving side of the solid-state image sensor for example, for an infrared cut filter for a wafer level lens
  • a back surface side (light receiving) of the solid-state image sensor It can be preferably used for an infrared cut filter on the side opposite to the side).
  • it can be preferably used as an infrared cut filter on the light receiving side of the solid-state imaging device.
  • the cured film of the present invention is formed by curing the above-described curable composition of the present invention.
  • the cured film of the present invention can be used as an infrared cut filter, an infrared transmission filter, a color filter, or the like.
  • the cured film of the present invention may have a pattern or may be a film (flat film) having no pattern.
  • the cured film of the present invention When used as an infrared transmission filter, it preferably has the following spectral characteristics (1) or (2). According to this aspect, a film that can transmit infrared rays (preferably, light having a wavelength of 900 nm or more) can be obtained in a state where there is little noise derived from visible light.
  • infrared rays preferably, light having a wavelength of 900 nm or more
  • the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 400 to 830 nm, and the light transmittance in the thickness direction of the film is the minimum in the wavelength range of 1000 to 1300 nm.
  • the value is preferably 70% or more.
  • the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is preferably 20% or less, and more preferably 10% or less.
  • the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more, and more preferably 80% or more.
  • the maximum value of the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 450 to 650 nm, and the light transmittance of the wavelength 835 nm in the film thickness direction is 20% or less.
  • the minimum value of the light transmittance in the film thickness direction in the wavelength range of 1000 to 1300 nm is preferably 70% or more.
  • the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 450 to 650 nm is preferably 20% or less, and more preferably 10% or less.
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 650 to 835 nm is preferably 50% or less, and more preferably 30% or less.
  • the transmittance of light having a wavelength of 835 nm in the thickness direction of the film is preferably 20% or less, and more preferably 10% or less.
  • the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more, and more preferably 80% or more.
  • the spectral characteristics of the cured film of the present invention are values 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 cured film of the present invention When the cured film of the present invention is used as an infrared cut filter or an infrared transmission filter, it can be used in combination with an infrared cut filter and an infrared transmission filter.
  • the filter By using a combination of an infrared cut filter and an infrared transmission filter, the filter can be preferably used for an infrared sensor that detects infrared rays having a specific wavelength.
  • one of the infrared cut filter and the infrared transmission filter is a cured film (cured film of the present invention) formed using the curable composition of the present invention, and the other is the curable film of the present invention. It is good also as a cured film formed using curable compositions other than a composition. Moreover, you may comprise both with the cured film of this invention.
  • the infrared cut filter may or may not be adjacent to the color filter in the thickness direction.
  • the infrared cut filter may be formed on a base material different from the base material on which the color filter is formed.
  • Other members for example, a microlens, a flattening layer, etc. constituting the solid-state imaging device may be interposed between the filter and the filter.
  • the film thickness of the cured 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 cured film of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a 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 a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • the optical filter of the present invention has the above-described cured film of the present invention.
  • the optical filter of the present invention can be preferably used as at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter.
  • an embodiment in which the optical filter of the present invention includes a pixel using the cured film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable embodiment.
  • the pattern forming method of the present invention comprises a step of forming a curable composition layer on a support using the curable composition of the present invention, and a photolithography method or a dry etching method on the curable composition layer. Forming a pattern.
  • the pattern formation method may be a pattern formation method by photolithography or a pattern formation method by dry etching.
  • a dry etching process is unnecessary, and thus the number of processes can be reduced.
  • the pattern forming method is performed by dry etching, the curable composition does not need a photolithographic function, so that an effect of increasing the concentration of a pigment or the like can be obtained.
  • Pattern formation by the photolithography method includes a step of forming a curable composition layer on a support using a curable composition, a step of exposing the curable composition layer in a pattern, and developing and removing unexposed portions. And a step of forming a pattern. As needed, you may provide the process (prebaking process) of baking a curable composition layer, and the process (post-baking process) of baking the developed pattern.
  • pattern formation by a dry etching method includes a step of forming a curable composition layer on a support using a curable composition and curing to form a cured product layer, and a photoresist layer on the cured product layer.
  • each step will be described.
  • Step of Forming Curable Composition Layer In the step of forming the curable composition layer, the curable 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 in the present invention 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.
  • various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be used.
  • the curable 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. Drying can be performed with a hot plate, oven, or the like.
  • Exposure process (When forming a pattern by photolithography) ⁇ Exposure process >> Next, the curable composition layer is exposed in a pattern (exposure process).
  • pattern exposure can be performed by exposing the curable 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 ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
  • the irradiation amount (exposure amount) is preferably 30 to 5000 mJ / cm 2 , for example.
  • the upper limit is preferably 3000 mJ / cm 2 or less, more preferably 2000 mJ / cm 2 or less, more preferably 1500 mJ / cm 2 or less.
  • the lower limit is more preferably 50 mJ / cm 2 or more, 80 mJ / cm 2 or more is particularly preferable.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • the exposure may be performed preferably in a substantially oxygen-free manner) in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume or more, preferably 30% by volume or more, more preferably 50% by volume or more). May be exposed.
  • the exposure illuminance can be appropriately set, and is usually 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 or more, preferably 15000 W / m 2 or more, more preferably 35000 W / m 2 or more).
  • 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 unexposed portion is developed and removed to form a pattern.
  • the development removal of the unexposed portion can be performed using a developer.
  • the curable composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
  • the developer an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds.
  • the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
  • Organic alkaline agents such as choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and dimethylbis (2-hydroxyethyl) ammonium hydroxide.
  • 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.
  • the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
  • 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-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. . Further, when a pattern is formed by a low temperature process, post baking is not necessary.
  • Pattern formation by dry etching is performed by curing a curable composition layer formed on a support to form a cured product layer, and then using the patterned photoresist layer as a mask for the resulting cured product layer.
  • Etching gas can be used.
  • a mode in which heat treatment after exposure and heat treatment after development are desirable.
  • a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g-rays, h-rays, i-rays), excimer lasers, deep ultraviolet rays, electron beams, ion beams and X-rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
  • the positive radiation sensitive composition a composition containing a quinonediazide compound and an alkali-soluble resin is preferable.
  • a positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by light irradiation with a wavelength of 500 nm or less to produce a carboxy group, resulting in becoming alkali-soluble from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. As a commercial item, "FHi622BC" (made by FUJIFILM Electronics Materials) etc. are mentioned, for example.
  • the thickness of the photoresist layer is preferably from 0.1 to 3 ⁇ m, more preferably from 0.2 to 2.5 ⁇ m, still more preferably from 0.3 to 2 ⁇ m.
  • the application method of a positive radiation sensitive composition can be suitably performed using the application
  • the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with resist through-hole groups.
  • the formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique.
  • a resist through hole group in the photoresist layer By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the cured product layer.
  • the exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
  • Any developer can be used as long as it does not affect the cured product layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist.
  • a combination of various solvents or an alkaline aqueous solution can be used.
  • an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable.
  • alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, dimethylbis (2-hydroxyethyl) ammonium hydroxide, and the like. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.
  • patterning is performed by dry etching so that a through hole group is formed in the cured product layer.
  • Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
  • a mixed gas of fluorine-based gas and oxygen gas (O 2 ) the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N 2 ) and oxygen gas (O 2 ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • N 2 nitrogen gas
  • O 2 oxygen gas
  • a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • the form containing these is preferable.
  • a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
  • Dry etching is performed by obtaining etching conditions in advance by the following method.
  • (1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
  • (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
  • (3) The first-stage etching is performed according to the etching time calculated in (2) above.
  • the second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
  • (5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.
  • the mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape.
  • the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
  • the second stage etching process and the over etching process after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
  • the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable.
  • the etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
  • the etching preferably includes an over-etching process.
  • the overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first.
  • the over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
  • the resist pattern that is, the etching mask
  • the removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.
  • Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned.
  • time to make stripping solution or a solvent stagnant It is preferable that it is several dozen seconds to several minutes.
  • examples of the step of removing the resist pattern using the cleaning water include a step of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle.
  • the washing water pure water can be preferably used.
  • examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.
  • the stripping solution generally contains an organic solvent, but may further contain an inorganic solvent.
  • organic solvent include (1) hydrocarbon compounds, (2) halogenated hydrocarbon compounds, (3) alcohol compounds, (4) ether or acetal compounds, (5) ketones or aldehyde compounds, (6) ester compounds, (7) polyhydric alcohol compounds, (8) carboxylic acids or acid anhydride compounds, (9) phenol compounds, (10) nitrogen compounds, (11) sulfur compounds, (12) Fluorine-containing compounds are exemplified.
  • the stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • the acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxy group.
  • Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine.
  • Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H 2 NCH 2 CH 2 OH).
  • cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ⁇ -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • the stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • acyclic nitrogen-containing compound at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic
  • the nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.
  • a deposit means an etching product deposited and deposited on the side wall of a cured product layer.
  • the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.
  • the solid-state imaging device of the present invention has the above-described cured film of the present invention.
  • the camera module of this invention has a solid-state image sensor and the cured film (preferably infrared cut filter) of this invention.
  • the configuration of the solid-state imaging element is not particularly limited as long as it is a configuration having the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • a device protective film comprising the film of the present invention such as an infrared cut filter or an infrared transmission filter on the device protective film.
  • the structure having a light collecting means for example, a microlens, etc., the same shall apply hereinafter
  • a light collecting means for example, a microlens, etc., the same shall apply hereinafter
  • the structure etc. which have a condensing means may be sufficient.
  • the infrared sensor of the present invention has the above-described cured 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 cured film of the present invention and functions as an infrared sensor.
  • reference numeral 110 denotes a solid-state image sensor.
  • the imaging area provided on the solid-state imaging device 110 includes an infrared cut filter 111 and a color filter 112.
  • the infrared cut filter 111 can be formed using, for example, the curable composition of the present invention.
  • a region 114 is provided between the infrared transmission filter 113 and the solid-state image sensor 110.
  • a resin layer for example, a transparent resin layer
  • the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
  • a micro lens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 113.
  • a planarization layer 116 is formed so as to cover the microlens 115.
  • the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thicknesses of both may be different. In the embodiment shown in FIG.
  • the color filter 112 is provided on the incident light h ⁇ side with respect to the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to cut the infrared filter.
  • the filter 111 may be provided closer to the incident light h ⁇ than the color filter 112.
  • the infrared cut filter 111 and the color filter 112 are stacked adjacent to each other, but the filters do not necessarily have to be adjacent to each other, and other layers are provided between them. Also good.
  • the infrared cut filter 111 and the color filter 112 are provided as separate members.
  • the color filter 112 contains the composition of the present invention, and the color filter 112 is used as an infrared cut filter. You may give the function of. In this case, the infrared cut filter 111 can be omitted.
  • the characteristics of the infrared cut filter 111 are selected according to the emission wavelength of an infrared light emitting diode (infrared LED) described later.
  • the infrared cut filter 111 transmits visible light (for example, light having a wavelength of 400 to 650 nm) and is in the near infrared region (preferably in the range of wavelength 700 to 1300 nm, more preferably in the range of wavelength 700 to 1000 nm). It is preferable that the filter shields at least a part of the light.
  • the infrared cut filter 111 can be composed of a cured film using the curable 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 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
  • the color filter 112 can also be formed of a cured film using the curable composition of the present invention.
  • the characteristics of the infrared transmission filter 113 are selected according to the emission wavelength of an infrared LED described later.
  • the infrared transmission filter 113 preferably has a maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm of 30% or less. % 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 light transmittance in the thickness direction of the film in the wavelength range of 800 nm or more is preferably 70% or more, and 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 113 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.
  • 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 113 having the spectral characteristics described above can be manufactured using a curable composition containing a colorant that blocks visible light.
  • the details of the coloring material that blocks visible light are the same as those described in the above-described composition of the present invention.
  • the infrared transmission filter 113 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 infrared transmission filter 113 having the spectral characteristics described above can be manufactured using a curable composition containing a colorant that blocks visible light and a compound having a maximum absorption wavelength in the wavelength range of 750 to 950 nm.
  • the details of the coloring material that blocks visible light are the same as those described in the above-described composition of the present invention.
  • Examples of the compound having the maximum absorption wavelength in the wavelength range of 750 to 950 nm include the material of the present invention using a near-infrared absorbing dye as the pigment A and the infrared absorbent described in the composition of the present invention described above. .
  • the cured 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.
  • organic EL organic electroluminescence
  • each colored pixel for example, red, green, blue
  • the infrared light contained in the backlight of the display device for example, white light emitting diode (white LED)
  • white LED white light emitting diode
  • It can be used for the purpose of forming an infrared pixel in addition to each colored display pixel.
  • image display devices For the definition of image display devices and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai Co., Ltd., issued in 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho Co., Ltd.) ) "Issued in 1989”).
  • 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.
  • Example 1 8.74 parts by mass of diphenylborinic acid ester, 10 parts by mass of the following compound (A-1-a), 4.27 parts by mass of the following compound (B-30), and 100 mL of toluene were stirred at 40 ° C. 7.36 parts by mass of titanium was dropped and reacted for 30 minutes. The mixture was heated to reflux at an external temperature of 130 ° C. for 3 hours, then cooled to room temperature, 57 mL of toluene was added, and this was filtered off. To the obtained crude crystals, 88 mL of methanol was added, and the mixture was heated to reflux at an external temperature of 80 ° C. for 1 hour.
  • Examples 2 to 8, 11 to 25 At the time of synthesis of each compound (Pigment A), the compound (C-2) was prepared in the same manner as in Example 1 except that the compounds shown in the following table were added as Compound B in the final step to synthesize each pigment. ) To (C-8) and (C-11) to (C-25) were produced.
  • Example 9 Compound (A-2-b) Compound (A-2-b) was synthesized according to the following scheme. Compound (A-2-a) was synthesized according to the method described in US Pat. No. 5,969,154 using 4- (1-methylheptoxy) benzonitrile as a starting material.
  • the total amount of crystals obtained, 18.3 parts by weight of malononitrile, 19.3 parts by weight of acetic acid, and 172 parts by weight of methanol were mixed, stirred at 60 ° C. for 1 hour, and then cooled to 10 ° C. or less.
  • the precipitated crystals were separated by filtration and washed with 200 parts by mass of methanol.
  • the obtained crystals were blown and dried at 40 ° C. for 12 hours to obtain 38.7 parts by mass of compound (A-3-b).
  • the mass X 2 of compound B in the material after washing with methanol was calculated. Further, the material after washing with methanol was blown and dried at 45 ° C. for 12 hours, and the mass X 3 of the solid content of the material after washing with methanol was measured. The resulting material, the mass X 2 of the compound B in the material after washing with methanol, washing the material after a solid content mass X 3 Metropolitan of methanol, the following equation to determine the X 1.
  • X 1 (X 2 / X 3 ) ⁇ 100 Methanol is a solvent satisfying the requirement that the solubility of the pigment A described in the following table is 0.02% by mass or less and the solubility of the compound B described in the following table is 0.2% by mass or more at 25 ° C. It is.
  • Pigment A The following compound.
  • Compound A-122 was synthesized with reference to the method described in WO09 / 060573.
  • Compound A-123 was synthesized with reference to the method described in JP2012-8532A.
  • Compound B the following compound
  • Compound (B-61) was synthesized according to the following scheme. 3.9 parts by weight of diphenylborinic acid 2-aminoethyl ester and 6.0 parts by weight of compound (A-2-b) were stirred in 60 parts by weight of toluene, and at a circumscribed temperature of 40 ° C., titanium tetrachloride was stirred. Was added dropwise over 10 minutes and stirred for 30 minutes. The external temperature was raised to 130 ° C. and heated to reflux for 3 hours. The mixture was allowed to cool until the internal temperature reached 30 ° C, and 40 parts by mass of methanol was added dropwise while maintaining the internal temperature at 30 ° C or lower.
  • composition (dispersion) > 10 parts by mass of the materials shown in the following table, 3.0 parts by mass of the dye derivatives shown in the following table, 7.8 parts by mass of the resin shown in the following table, 109 parts by mass of the organic solvent shown in the following table, and 0.5 mm Dispersion treatment was performed for 520 parts by mass of zirconia beads with a paint shaker for 30 minutes. Thereafter, filtration was performed using DFA4201NXEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole, and the beads were separated by filtration to prepare a composition (dispersion).
  • the examples had good dispersibility.
  • the comparative example which does not contain the material of this invention was inferior in the dispersibility.
  • the same effect can be obtained by using materials before washing with methanol as materials C-1 to C-25.
  • Example 201 to 225 ⁇ Preparation of curable composition> (Examples 201 to 225, Comparative Examples 201 to 203) The following components were mixed to prepare the curable composition of Example 201. Further, in the curable composition of Example 201, the dispersion liquid of Example 101 was changed to the dispersion liquids of Examples 102 to 125 and Comparative Examples 101 to 103, and Examples 202 to 225 and Comparative Examples 201 to 203 were changed. A near-infrared absorbing composition was prepared.
  • Example 226 In a glass separable flask equipped with a stirrer and a thermometer, 50.0 parts by mass of a compound having an epoxy group (manufactured by NOF Corporation, Marproof G-0150M weight average molecular weight 10,000), propylene glycol methyl ether acetate 100 A mass part was added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, 0.75 parts by mass of the composition (dispersion liquid) of Example 126 was added and stirred at 20 to 35 ° C. until uniform. Further, 0.500 parts by mass of butanedioic acid (1 part by mass with respect to 100 parts by mass of the compound having an epoxy group) was added and stirred at 20 to 35 ° C. for 1 hour to obtain a curable composition.
  • a compound having an epoxy group manufactured by NOF Corporation, Marproof G-0150M weight average molecular weight 10,000
  • propylene glycol methyl ether acetate 100 A mass part was added and dissolved by stirring at 20 to 35 ° C
  • Example 22-7 In a container, 100 parts by mass of the following resin A (binder polymer), 0.08 parts by mass of the composition of Example 127 (dispersion), and propylene glycol methyl ether acetate are added to bring the concentration of the resin A to 20% by mass. It adjusted and obtained the curable composition.
  • Each of the curable compositions of Examples 201 to 225 and Comparative Examples 201 to 203 was spin-coated on an 8-inch (200 mm) glass wafer and dried on a hot plate at 100 ° C. for 120 seconds to produce a cured film.
  • the curable composition of Example 226 was dropped on a glass substrate placed on a spin coater, the substrate surface was coated by rotating the substrate at 1000 rpm for 30 seconds, and then dried at 80 ° C. for 10 minutes. The solvent was removed and heat cured at 150 ° C. for 3 hours to obtain a cured film.
  • the curable composition of Example 227 was cast on a smooth glass substrate, dried at 20 ° C.
  • the examples had good in-plane uniformity. Since the dispersion used in the curable compositions of Examples had good pigment dispersibility, the viscosity of the curable composition was low and the coating property was good. Therefore, in the examples, it is considered that unevenness is less likely to occur in the coating film, and the in-plane uniformity is improved. On the other hand, the comparative example which does not contain the material of this invention was inferior in-plane uniformity. In an Example, an infrared rays transmission filter is obtained by further mix

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Abstract

L'invention concerne un matériau exerçant une excellente dispersibilité de pigment dans une composition. L'invention concerne également une composition exerçant une excellente dispersibilité de pigment, une composition durcissable, un film durci, un filtre optique, un élément d'imagerie solide, un capteur de rayon infrarouge, un module de caméra, et un procédé de production dudit matériau. Ledit matériau contient un pigment A et un composé B ayant une structure présentant une adsorptivité à la résine. Dans la formule (I), X1 est supérieur ou égal à 0,99. X2 représente la masse du composé B dans le matériau qui est immergé dans un solvant dans lequel, à 25 °C, la solubilité du pigment A est inférieure ou égale à 0,02 % en masse et la solubilité du composé B est supérieure ou égale à 0,2 % en masse. X3 représente la masse de matières solides du matériau immergé dans le solvant. Formule (I) : X1=(X2/X3)×100
PCT/JP2016/070210 2015-09-04 2016-07-08 Matériau, composition, composition durcissable, film durci, filtre optique, élément d'imagerie solide, capteur de rayon infrarouge, module de caméra et procédé de production dudit matériau WO2017038252A1 (fr)

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WO2018230387A1 (fr) * 2017-06-12 2018-12-20 富士フイルム株式会社 Composition durcissable, film durci, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, capteur infrarouge, auxiliaire de dispersion, dispersion liquide et procédé de production de dispersion liquide
WO2019013108A1 (fr) * 2017-07-13 2019-01-17 富士フイルム株式会社 Composition, film, filtre de transmission infrarouge, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
WO2019049635A1 (fr) * 2017-09-11 2019-03-14 富士フイルム株式会社 Pigment organique absorbant les rayons infrarouges proches, composition de résine, procédé de production de pigment organique absorbant les rayons infrarouges proches, procédé de réglage du spectre d'un pigment organique absorbant les rayons infrarouges proches, film, stratifié, filtre bloquant les rayons infrarouges proches, filtre à transmission de rayons infrarouges proches, élément d'imagerie à semi-conducteur, dispositif d'affichage d'images et capteur de rayons infrarouges
WO2019054281A1 (fr) 2017-09-15 2019-03-21 富士フイルム株式会社 Composition, film, stratifié, filtre de transmission infrarouge, dispositif d'imagerie à semi-conducteurs et capteur infrarouge
WO2020036037A1 (fr) * 2018-08-15 2020-02-20 富士フイルム株式会社 Composition, film, filtre optique, corps stratifié, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
WO2020059509A1 (fr) 2018-09-20 2020-03-26 富士フイルム株式会社 Composition durcissable, film durci, filtre de transmission infrarouge, stratifié, élément d'imagerie à l'état solide, capteur, et procédé de formation de motif
JPWO2021149596A1 (fr) * 2020-01-21 2021-07-29
WO2022130773A1 (fr) 2020-12-17 2022-06-23 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
WO2022131191A1 (fr) 2020-12-16 2022-06-23 富士フイルム株式会社 Composition, membrane, filtre optique, élément de capture d'image solide, appareil d'affichage d'image et capteur de rayons infrarouges
WO2023042605A1 (fr) * 2021-09-14 2023-03-23 富士フイルム株式会社 Composition, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge

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