WO2019021790A1 - Curable composition, cured film, method for producing cured film, near-infrared blocking filter, solid-state imaging element, image display device and infrared sensor - Google Patents

Curable composition, cured film, method for producing cured film, near-infrared blocking filter, solid-state imaging element, image display device and infrared sensor Download PDF

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WO2019021790A1
WO2019021790A1 PCT/JP2018/025803 JP2018025803W WO2019021790A1 WO 2019021790 A1 WO2019021790 A1 WO 2019021790A1 JP 2018025803 W JP2018025803 W JP 2018025803W WO 2019021790 A1 WO2019021790 A1 WO 2019021790A1
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group
compound
curable composition
mass
cured film
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PCT/JP2018/025803
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French (fr)
Japanese (ja)
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峻輔 北島
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富士フイルム株式会社
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Priority to JP2019532480A priority Critical patent/JP6853363B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a curable composition, a cured film, a method for producing a cured film, a near infrared cut filter, a solid-state imaging device, an image display device, and an infrared sensor.
  • CCDs charge coupled devices
  • CMOS complementary metal oxide semiconductors
  • the near infrared cut filter is manufactured, for example, using a curable composition containing a near infrared absorbing dye (see Patent Document 1).
  • the near-infrared absorbing dye tends to aggregate at the time of film formation.
  • the near infrared absorbing dye tends to aggregate.
  • the spectral characteristics may vary or the smoothness of the film surface may be reduced.
  • the size of the aggregate increases, it is likely that the aggregate will fall off from the membrane, and pores of the size of the aggregate may be generated at the location where the aggregate was present.
  • an object of the present invention is to provide a curable composition capable of producing a cured film having good water-resistant adhesion and suppressing the generation of aggregates derived from a near-infrared absorbing dye.
  • Another object of the present invention is to provide a cured film, a method for producing the cured film, a near infrared cut filter, a solid-state imaging device, an image display device, and an infrared sensor.
  • a cured film obtained using a curable composition containing a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator is It has been found that the water adhesion is good and the amount of aggregates derived from the near infrared absorbing dye is small, and the present invention has been completed. Accordingly, the present invention provides the following. ⁇ 1> A curable composition comprising a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
  • the curable composition as described in ⁇ 1> or ⁇ 2> which is a compound which has a ⁇ 3> cyclic ether group is a compound containing an aromatic ring.
  • ⁇ 6> The curable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the thermal radical polymerization initiator is at least one selected from a pinacol compound and an ⁇ -hydroxyacetophenone compound.
  • the thermal radical polymerization initiator is at least one selected from a pinacol compound and an ⁇ -hydroxyacetophenone compound.
  • the near-infrared absorbing dye is a compound having a ⁇ -conjugated plane including an aromatic ring of a single ring or a condensed ring.
  • the near infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, squarylium compounds and cyanine compounds.
  • ⁇ 9> A cured film obtained from the curable composition according to any one of ⁇ 1> to ⁇ 8>.
  • the manufacturing method of the cured film as described in ⁇ 10> whose ⁇ 11> support body is a glass base material containing copper.
  • the near-infrared cut off filter which has a cured film as described in ⁇ 12> ⁇ 9>.
  • the near-infrared cut off filter as described in ⁇ 12> which has the said cured film on the surface of the glass base material containing ⁇ 13> copper.
  • the solid-state image sensor which has a cured film as described in ⁇ 14> ⁇ 9>.
  • the image display apparatus which has a cured film as described in ⁇ 15> ⁇ 9>.
  • the infrared sensor which has a cured film as described in ⁇ 16> ⁇ 9>.
  • this invention can provide a cured film, the manufacturing method of a cured film, a near-infrared cut off filter, a solid-state image sensor, an image display apparatus, and an infrared sensor.
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
  • the notation not describing substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • particle beams such as electron beams and ion beams.
  • active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like can be mentioned.
  • (meth) acrylate represents both or either of acrylate and methacrylate
  • (meth) acryl represents both or either of acrylic and methacryl
  • Allyl represents both or any of allyl and methallyl
  • (meth) acryloyl represents both or any of acryloyl and methacryloyl.
  • the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
  • the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.), and TSKgel Super AWM-H (manufactured by Tosoh Corp.), 6 as a column. It can be determined by using a solution of 10 mmol / L lithium bromide NMP (N-methyl pyrrolidinone) as an eluent, using a .0 mm ID (inner diameter) x 15.0 cm).
  • near-infrared light refers to light having a wavelength of 700 to 2,500 nm.
  • total solids refers to the total mass of all components of the composition excluding the solvent.
  • process not only refers to an independent process, but also to the term “process” if the intended function of the process is achieved even if it can not be distinguished clearly from other processes. include.
  • the curable composition of the present invention is characterized by containing a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
  • a near infrared absorbing dye a compound having a cyclic ether group
  • a radically polymerizable compound a compound having a cyclic ether group
  • a thermal radical polymerization initiator a thermal radical polymerization initiator.
  • the polymerization reaction of the polymerizable compound proceeds rapidly, and the film can be rapidly cured. Therefore, it is presumed that the near infrared absorbing dye is rapidly incorporated into the crosslinked network in the membrane.
  • the compound having a cyclic ether group cures slower than the radically polymerizable compound, but the compound having a cyclic ether group is considered to easily interact with the near infrared absorbing dye, and in the vicinity of the near infrared absorbing dye It is inferred that curing of the compound having a cyclic ether group proceeds.
  • the curable composition of the present invention was able to effectively suppress the aggregation of the near infrared absorbing dye at the time of heating, and was able to produce a cured film with few aggregates derived from the near infrared absorbing dye.
  • Ru it is presumed that the cyclic ether group of the compound having a cyclic ether group easily reacts with a hydroxyl group or the like on the support to thereby obtain excellent adhesion to the support.
  • the compound having a cyclic ether group is a compound that is hard to cure and shrink
  • a cured film that is hard to cure and shrink can be formed by including the compound having a cyclic ether group in the curable composition. Be done.
  • a cured film having a high crosslinking density can be formed by the radically polymerizable compound, it is possible to effectively suppress the entry of water into the film.
  • a cured film having high adhesion to the support can be formed on the support while suppressing curing shrinkage, so even if such a cured film is immersed in water Then, it is possible to effectively suppress the entry of water into the interface between the support and the cured film, and it is therefore presumed that excellent water-resistant adhesion is obtained.
  • each component of the curable composition of this invention is demonstrated.
  • the curable composition of the present invention contains a near infrared absorbing dye.
  • the near infrared absorbing dye may be a pigment (also referred to as a near infrared absorbing pigment), or may be a dye (also referred to as a near infrared absorbing dye). It is also preferable to use a near infrared absorbing dye and a near infrared absorbing pigment in combination.
  • the ratio is preferably 1: 99.9, more preferably 99.9: 0.1 to 10:90, and still more preferably 99.9: 0.1 to 20:80.
  • the near infrared absorbing dye preferably has a solubility of 1 g or more, preferably 2 g or more, in 100 g of at least one solvent selected from cyclopentanone, cyclohexanone and dipropylene glycol monomethyl ether at 23 ° C.
  • the content is more preferably 5 g or more.
  • the near infrared absorbing pigment preferably has a solubility of 100 g of each of cyclopentanone, cyclohexanone and dipropylene glycol monomethyl ether at 23 ° C. of preferably less than 1 g, and more preferably 0.1 g or less Preferably, it is more preferably 0.01 g or less.
  • the near infrared absorbing dye is preferably a compound having a ⁇ conjugated plane including a single ring or a fused aromatic ring. Due to the interaction between aromatic rings in the ⁇ conjugated plane of the near infrared absorbing dye, the J aggregate of the near infrared absorbing dye is easily formed during the production of the cured film, and a cured film having excellent spectral characteristics in the near infrared region is produced. it can. Moreover, it is easy to interact with the compound which has cyclic ether group, and it is easy to form the cured film more excellent in water-resistant adhesiveness. In particular, when a compound having an aromatic ring is used as the compound having a cyclic ether group, the compound more easily interacts with the compound having a cyclic ether group, and the water-resistant adhesion can be remarkably improved.
  • the number of atoms other than hydrogen constituting the ⁇ conjugated plane possessed by the near infrared absorbing dye is preferably 6 or more, more preferably 14 or more, still more preferably 20 or more, and 25 It is more preferable that it is the above, and it is especially preferable that it is 30 or more.
  • the upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
  • the ⁇ conjugated plane possessed by the near infrared absorbing dye preferably contains two or more, more preferably three or more, and still more preferably four or more, of a single ring or a fused ring aromatic ring. It is particularly preferred to include.
  • the upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less.
  • the above-mentioned aromatic ring includes benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzoimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzooxazole ring, imidazoline ring, pyrazine And rings, quinoxaline rings, pyrimidine rings, quin
  • the near infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the range of 700 to 1,300 nm, and more preferably a compound having a maximum absorption wavelength in the range of 700 to 1,000 nm.
  • “having a maximum absorption wavelength in the wavelength range of 700 to 1,300 nm” means that the wavelength showing the maximum absorbance in the absorption spectrum of the near-infrared absorbing dye in the solution is 700 to It means that it exists in the range of 1,300 nm.
  • a measurement solvent used for the measurement of the absorption spectrum in the solution of a near-infrared absorption pigment chloroform, methanol, dimethyl sulfoxide, ethyl acetate, tetrahydrofuran are mentioned.
  • the near infrared absorbing dye is a compound that dissolves in chloroform
  • chloroform is used as a measurement solvent. If it is a compound which does not dissolve in chloroform, methanol is used.
  • dimethyl sulfoxide is used when it does not dissolve in either chloroform or methanol.
  • Near infrared absorbing dye has an absorption maximum wavelength in a wavelength range of 700 ⁇ 1,000 nm, and the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength in the wavelength 500 nm, 0. It is preferably 08 or less, more preferably 0.04 or less. According to this aspect, it is easy to manufacture a cured film having excellent visible transparency and infrared shielding properties.
  • the waveform of the absorption spectrum of the obtained cured film is wider than in the case of using one type of near-infrared absorbing dye, and it is possible to shield near-infrared rays in a wide wavelength range.
  • the first near-infrared absorbing dye having the maximum absorption wavelength in the wavelength range of 700 to 1,000 nm and the maximum absorption wavelength of the first near-infrared absorbing dye At least a second near infrared absorbing dye having a maximum absorption wavelength in a wavelength range of 700 to 1,000 nm on the short wavelength side, the maximum absorption wavelength of the first near infrared absorbing dye, and the second near infrared absorption dye;
  • the difference from the maximum absorption wavelength of the infrared absorbing dye is preferably 1 to 150 nm.
  • near infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, At least one selected from a pyrromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squalilium compound, a phthalocyanine compound, a naphthalocyanine compound and a quaterrylene compound is more preferable.
  • diimmonium compounds include the compounds described in JP-A-2008-528706, the contents of which are incorporated herein.
  • the phthalocyanine compound for example, a compound described in paragraph 0093 of JP-A-2012-77153, an oxytitanium phthalocyanine described in JP-A-2006-343631, a paragraph number 0013 to 0029 of JP-A-2013-195480.
  • vanadium phthalocyanine described in Japanese Patent No. 6081771 the contents of which are incorporated herein.
  • naphthalocyanine compound the compound as described in stage number 0093 of Unexamined-Japanese-Patent No. 2012-77153 is mentioned, for example, This content is integrated in this specification.
  • the cyanine compound the phthalocyanine compound, the naphthalocyanine compound, the dimonium compound and the squarylium compound, the compounds described in paragraphs [0010] to [0081] of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated.
  • cyanine compounds can be referred to, for example, "functional dyes, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein. .
  • the near infrared absorbing dye a compound described in JP-A-2016-146619 can also be used, and the contents thereof are incorporated in the present specification.
  • the pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
  • R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R 2 and R 3 represent R 4 may be combined with 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 is an R R 4A and R 4B may each independently represent a substituent, which may be covalently bonded or coordinated with at least one selected from 1 a 1 , R 1 b and R 3 .
  • R 4A and R 4B may be bonded to each other to form a ring.
  • Formula (PP) Paragraph No. 0017 of the Unexamined-Japanese-Patent No. 2009-263614, Paragraph No. 0011 of the Unexamined-Japanese-Patent No. 2011-68731, Paragraph No. 0010 of the international publication WO2015 / 166873 The contents of which are incorporated herein by reference.
  • R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
  • the alkyl group, the aryl group and the heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in Paragraph Nos. 0020 to 0022 of JP 2009-263614 A, and the following substituent T.
  • An alkyl group preferably an alkyl group having 1 to 30 carbon atoms
  • an alkenyl group preferably an alkenyl group having 2 to 30 carbon atoms
  • an alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
  • an aryl group preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group
  • acyl group preferably having 1 to 30 carbon atoms
  • alkoxycarbonyl group preferably having 2 to 30 carbon atoms
  • aryloxycarbonyl group preferably having 2 to 30 carbon atoms
  • an acyloxy group preferably an acylo group having 2 to 30
  • an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably 7 to carbon atoms) 30) aryloxycarbonylamino group), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably having 1 to 30 carbon atoms) Alkylthio group), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 1 to 30 carbon atoms) Preferably having 6 to 30 carbon
  • R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, an aryl group having an acyloxy group as a substituent and the like.
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent.
  • the substituent include the above-mentioned substituent T.
  • At least one of R 2 and R 3 is preferably an electron-withdrawing group.
  • a substituent having a positive Hammett's substituent constant ⁇ value acts as an electron-withdrawing group.
  • the substituent constants determined by the Hammett rule include ⁇ p values and ⁇ m values. These values can be found in many general books.
  • a substituent having a Hammett's substituent constant ⁇ value of 0.2 or more can be exemplified as the electron-withdrawing group.
  • the ⁇ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more.
  • the upper limit is not particularly limited, but is preferably 0.80 or less.
  • a cyano group is preferable.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the Hammett's substituent constant ⁇ value can be referred to, for example, paragraph Nos. 0017 to 0018 of JP-A-2011-68731, the contents of which are incorporated herein.
  • R 2 preferably represents an electron-withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5- or 6-membered ring.
  • the heteroaryl group is preferably a single ring or a fused ring, preferably a single ring or a fused ring having 2 to 8 condensations, and more preferably a single ring or a fused ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2.
  • a hetero atom a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • Two R 2 s in Formula (PP) may be identical to or different from each other.
  • two R 3 's in Formula (PP) may be the same or different.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR 4A R 4B , and a hydrogen atom, an alkyl group, an aryl group or —BR
  • the group represented by 4A R 4B is more preferably a group represented by -BR 4A R 4B .
  • the substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and an aryl group Particularly preferred. These groups may further have a substituent.
  • Two R 4 's in the formula (PP) may be the same or different.
  • R 4A and R 4B may be bonded to each other to form a ring.
  • Ph represents a phenyl group.
  • pyrrolopyrrole compounds compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A, WO 2015/166873 And the compounds described in Paragraph No. 0010 to 0033 of the publication, the contents of which are incorporated herein.
  • each of A 1 and A 2 independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);
  • Z 1 represents a nonmetal atomic group forming a nitrogen-containing heterocyclic ring
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group
  • d represents 0 or 1.
  • the wavy line represents a connecting hand.
  • the squarylium compound is preferably a compound represented by the following formula (SQ-1).
  • Ring A and ring B each independently represent an aromatic 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
  • k B represents an integer of 0 to n B
  • n A and n B respectively represent the largest integers which can be substituted on ring A or ring B
  • X A and G A , X B and G B , and X A and X B may bond to each other to form a ring, and when there are a plurality of G A and G B respectively, they may be bonded to each other to form a ring structure May be formed.
  • the substituent represented by G A and G B include the substituent T described by the formula (PP) as described above.
  • Examples of the substituent represented by X A and X B preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2, -NHCOR X1, -CONR X1 R X2, -NHCONR X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 and -PO (OH) 2 are more preferable, and -OH, -SH and -NR X1 R X2 are more preferable.
  • Each of R X1 and R X1 independently represents a hydrogen atom or a substituent.
  • a substituent which X A and X B represent an alkyl group, an aryl group, or heteroaryl group is mentioned, An alkyl group is preferable.
  • Ring A and ring B each independently represent an aromatic ring.
  • the aromatic ring may be a single ring or a fused ring.
  • Specific examples of the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene 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, in
  • X A and G A , X B and G B , and X A and X B may bond to each other to form a ring, and when there are a plurality of G A and G B respectively, they may be bonded to each other to form a ring You may form.
  • the ring is preferably a 5- or 6-membered ring.
  • the ring may be a single ring or may be a fused ring.
  • X A and G A , X B and G B , X A and X B , G A or B B bond together to form a ring, these may be directly bonded to form a ring;
  • the ring may be formed through a divalent linking group consisting of the groups -CO-, -O-, -NH-, -BR- and combinations thereof.
  • R represents a hydrogen atom or a substituent.
  • the substituent T demonstrated by Formula (PP) mentioned above is mentioned, An alkyl group or an aryl group is preferable.
  • kA represents an integer of 0 to nA
  • kB represents an integer of 0 to nB
  • n A represents a maximum integer replaceable to ring A
  • n B represents a maximum integer replaceable to ring B Represent.
  • Each of kA and kB is preferably independently 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.
  • the squarylium compound is also preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12).
  • Formula (SQ-10) Formula (SQ-11) Formula (SQ-12)
  • each X is a group of one or more hydrogen atoms optionally substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group.
  • n1 is 2 or 3.
  • n2 and n3 are each independently an integer of 0 to 2
  • n2 + n3 is 1 or 2.
  • Each of R 1 and R 2 independently represents an alkyl group or an aryl group.
  • the alkyl group and the aryl group may have a substituent or may be unsubstituted.
  • the substituent T demonstrated by the formula (PP) mentioned above is mentioned.
  • R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
  • n is 2 or 3.
  • the cyanine compound is preferably a compound represented by the formula (C).
  • Formula (C) In the formula, each of Z 1 and Z 2 independently represents a nonmetallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed.
  • R 101 and R 102 each independently represent 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
  • a and b are each independently 0 or 1;
  • X 1 represents an anion
  • c represents the number necessary to balance the charge
  • the site represented by Cy in the formula is an anion moiety
  • X 1 represents a cation
  • c represents the number necessary to balance the charge
  • c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule It is 0.
  • the following compounds may be mentioned. Further, as the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, compounds described in paragraphs 0026 to 0030 of JP 2002-194040 A, JP 2015-172004 A Compounds described in JP-A-2015-172102, compounds described in JP-A-2008-88426, and compounds described in JP-A-2017-031394, the contents of which are incorporated herein by reference. It is incorporated in the specification.
  • the near infrared absorbing dye used in the present invention is also exemplified as a preferred compound as a compound used in the examples described later.
  • the content of the near infrared absorbing dye is preferably 3 to 50% by mass with respect to the total solid content of the curable composition. 40 mass% or less is preferable, and, as for the upper limit, 35 mass% or less is more preferable. 4 mass% or more is preferable, and, as for a lower limit, 5 mass% or more is more preferable.
  • the near infrared absorbing dye may be used alone or in combination of two or more. In the case of 2 or more types, it is preferable that the total amount of them becomes the said range.
  • the curable composition of the present invention may further contain a near infrared absorber (also referred to as another near infrared absorber) other than the above-described near infrared absorbing dye.
  • a near infrared absorber also referred to as another near infrared absorber
  • Other near-infrared absorbers include inorganic pigments (inorganic particles).
  • the shape of the inorganic pigment is not particularly limited, and may be spherical, non-spherical, sheet-like, wire-like or tube-like.
  • metal oxide particles or metal particles are preferable.
  • metal oxide particles examples include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine-doped tin dioxide (F-doped) SnO 2 ) particles, niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, etc. may be mentioned.
  • the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like.
  • a tungsten oxide type compound can also be used as an inorganic pigment.
  • the tungsten oxide based compound is preferably cesium tungsten oxide. For details of the tungsten oxide based compound, paragraph 0080 of JP-A-2016-006476 can be referred to, and the contents thereof are incorporated in the present specification.
  • the content of the other near infrared absorber is 0.01 to 50 based on the total solid content of the curable composition of the present invention. % By weight is preferred. 0.1 mass% or more is preferable, and, as for a lower limit, 0.5 mass% or more is more preferable. 30 mass% or less is preferable, and, as for the upper limit, 15 mass% or less is more preferable.
  • the content of the other near infrared absorber in the total mass of the above-mentioned near infrared absorbing dye and the other near infrared absorber is preferably 1 to 99% by mass.
  • the curable composition of this invention does not contain another near-infrared absorber substantially.
  • the content of the other near-infrared absorber in the total mass of the above-mentioned near-infrared absorbing dye and the other near-infrared absorber is 0.5% by mass or less as substantially free of the other near-infrared absorber It is more preferable that it is 0.1 mass% or less, and it is still more preferable that it does not contain other near-infrared absorbers.
  • the curable composition of the present invention contains a radically polymerizable compound.
  • the radically polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and ethylenic More preferably, it is a compound having three or more groups having unsaturated bonds.
  • the upper limit of the number of groups having an ethylenically unsaturated bond in the radically polymerizable compound is, for example, preferably 15 or less, more preferably 6 or less.
  • a (meth) acryloyl group is preferable.
  • the radically polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
  • the radically polymerizable compound may be in the form of a monomer or a polymer, but a monomer is preferred.
  • the monomer type radically polymerizable compound preferably has a molecular weight of 100 to 3,000.
  • the upper limit is more preferably 2,000 or less, further preferably 1,500 or less.
  • the lower limit is more preferably 150 or more, and still more preferably 250 or more.
  • a radically polymerizable compound is a compound which does not have molecular weight distribution substantially.
  • a compound having a degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 to 1.5 is preferable, 1.0 to 1.3 is more preferable.
  • ethyleneoxy modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; Shin-Nakamura Chemical Co., Ltd. product), dipentaerythritol triacrylate (as a commercial product, KAYARAD D- 330; Nippon Kayaku Co., Ltd.
  • dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product, dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd. product, A-DPH-12E; Shin Nakamura Chemical Industry Co., Ltd.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT
  • 1, 6 -Hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
  • RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • RP-1040 can be mentioned.
  • the radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group or a phosphoric acid group.
  • Examples of commercially available products of radically polymerizable compounds having an acid group include Alonics M-305, M-510, M-520 (all manufactured by Toagosei Co., Ltd.).
  • the acid value of the radically polymerizable compound is preferably 0.1 to 40 mg KOH / g.
  • the lower limit is more preferably 5 mg KOH / g or more.
  • the upper limit is more preferably 30 mg KOH / g or less.
  • a compound having a caprolactone structure is also a preferred embodiment.
  • examples of radically polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
  • the description of paragraphs 0042 to 0045 in JP 2013-253224 A can be referred to for a radically polymerizable compound having a caprolactone structure, the contents of which are incorporated herein.
  • the radically polymerizable compound can also be a compound having an alkyleneoxy group.
  • the radically polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. More preferably, they are 3- to 6-functional (meth) acrylate compounds.
  • Commercially available products of radically polymerizable compounds having an alkyleneoxy group include, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) resin having three isobutylene oxy groups. And the like) and KAYARAD TPA-330 which is an acrylate.
  • JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable as urethane compounds having an ethylene oxide skeleton.
  • 8UH-1006, 8UH-1012 all manufactured by Taisei Fine Chemical Co., Ltd.
  • light acrylate POB-A0 manufactured by Kyoeisha Chemical Co., Ltd.
  • the content of the radically polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. 0.5 mass% or more is preferable, and, as for a lower limit, 1 mass% or more is more preferable. 30 mass% or less is preferable, and, as for the upper limit, 20 mass% or less is more preferable. Further, the content of the radically polymerizable compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. 3 mass% or more is preferable, and, as for a lower limit, 10 mass% or more is more preferable. 40 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable.
  • the content of the radically polymerizable compound is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye.
  • the upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less.
  • the lower limit is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 60 parts by mass or more.
  • the curable composition of the present invention may contain only one type of radically polymerizable compound, or may contain two or more types. When two or more radically polymerizable compounds are contained, the total amount thereof is preferably in the above range.
  • Thermal radical polymerization initiator is a compound that generates radicals by the energy of heat to initiate or accelerate the polymerization reaction of the radically polymerizable compound.
  • the thermal radical polymerization initiator may be a compound which generates a radical by the action of heat and light.
  • thermal radical polymerization initiators examples include pinacol compounds, ⁇ -hydroxyacetophenone compounds, ⁇ -aminoacetophenone compounds, benzyl dimethyl ketal compounds, organic peroxides, azo compounds and the like, and the effects of the present invention are more remarkably obtained.
  • Pinacol compounds and ⁇ -hydroxyacetophenone compounds are preferable, and pinacol compounds are more preferable because they are easy to use.
  • thermal radical polymerization initiators to be used in combination with pinacol compounds include ⁇ -hydroxyacetophenone compounds, ⁇ -aminoacetophenone compounds, benzyl dimethyl ketal compounds, organic peroxides, azo compounds, etc. ⁇ -hydroxyacetophenone compounds preferable.
  • the pinacol compound is preferably a benzopinacol compound.
  • Examples of pinacol compounds include compounds represented by the following formulas (T-1) to (T-3).
  • Rt 1 to Rt 4 each independently represent a substituent
  • m 1 to m 4 each independently represent an integer of 0 to 4.
  • m1 pieces of Rt 1 may be identical to or different from each other.
  • m1 pieces two of the Rt 1 of Rt 1 each other may bond to each other to form a ring.
  • m2 amino Rt 2 respectively may be the same or may be different.
  • m2 amino bonded to each other two Rt 2 together of Rt 2 may form a ring.
  • m3 amino Rt 3 may each be the same or may be different.
  • m3 or two Rt 3 out of Rt 3 together may be bonded to each other to form a ring.
  • m4 Rt 4 may be identical to or different from each other.
  • two Rt 4 of m4 Rt 4 may be bonded to each other to form a ring.
  • Rt 1 and Rt 2 , Rt 1 and Rt 3 , Rt 1 and Rt 4 , Rt 2 and Rt 3 , Rt 2 and Rt 4 , and Rt 3 and Rt 4 may form a ring.
  • Rt 5 and Rt 6 each independently represent a hydrogen atom, an alkyl group, an aryl group, Ti (R M1 ) (R M2 ) (R M3 ), Zr (R M1 ) (R M2 ) ( RM3 ), Si ( RM1 ) ( RM2 ) ( RM3 ) or B ( RM1 ) ( RM2 ) is represented, and RM1 to RM3 each independently represent a substituent.
  • M 1 represents Ti ( RM 4 ) ( RM 5 ), Zr ( RM 4 ) ( RM 5 ), Si ( RM 4 ) ( RM 5 ) or B ( RM 4 ), Each of R M4 and R M5 independently represents a substituent.
  • M 2 represents Ti ( RM 6 ), Zr ( RM 6 ), Si ( RM 6 ) or B, RM 6 represents a substituent, and L 1 represents a divalent linking group Represents
  • the substituent represented by Rt 1 to Rt 4 and R M1 to R M6 is an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR X1 , -SR X1 , -COR X1 ,- COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 Etc.
  • Each of R X1 and R X2 independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • the halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the carbon number of the alkyl group as a substituent, the alkyl group represented by R X1 and R X2, and the alkyl group represented by Rt 5 and Rt 6 in the formula (T-1) is preferably 1 to 20.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the carbon number of the aryl group as a substituent, the aryl group represented by R X1 and R X2, and the aryl group represented by Rt 5 and Rt 6 in the formula (T-1) is preferably 6 to 20, and more preferably 6 to 15 And 6 to 10 are more preferable.
  • the aryl group may be a single ring or a fused ring.
  • the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring.
  • the heterocyclic group may be a single ring or may be a fused ring.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.
  • the number of hetero atoms constituting the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • part or all of hydrogen atoms may be substituted by the above-mentioned substituent.
  • M1 to m4 each independently represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
  • a preferable aryl group is represented, preferably a hydrogen atom), -SO 2- , -CO-, -COO-, -OCO-, -O-, -S- and a combination thereof.
  • Rt 5 and Rt 6 are a hydrogen atom, and more preferably both Rt 5 and Rt 6 is a hydrogen atom.
  • pinacol compounds include benzopinacol, 1-hydroxy-2-trimethylsiloxy-1, 1, 2, 2-tetraphenylethane and the like. Further, with regard to the pinacol compound, the descriptions in JP-A-2014-521772, JP-A-2014-523939, and JP-A-2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the ⁇ -hydroxyacetophenone compound include compounds represented by the following formula (T-11).
  • Formula (T-11) Wherein Rt 11 represents a substituent, Rt 12 and Rt 13 are each independently, represent a hydrogen atom or a substituent, may form a ring Rt 12 and Rt 13 are mutually, m represents an integer of 0 to 4;
  • the substituent Rt 11 represents, and a substituted group mentioned above, an alkyl group, an alkoxy group are preferred.
  • the alkyl group and the alkoxy group may be unsubstituted or may have a substituent.
  • a substituent a hydroxy group etc. are mentioned.
  • Rt 12 and Rt 13 each independently represent a hydrogen atom or a substituent.
  • substituents include the above-mentioned substituents, and an alkyl group and an aryl group are preferable.
  • Rt 12 and Rt 13 ring bonded to each other rings preferably 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms may form.
  • ⁇ -hydroxyacetophenone compound examples include 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-l. On etc. are mentioned.
  • ⁇ -hydroxyacetophenone compounds examples include IRGACURE-184, IRGACURE-2959 (manufactured by BASF AG), and the like.
  • ⁇ -aminoacetophenone compound 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Examples include 1-butanone, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.
  • Examples of commercially available ⁇ -aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (manufactured by BASF Corporation).
  • Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone and the like.
  • Examples of commercially available products include IRGACURE-651 (manufactured by BASF).
  • azo compound 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis ( 2-Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2- Propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like.
  • azo compound Commercial products of the azo compound include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, VA-080, VA- 086, VF-096, VAm-110, VAm-111, VA-044, VA-046B, VA-060, VA-061, V-50, VA-057, VA-067, VR-110 (more, Wako Pure) Pharmaceutical Industries Ltd. make) etc. are mentioned.
  • organic peroxide methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide Peroxide, paramethan hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide Tert-Butylcumyl peroxide, dicumyl peroxide, bis (tert-butylperoxyisopropyl
  • the molar absorption coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, more preferably 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and 10 L ⁇ mol still more preferably -1 ⁇ cm -1 or less. If the molar absorptivity of the thermal radical polymerization initiator at a wavelength of 365 nm is 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, generation of radicals from the thermal radical polymerization initiator is effective during storage of the curable composition. The storage stability of the curable composition is good.
  • the molar absorption coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is prepared by dissolving the thermal radical polymerization initiator in a solvent to prepare a 5 mol% solution (measurement solution) of the thermal radical polymerization initiator. It was calculated by measuring the absorbance of the measurement solution of Specifically, the measurement solution described above is placed in a 1 cm wide glass cell, the absorbance is measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies, and the molar ratio at a wavelength of 365 nm is applied according to the following equation. The extinction coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) was calculated.
  • ⁇ is the molar absorption coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
  • A is the absorbance
  • c is the concentration of the measurement solution (mol / L)
  • l is the optical path length (cm).
  • Acetonitrile and chloroform are mentioned as a solvent used for preparation of a measurement solution in measurement of the molar absorption coefficient of a thermal radical polymerization initiator.
  • the thermal radical polymerization initiator is a compound that dissolves in acetonitrile
  • acetonitrile is used to prepare a measurement solution.
  • the thermal radical polymerization initiator is a compound which is insoluble in acetonitrile but soluble in chloroform
  • chloroform is used to prepare a measurement solution.
  • the thermal radical polymerization initiator is a compound which is insoluble in acetonitrile and chloroform but soluble in dimethyl sulfoxide, dimethyl sulfoxide is used to prepare a measurement solution.
  • the thermal decomposition temperature of the thermal radical polymerization initiator is preferably 120 to 270.degree.
  • the upper limit of the thermal decomposition temperature is preferably 250 ° C. or less, more preferably 220 ° C. or less, and still more preferably 190 ° C. or less.
  • the lower limit of the thermal decomposition temperature is preferably 120 ° C. or more, more preferably 150 ° C. or more, and still more preferably 170 ° C. or more. If the thermal decomposition temperature of the thermal radical polymerization initiator is 120 ° C. or higher, generation of radicals from the thermal radical polymerization initiator can be effectively suppressed during storage of the curable composition, and storage of the curable composition The stability is good. If the thermal decomposition temperature of the thermal radical polymerization initiator is 270 ° C. or less, radicals can be generated rapidly by heating, and the curability of the curable composition is good.
  • the thermal decomposition temperature of the thermal radical polymerization initiator is a value measured by thermal weight / differential heat (TG-DTA) measurement.
  • the weight percent temperature of the thermal radical polymerization initiator is preferably 90 to 220 ° C.
  • the upper limit of the weight 1% temperature is preferably 215 ° C. or less, more preferably 210 ° C. or less, and still more preferably 200 ° C. or less.
  • the lower limit of the weight 1% temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 150 ° C. or higher. If the temperature by weight of the thermal radical polymerization initiator is in the above-mentioned range, it is easy to achieve both low temperature curability and storage stability of the composition.
  • the 1% temperature by weight of the thermal radical polymerization initiator is a temperature at which the weight decreases by 1% as measured by TG-DTA measurement for the initiator alone.
  • the content of the thermal radical polymerization initiator is preferably 0.1 to 10% by mass with respect to the total solid content of the curable composition. 0.5 mass% or more is preferable, and, as for a lower limit, 1 mass% or more is more preferable.
  • the upper limit is more preferably 5% by mass or less.
  • the content of the thermal radical polymerization initiator is preferably 0.05 to 200 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. 1 mass part or more is preferable, 10 mass parts or more are more preferable, 50 mass parts or more may be sufficient, 80 mass parts or more may be sufficient, and a lower limit may exceed 100 mass parts.
  • the upper limit is preferably 150 parts by mass or less, and more preferably 120 parts by mass or less.
  • the ratio between the thermal radical polymerization initiator and the radically polymerizable compound is in the above range, the water-resistant adhesion is better, and it is easy to form a cured film in which the generation of aggregates derived from the near-infrared absorbing dye is further suppressed .
  • the content of the ⁇ -hydroxyacetophenone compound is 1 to 70 parts by mass with respect to 100 parts by mass of the pinacol compound. Is preferable, 3 to 60 parts by mass is more preferable, and 5 to 50 parts by mass is more preferable.
  • the curable composition of the present invention may contain only one type of thermal radical polymerization initiator, or may contain two or more types. When 2 or more types of thermal radical polymerization initiators are included, it is preferable that the total amount of them becomes the said range. Further, in the present invention, it may be configured not to substantially contain the photo radical polymerization initiator.
  • substantially free means that, for example, the content of the photo radical polymerization initiator is 1% by mass or less of the content of the thermal radical polymerization initiator.
  • the curable composition of the present invention contains a compound having a cyclic ether group.
  • a cyclic ether group an epoxy group and oxetanyl group are mentioned, and an epoxy group is preferable.
  • the compound having a cyclic ether group is preferably a compound having two or more cyclic ether groups in one molecule.
  • the upper limit of the number of cyclic ether groups in the compound having cyclic ether groups is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less.
  • the cyclic ether group equivalent of the compound having a cyclic ether group (molecular weight of the compound having a cyclic ether group / number of cyclic ether groups in the compound having a cyclic ether group) is preferably 50 to 400 g / mol.
  • the lower limit of the cyclic ether group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more.
  • the upper limit is preferably 350 g / mol or less, more preferably 300 g / mol or less.
  • the epoxy group equivalent (molecular weight of the compound having an epoxy group / number of epoxy groups in the compound having an epoxy group) is 50 to 400 g / mol Is preferred.
  • the lower limit of the epoxy group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more.
  • the upper limit is preferably 350 g / mol or less, more preferably 300 g / mol or less.
  • the compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more) It is also good.
  • the molecular weight (weight average molecular weight in the case of a polymer) of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.
  • the compound having a cyclic ether group used in the present invention is preferably a compound having a repeating unit.
  • the cyclic ether group may be on the side chain of the repeating unit or may be on the main chain terminal.
  • compounds having a cyclic ether group in a side chain are preferable because they are surface-adsorbed to a support to easily obtain more excellent water adhesion.
  • the compound having a cyclic ether group is preferably a compound having a structure having an aromatic ring and / or an aliphatic ring, and more preferably a compound having a structure having an aromatic ring.
  • a compound having an aromatic ring is used as the compound having a cyclic ether group, the compound easily interacts with a near infrared absorbing dye and easily forms a cured film having more excellent water resistance.
  • the aromatic ring is preferably an aromatic hydrocarbon ring.
  • the aromatic ring may be a single ring or a fused ring.
  • Specific examples of the aromatic ring include a benzene ring, a naphthalene ring and the like, and it is preferable to include at least a naphthalene ring because the compatibility with the near infrared absorbing dye is enhanced and the excellent water adhesion is easily obtained .
  • the number of aromatic rings is preferably one or more, and the compatibility with the near infrared absorbing dye is enhanced, and excellent water-resistant adhesion is obtained. It is more preferable that it is 2 or more from the reason of being easy.
  • the upper limit is preferably 5 or less, more preferably 4 or less.
  • the number of aromatic rings in one repeating unit is preferably 1 to 10. Seven or less are preferable and, as for the upper limit, five or less are more preferable.
  • the lower limit is preferably 2 or more.
  • the number of aromatic rings in the compound having a cyclic ether group is a total value of the number of monocyclic aromatic rings and the number of rings constituting a fused ring. For example, in the case of a compound having a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having this cyclic ether group is two.
  • the number of aromatic rings of the compound having a cyclic ether group is three.
  • the cyclic ether group When the compound having a cyclic ether group is a compound having a structure having an aromatic ring and / or an aliphatic ring, the cyclic ether group may be bonded to an aromatic ring and / or an aliphatic ring via a single bond or a linking group. It is preferred that they be linked.
  • an alkylene group an arylene group, -NR'- (R 'represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, hydrogen Atoms are preferable), -SO 2- , -CO-, -COO-, -OCO-, -O-, -S- and a group formed by combining these.
  • EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation) as cresol novolac epoxy resins And EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all, made by ADEKA), Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (all manufactured by Daicel Co., Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Co., Ltd.), and the like.
  • OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd.), OXE-10, OXE-30 (all, Osaka Organic Chemical Industry Co., Ltd.) and the like.
  • the content of the compound having a cyclic ether group is preferably 1 to 45% by mass with respect to the total solid content of the curable composition. 2 mass% or more is preferable, and, as for a lower limit, 3 mass% or more is more preferable. 40 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable.
  • the content of the compound having a cyclic ether group is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the near infrared absorbing dye.
  • the upper limit is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and still more preferably 300 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. If the ratio of the compound having a cyclic ether group to the near infrared absorbing dye is in the above range, the cured film is formed with better water resistance and more suppressed generation of aggregates derived from the near infrared absorbing dye. easy.
  • the curable composition of the present invention may contain only one type of compound having a cyclic ether group, or may contain two or more types. When two or more compounds having a cyclic ether group are contained, the total amount thereof is preferably in the above range.
  • the curable composition of the present invention can further contain a radical photopolymerization initiator.
  • a radical photopolymerization initiator a compound which generates radicals for light in the ultraviolet region to the visible region is preferable.
  • trihalomethyl triazine compounds trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, ⁇ -aminoacetophenone compounds, ⁇ -hydroxyacetophenone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, oniums
  • the compounds include benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds.
  • the photo radical polymerization initiator is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm.
  • the photo radical polymerization initiator is preferably a compound having a high absorbance at 365 nm and 405 nm.
  • the molar absorption coefficient of the radical photopolymerization initiator at a wavelength of 365 nm is preferably more than 5 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 , more preferably more than 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 , and 15 L ⁇ mol ⁇ 1 - more preferably of greater than cm -1, even more preferably greater than 50L ⁇ mol -1 ⁇ cm -1, and particularly preferably more than 100L ⁇ mol -1 ⁇ cm -1.
  • the content of the photoradical polymerization initiator is preferably 20% by mass or less, preferably 15% by mass, based on the total solid content of the curable composition. 10 mass% is more preferable.
  • the lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the photo radical polymerization initiator may be used alone or in combination of two or more. When two or more types of photo radical polymerization initiators are used in combination, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain a resin as a component other than the above-described compound having a cyclic ether group and the radically polymerizable compound.
  • the resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder.
  • grains, such as a pigment is also called a dispersing agent.
  • such application of the resin is an example, and the resin can also be used for purposes other than such application.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • 3,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.
  • One of these resins may be used alone, or two or more thereof may be mixed and used.
  • cyclic olefin resin norbornene resin can be preferably used from a viewpoint of heat resistance improvement.
  • Examples of commercially available products of norbornene resin include ARTON series (for example, ARTON F 4520) manufactured by JSR Corporation.
  • ARTON series for example, ARTON F 4520
  • JSR Corporation examples of commercially available products of norbornene resin
  • a resin described in an example of International Publication WO 2016/088645, a resin described in JP-A-2017-57265, a resin described in JP-A-2017-32685, JP-A-2017 It is also possible to use the resin described in Japanese Patent Application Laid-Open No. 0-75248 and the resin described in JP-A-2017-066240, the contents of which are incorporated herein.
  • the resin used in the present invention may have an acid group.
  • an acid group a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable.
  • These acid groups may be of only one type, or of two or more types.
  • the resin having an acid group can also be used as an alkali-soluble resin.
  • a polymer having a carboxyl group in a side chain is preferable.
  • alkali-soluble polymers such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, novolac resin, etc.
  • a phenolic resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxy group are mentioned.
  • copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin.
  • Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, ⁇ -methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfur
  • N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenyl maleimide, N-cyclohexyl maleimide and the like can also be used.
  • These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.
  • the resin having an acid group may further have a polymerizable group.
  • the polymerizable group include (meth) allyl group and (meth) acryloyl group.
  • Commercially available products include Dianal NR series (Mitsubishi Rayon Co., Ltd.), Photomer 6173 (Carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all are Osaka organic) Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all from Daicel Co., Ltd.), Ebecryl 3800 (Daicel UBC Co., Ltd.), Acrycure RD-F8 (Co., Ltd.) Nippon Catalyst Co., Ltd. and the like.
  • Resin having an acid group is benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth)
  • a multicomponent copolymer consisting of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, those obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No.
  • the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). It is also preferable that it is a polymer containing a repeating unit derived from a component.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168539 can be referred to.
  • ether dimer for example, paragraph “0317” of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
  • the ether dimer may be only one type, or two or more types.
  • the resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
  • Represents an alkyl group of n represents an integer of 1 to 15.
  • the resin having an acid group is described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding US patent application publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408.
  • No. 0076-0099 can be referred to, and the contents thereof are incorporated herein.
  • the resin which has an acidic radical can also use a commercial item.
  • Acrybase FF-426 manufactured by Fujikura Kasei Co., Ltd.
  • the like can be mentioned.
  • the acid value of the resin having an acid group is preferably 30 to 200 mg KOH / g.
  • the lower limit is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more.
  • 150 mgKOH / g or less is preferable and 120 mgKOH / g or less of an upper limit is more preferable.
  • resin which has an acidic radical resin of the following structure etc. are mentioned, for example.
  • resin of the following structural formulae Me represents a methyl group.
  • a resin having repeating units represented by formulas (A3-1) to (A3-7).
  • R 5 represents a hydrogen atom or an alkyl group
  • L 4 to L 7 each independently represent a single bond or a divalent linking group
  • R 10 to R 13 each independently represent an alkyl group or an aryl group .
  • Each of R 14 and R 15 independently represents a hydrogen atom or a substituent.
  • R 5 represents a hydrogen atom or an alkyl group.
  • the carbon number of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
  • R 5 is preferably a hydrogen atom or a methyl group.
  • L 4 to L 7 each independently represent a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , and -NR 10- (R 10 is a hydrogen atom or Represents an alkyl group, preferably a hydrogen atom) Or a group consisting of a combination of these.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10.
  • the alkylene group may have a substituent, but is preferably unsubstituted.
  • the alkylene group may be linear, branched or cyclic.
  • the cyclic alkylene group may be either monocyclic or polycyclic.
  • the carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
  • the alkyl group represented by R 10 to R 13 may be linear, branched or cyclic, preferably cyclic.
  • the alkyl group may have a substituent or may be unsubstituted.
  • the carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • the carbon number of the aryl group represented by R 10 to R 13 is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6.
  • R 10 is preferably a cyclic alkyl group or an aryl group.
  • R 11 and R 12 are preferably linear or branched alkyl groups.
  • R 13 is preferably a linear alkyl group, a branched alkyl group or an aryl group.
  • the substituent represented by R 14 and R 15 is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group , Alkylthio group, arylthio group, heteroarylthio group, -NR a1 R a2 , -COR a3 , -COOR a4 , -OCOR a5 , -NHCOR a6 , -CONR a7 R a8 , -NHCONR a9 R a10 , -NHCOOR a11 , And -SO 2 R a12 , -SO 2 OR a13 , -NHSO 2 R a14 or -SO 2 NR a15 R a16 .
  • Each of R a1 to R a16 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • at least one of R 14 and R 15 preferably represents a cyano group or -COOR a4 .
  • R a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.
  • Examples of commercially available resins having a repeating unit represented by the formula (A3-7) include ARTON F 4520 (manufactured by JSR Corporation).
  • ARTON F 4520 manufactured by JSR Corporation
  • the descriptions in paragraphs “0053” to “0075” and “0127 to 0130” of JP 2011-100084 A can be referred to, and the contents thereof are described in this specification. Incorporated into the book.
  • the curable composition of the present invention can also contain a resin as a dispersant.
  • a dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. Resins consisting only of groups are more preferred.
  • the acid group of the acidic dispersant is preferably a carboxyl group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mg KOH / g, more preferably 50 to 105 mg KOH / g, and still more preferably 60 to 105 mg KOH / g.
  • a basic dispersing agent (basic resin) represents resin whose quantity of a basic group is larger than the quantity of an acidic radical.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50% by mole, where the total amount of the amount of acid groups and the amount of basic groups is 100% by mole.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • the resin used as the dispersant preferably contains a repeating unit having an acid group.
  • the resin used as the dispersing agent contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixel when forming a pattern by photolithography.
  • the resin used as the dispersant is a graft copolymer.
  • the graft copolymer is excellent in the dispersibility of the pigment and the dispersion stability after aging since it has an affinity to a solvent by the graft chain.
  • the details of the graft copolymer can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the following resin is mentioned as a specific example of a graft copolymer.
  • the following resin is also a resin having an acid group (alkali soluble resin).
  • examples of the graft copolymer include the resins described in Paragraph Nos. 0072 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein.
  • an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain comprises a structural unit having a partial structure X having a functional group having a pKa of 14 or less and a side chain containing a side chain Y having an atom number of 40 to 10,000, and having a main chain and a side chain
  • the resin which has a basic nitrogen atom in at least one side is preferable.
  • the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • oligoimine dispersant With regard to the oligoimine dispersant, the description in paragraphs [0102] to [0166] of JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. Specific examples of the oligoimine dispersant include the following.
  • the following resin is also a resin having an acid group (alkali soluble resin). Further, as the oligoimine dispersant, the resins described in paragraph Nos. 0168 to 0174 of JP 2012-255128 A can be used.
  • the dispersant is also available as a commercial product, and as such specific examples, Disperbyk-111 (manufactured by BYK Chemie), Solsparse 76500 (manufactured by Nippon Lubrizol Co., Ltd.) and the like can be mentioned.
  • pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
  • the resin etc. which have an acidic radical mentioned above can also be used as a dispersing agent.
  • the content of the resin is preferably 1 to 60% by mass with respect to the total solid content of the curable composition of the present invention. 5 mass% or more is preferable, and, as for a lower limit, 7 mass% or more is more preferable. 50 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable.
  • the content of the dispersant is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition.
  • the upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. 0.5 mass% or more is preferable, and, as for a minimum, 1 mass% or more is more preferable.
  • the content of the dispersant is preferably 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, and more preferably 60 parts by mass or less. 2.5 mass parts or more are preferable, and 5 mass parts or more are more preferable for a minimum.
  • the curable composition of the present invention can contain a chromatic coloring agent.
  • a chromatic coloring agent means a coloring agent other than a white coloring agent and a black coloring agent.
  • the chromatic coloring agent is preferably a coloring agent having absorption in the wavelength range of 400 nm to less than 650 nm.
  • the chromatic coloring agent may be a pigment or a dye.
  • the pigment is preferably an organic pigment.
  • Examples of the organic pigment include the following. Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 35, 53, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167
  • the dye is not particularly limited, and known dyes can be used.
  • the chemical structure includes pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used. In addition, multimers of these dyes may be used. Further, dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
  • the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the curable composition of the present invention. . 0.5 mass% or more is preferable, and, as for a lower limit, 1.0 mass% or more is more preferable. 60 mass% or less is preferable, and, as for the upper limit, 50 mass% or less is more preferable.
  • the total amount of the chromatic coloring agent and the near-infrared absorbing dye is preferably 1 to 80% by mass with respect to the total solid content of the curable composition of the present invention. 5 mass% or more is preferable, and, as for a lower limit, 10 mass% or more is more preferable.
  • the curable composition of the present invention contains two or more types of chromatic coloring agents, the total amount thereof is preferably within the above range. It is also preferable that the curable composition of the present invention contains substantially no chromatic coloring agent.
  • the phrase "containing substantially no chromatic colorant" means that the content of the chromatic colorant is preferably 0.05% by mass or less, based on the total solid content of the curable composition, 0.01% by mass It is more preferable that it is the following and it is still more preferable that it does not contain a chromatic coloring agent.
  • the curable composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter, also referred to as a coloring material that blocks visible light).
  • the color material that blocks visible light is preferably a color material that absorbs light in the violet to red wavelength range.
  • the coloring material for blocking visible light is preferably a coloring material for blocking light in a wavelength range of 450 to 650 nm.
  • the coloring material that blocks visible light is a coloring material that transmits light with a wavelength of 900 to 1300 nm.
  • the coloring material that blocks visible light satisfy at least one of the following requirements (A) and (B).
  • a black color is formed by a combination of two or more chromatic colorants, including two or more chromatic colorants.
  • the organic black colorant examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds and the like, with bisbenzofuranone compounds and perylene compounds being preferred.
  • the bisbenzofuranone compounds those described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication WO 2014/208348, JP-A-2015-525260, etc.
  • the compound is mentioned, for example, it is available as "Irgaphor Black” made by BASF.
  • perylene compounds C.I. I. Pigment Black 31, 32 and the like.
  • the azomethine compound examples include compounds described in JP-A-1-170601, JP-A-2-32664 and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika.
  • Examples of combinations of chromatic colorants in the case of forming a black color by the combination of two or more chromatic colorants include the following. (1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant and a red colorant. (2) An embodiment containing a yellow colorant, a blue colorant and a red colorant. (3) An embodiment containing a yellow colorant, a purple colorant and a red colorant. (4) An embodiment containing a yellow colorant and a purple colorant. (5) An embodiment containing a green coloring agent, a blue coloring agent, a purple coloring agent and a red coloring agent. (6) An embodiment containing a purple colorant and an orange colorant. (7) An embodiment containing a green colorant, a purple colorant and a red colorant. (8) An embodiment containing a green colorant and a red colorant.
  • the content of the coloring material that blocks visible light is preferably 60% by mass or less based on the total solid content of the curable composition. 50 mass% or less is more preferable, 30 mass% or less is more preferable, 20 mass% or less is still more preferable, and 15 mass% or less is especially preferable.
  • the lower limit may be, for example, 0.1% by mass or more and may be 0.5% by mass or more.
  • the curable composition of this invention does not contain the coloring material which shades visible light substantially.
  • the content of the coloring material for blocking visible light is preferably 0.05% by mass or less based on the total solid content of the curable composition that substantially no coloring material for blocking visible light is contained. It is more preferable that it is 0.01 mass% or less, and it is further more preferable not to contain the coloring material which shields visible light.
  • the curable composition of the present invention can further contain a pigment derivative.
  • the pigment derivative includes a compound in which at least one group selected from an acid group and a basic group is bonded to a dye skeleton.
  • the compound represented by Formula (B1) is preferable.
  • P represents a dye skeleton
  • L represents a single bond or a linking group
  • X represents an acid group or a basic group
  • m represents an integer of 1 or more
  • n represents an integer of 1 or more
  • the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.
  • the dye skeleton represented by P includes pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, thiazine indigo dye skeleton, azo dye skeleton, quinophthalone Dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzoimidazole dye skeleton, and at least one selected from benzoimidazole dye skeleton And at least one selected from pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton and
  • the linking group represented by L includes a group consisting of a hydrocarbon group, a heterocyclic group, -NR-, -SO 2- , -S-, -O-, -CO- or a combination thereof.
  • R represents a hydrogen atom, an alkyl group or an aryl group.
  • Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group.
  • a group represented by -NHCOR X1 is preferable.
  • the sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 .
  • the imide group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 .
  • Each of R X1 to R X6 independently represents a hydrocarbon group or a heterocyclic group.
  • the hydrocarbon group and the heterocyclic group which R X1 to R X6 represent may further have a substituent.
  • the substituent T described in the above-mentioned formula (PP) can be mentioned, and a halogen atom is preferable, and a fluorine atom is more preferable.
  • An amino group is mentioned as a basic group which X represents.
  • a salt structure which X represents the salt of the acid group or basic group mentioned above is mentioned.
  • Hei 3-45662 Hei 4-285669, Hei 6-145546, Hei 6-212088, Hei 6-240158, Hei 10-30063, Compounds described in JP-A-10-195326, International Publication WO 2011/024896, paragraphs 0086 to 0098, International Publication WO 2012/102399, paragraphs 0063 to 0094, etc., Patent 5299151 Can also be used, the contents of which are incorporated herein.
  • the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. 3 mass parts or more are preferable, and 5 mass parts or more of a lower limit are more preferable. 40 mass parts or less are preferable, and 30 mass parts or less are more preferable.
  • a pigment derivative may use only 1 type and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the curable composition of the present invention preferably contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
  • the organic solvent include, for example, esters, ethers, ketones, aromatic hydrocarbons and the like. For details of these, reference can be made to paragraph No. 0223 of International Publication WO 2015/166779, the content of which is incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • the organic solvent may be used singly or in combination of two or more. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, or 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content.
  • the metal content of the solvent is preferably, for example, 10 parts by weight (pps) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • a method of removing impurities such as metal from the solvent for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned.
  • distillation molecular distillation, thin film distillation, etc.
  • filtration using a filter As a filter hole diameter of a filter used for filtration, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.
  • the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass, with respect to the total amount of the curable composition.
  • the total amount thereof is preferably in the above range.
  • the curable composition does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent because of environmental reasons and the like.
  • the content of the solvent is preferably 10 to 97% by mass with respect to the total amount of the curable composition.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and 70% by mass It is particularly preferable to be the above.
  • the upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less.
  • the curable composition of the present invention can contain a polymerization inhibitor.
  • a polymerization inhibitor hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts and the like). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor is preferably 0.001 to 5% by mass with respect to the total solid content of the curable composition.
  • the curable composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, for example And the like, and (meth) acryloyl group and epoxy group are preferable.
  • the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604, the contents of which are It is incorporated in the specification.
  • the silane coupling agent is preferably a silane coupling agent having a urea group.
  • the content of the silane coupling agent is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass, with respect to the total solid content of the curable composition. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the surfactant can be referred to in paragraphs [0238 to 0245] of International Publication WO 2015/166779, the content of which is incorporated herein.
  • the surfactant is preferably a fluorine-based surfactant.
  • the liquid properties in particular, the fluidity
  • the liquid saving property can be further improved.
  • a film with small thickness unevenness can also be formed.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • the fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.
  • fluorine-based surfactant examples include the surfactants described in paragraph Nos. 0060 to 0064 of JP-A-2014-41318 (paragraph Nos. 0060 to 0064 of corresponding international publication 2014/17669) and the like, and the like. Examples thereof include the surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, the contents of which are incorporated herein.
  • the fluorine-based surfactant is a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied to volatilize the fluorine atom is also preferable. It can be used.
  • a fluorochemical surfactant Megafuck DS series (Chemical Chemical Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS -21 can be mentioned.
  • the fluorine-based surfactant a block polymer can also be used.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (meth)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorinated surfactant used in the present invention.
  • the weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of repeating units is mol%.
  • the fluorine-based surfactant it is preferable to use a compound having a fluorine atom and a curable group (hereinafter, also referred to as a fluorine-containing curable compound).
  • a fluorine-containing curable compound a compound having a fluorine atom and a curable group
  • the heat resistance of the resulting film can be further improved.
  • excellent solvent resistance can be obtained. It is speculated that the reason why excellent solvent resistance can be obtained by using a fluorine-containing curable compound is as follows.
  • a fluorine-containing curable compound has a low surface free energy, for example, in a coating film formed by applying a composition on a support such as a substrate, the fluorine-containing compound is present in the vicinity of the coating film surface opposite to the support
  • the curable compound is likely to be unevenly distributed.
  • a region having a large proportion of the cured product of the fluorine-containing curable compound is formed on the surface far from the substrate. . Due to the presence of such a region, even if the film is immersed in a solvent, the near infrared absorbing dye is unlikely to leak from the film surface, and excellent solvent resistance can be obtained.
  • a (meth) acryloyloxy group is preferable.
  • the fluorine-containing curable compound preferably has at least one selected from the group consisting of a fluorine atom-substituted alkylene group, a fluorine atom-substituted alkyl group, and a fluorine atom-substituted aryl group.
  • the fluorine atom-substituted alkylene group is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the fluorine atom-substituted alkyl group is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the carbon number in the fluorine atom-substituted alkylene group and the fluorine atom-substituted alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. preferable.
  • the aryl group substituted with a fluorine atom is preferably such that the aryl group is directly substituted with a fluorine atom or substituted with a trifluoromethyl group.
  • the fluorine atom-substituted alkylene group, the fluorine atom-substituted alkyl group, and the fluorine atom-substituted aryl group may further have a substituent other than a fluorine atom.
  • paragraphs 0266 to 0272 of JP-A-2011-100089 can be referred to, and the contents thereof are incorporated in the present specification.
  • the fluorine-containing curable compound is preferably a compound containing a fluoroether group and a curable group.
  • group X group represented by Formula (X)
  • the fluoroether group is preferably a perfluoroalkylene ether group.
  • the perfluoroalkylene ether groups which means that L A in formula (X) is a perfluoroalkylene group.
  • the perfluoroalkylene group means a group in which all hydrogen atoms in the alkylene group are substituted with a fluorine atom.
  • L A represents an alkylene group substituted by a fluorine atom.
  • the carbon number of the fluorine atom-substituted alkylene group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the fluorine atom-substituted alkylene group may be linear or branched.
  • n represents an integer of 1 or more, preferably 1 to 50, and more preferably 1 to 20. When n is 2 or more, a plurality of - (L A -O) - L A medium may be the same or different.
  • the fluorine-containing curable compound may be a monomer or a polymer, but is preferably a polymer.
  • the polymer is preferably a polymer having a repeating unit having a fluoroether group and a repeating unit having a curable group.
  • the polymer is preferably a polymer having a repeating unit represented by the following formula (B1), at least one of a repeating unit represented by the following formula (B2) and a repeating unit represented by the formula (B3), It is more preferable that it is a polymer which has a repeating unit represented by a following formula (B1), and a repeating unit represented by a following formula (B3).
  • R 1 to R 11 each independently represent a hydrogen atom, an alkyl group or a halogen atom.
  • L 1 to L 4 each independently represent a single bond or a divalent linking group.
  • X 1 represents a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group
  • X 2 represents a fluorine atom-substituted alkyl group or a fluorine atom-substituted aryl group
  • X 3 represents a group of formula (X) Represents a group represented by
  • R 1 to R 11 are preferably each independently a hydrogen atom or an alkyl group.
  • R 1 to R 11 represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable.
  • R 1 to R 11 represent a halogen atom, a fluorine atom is preferred.
  • L 1 to L 4 represent a divalent linking group
  • an alkylene group which may be substituted by a halogen atom, or a halogen atom is substituted which may be an arylene group, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, - SO 2 NR 12 -, - O -, - S -, - SO 2 -, or, of A combination is mentioned.
  • the above R 12 represents a hydrogen atom or a methyl group.
  • the content of the repeating unit represented by the above formula (B1) is preferably 30 to 95 mol%, more preferably 45 to 90 mol%, based on all repeating units in the fluorine-containing curable compound. More preferable.
  • the total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) is 5 to 70 mol% with respect to all the repeating units in the fluorine-containing curable compound. Is preferable, and 10 to 60 mol% is more preferable.
  • content of the repeating unit represented by Formula (B2) is 0 mol%.
  • the content of the repeating unit represented by the formula (B3) is preferably in the above range.
  • the fluorine-containing curable compound may have another repeating unit other than the repeating units represented by the above formulas (B1) to (B3).
  • the content of the other repeating units is preferably 10 mol% or less, and more preferably 1 mol% or less, based on all the repeating units in the fluorine-containing curable compound.
  • the weight average molecular weight is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000.
  • the degree of dispersion is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.
  • the fluorine-containing curable compound for example, Megafuck RS-72-K, Megafuck RS-75, Megafuck RS-76-E, Megafuck RS-76-NS, Megafuck RS manufactured by DIC Corporation. -77 mag can be used.
  • the fluorine-containing curable compound compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965 and compounds described in paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can be used. It can also be used.
  • a polymer having a repeating unit represented by (B1-1) and a repeating unit represented by formula (B3-1) can also be used as the fluorine-containing curable compound.
  • X represents a fluoromethylene group or a fluoroethylene group
  • r represents the number of repeating units.
  • nonionic surfactants glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronics 304, 701, 704, 901, 904, 150R1 (BA).
  • BA nonionic surfactants
  • the content of the surfactant is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% to 3.0% by mass, with respect to the total solid content of the curable composition of the present invention.
  • the surfactant may be only one type, or two or more types. In the case of two or more types, the total amount is preferably in the above range.
  • the curable composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds and the like can be used. The details of these can be referred to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, the contents of which are incorporated herein.
  • Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
  • the benzotriazole compound MYUA series (Chemical Industry Daily, February 1, 2016) made by Miyoshi Yushi may be used.
  • the content of the UV 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 ultraviolet absorber may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the curable composition of the present invention may contain, if necessary, a sensitizer, a curing accelerator, a filler, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter and other auxiliary agents (eg, conductive particles, fillers) Defoamer, flame retardant, leveling agent, peeling accelerator, antioxidant, latent antioxidant, perfume, surface tension regulator, chain transfer agent, etc.).
  • auxiliary agents eg, conductive particles, fillers
  • Defoamer e.g, flame retardant, leveling agent, peeling accelerator, antioxidant, latent antioxidant, perfume, surface tension regulator, chain transfer agent, etc.
  • a phenol compound, a phosphorous acid ester compound, a thioether compound etc. are mentioned as antioxidant.
  • a phenolic compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. You may mix and use these 2 or more types.
  • the phenolic compound any phenolic compound known as a phenolic antioxidant can be used.
  • a preferable phenol compound a hindered phenol compound is mentioned. In particular, compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group are preferred.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule.
  • a phosphorus antioxidant can also be used conveniently for antioxidant.
  • a phosphorus antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl And at least one compound selected from the group consisting of oxy] ethyl] amine and ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl).
  • the polyfunctional hindered amine antioxidant described in International Publication WO17 / 006600 can also be used as an antioxidant.
  • the content of the antioxidant is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass, with respect to the total solid content of the curable composition.
  • One type of antioxidant may be sufficient, and 2 or more types may be sufficient as it.
  • a latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C., or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • the compound is a compound which functions as an antioxidant by eliminating the protective group.
  • the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219.
  • Examples of commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like.
  • the viscosity (23 ° C.) of the curable composition of the present invention is preferably, for example, 1 to 100 mPa ⁇ s when a film is formed by coating.
  • the lower limit is preferably 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, still more preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • a storage container of the curable composition of this invention A well-known storage container can be used.
  • a container for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use.
  • a container for example, the container described in JP-A-2015-123351 can be mentioned.
  • the application of the curable composition of the present invention is not particularly limited.
  • it can be preferably used for forming a near infrared cut filter or the like.
  • the curable composition of this invention WHEREIN:
  • transmit only the near infrared rays more than a specific wavelength can also be formed by containing the color material which shields visible light.
  • the curable composition of the present invention can be prepared by mixing the above-mentioned components. In the preparation of the curable composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare a curable composition, and if necessary, two or more solutions containing each component as appropriate The dispersion may be prepared in advance and mixed at the time of use (at the time of application) to prepare a curable composition.
  • the curable composition of the present invention contains particles such as pigments
  • mechanical force used to disperse the particles includes compression, squeezing, impact, shearing, cavitation and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
  • a bead having a small diameter, treatment under conditions in which the pulverizing efficiency is enhanced by increasing the packing ratio of beads, or the like.
  • the process of dispersing particles and the dispersing machine are the dispersion technology and industrial application centering on "Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005" and "suspension (solid / liquid dispersion system)" The process and the dispersing machine described in Paragraph No.
  • JP-A-2015-157893 published on October 10, 1978, can be preferably used.
  • the particles may be subjected to a refinement process in a salt milling step.
  • the materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
  • a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP)
  • Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
  • the pore diameter of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is in the above range, fine foreign particles can be reliably removed. It is also preferable to use a fibrous filter medium.
  • the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, filter cartridges of SBP type series (SBP 008 and the like), TPR type series (TPR 002, TPR 005 and the like), and SHPX type series (SHPX 003 and the like) manufactured by Loki Techno, Inc. can be mentioned.
  • filters different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above.
  • the pore size here can refer to the nominal value of the filter manufacturer.
  • the second filter can be made of the same material as the first filter.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.
  • the cured film of the present invention is obtained from the above-mentioned curable composition of the present invention.
  • the cured film of the present invention can be preferably used as a near infrared cut filter. Moreover, it can also be used as a heat ray blocking filter or an infrared rays transmission filter.
  • the cured film of the present invention may be used by being laminated on a support, or may be used by peeling it from the support.
  • the cured film of the present invention may have a pattern or may be a film having no pattern (flat film).
  • the thickness of the cured film of the present invention can be appropriately adjusted according to the purpose. 20 micrometers or less are preferable, as for the thickness of a cured film, 10 micrometers or less are more preferable, and 5 micrometers or less are more preferable.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
  • the cured film of the present invention preferably has a maximum absorption wavelength in the range of 700 to 1300 nm, more preferably a maximum absorption wavelength in the range of 700 to 1000 nm, and a maximum absorption wavelength in the range of 720 to 980 nm. It is more preferable that the light absorption wavelength is in the range of 740 to 960 nm.
  • the cured film of the present invention When the cured film of the present invention is used as a near infrared cut filter, the cured film of the present invention preferably satisfies at least one of the following (1) to (4), and (1) to (4) It is further preferred that all the conditions of (1)
  • the transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.
  • the transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
  • the cured film of the present invention can also be used in combination with a color filter containing a chromatic coloring agent.
  • a color filter can be manufactured using a coloring composition containing a chromatic coloring agent.
  • the chromatic coloring agents include the chromatic coloring agents mentioned as those which may be contained in the curable composition of the present invention.
  • the cured film of the present invention may contain a chromatic coloring agent to provide a near infrared cut filter and a filter having a function as a color filter.
  • the color filter is arrange
  • the cured film of the present invention and a color filter can be laminated and used as a laminate.
  • the cured film of the present invention and the color filter may or may not be adjacent in the thickness direction.
  • the cured film of the present invention may be formed on a support other than the support on which the color filter is formed.
  • another member for example, a microlens, a planarizing layer, etc. constituting the solid-state imaging device may be interposed.
  • the near-infrared cut filter means a filter that transmits light in the visible region (visible light) and blocks at least part of light in the near-infrared region (near infrared).
  • the near infrared cut filter may transmit all light of wavelengths in the visible region, and among light of wavelengths in the visible region, transmits light of a specific wavelength region and blocks light of a specific wavelength region
  • the color filter means a filter that transmits light in a specific wavelength range and blocks light in a specific wavelength range, out of light of wavelengths in the visible range.
  • the infrared transmission filter means a filter that shields visible light and transmits at least a part of near infrared light.
  • the cured film of the present invention is preferably used by being laminated on a glass containing copper since it is excellent in adhesion to a glass containing copper and water-resistant adhesion.
  • copper-containing glass include copper-containing phosphate glass and copper-containing fluorophosphate glass.
  • the content of copper in the glass containing copper is preferably 0.1 to 20% by mass, more preferably 0.3 to 17% by mass, and 0.5 to 15% by mass Is more preferred.
  • the copper-containing glass preferably has a maximum absorption wavelength in the wavelength range of 700 to 1100 nm.
  • the lower limit is preferably 800 nm or more, and more preferably 900 nm or more.
  • the upper limit is preferably 1050 nm or less, more preferably 1000 nm or less.
  • a commercial product can also be used for the glass containing copper.
  • Commercially available products of copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.) and the like.
  • the cured film of the present invention can be used for various devices such as solid-state imaging devices such as CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.
  • solid-state imaging devices such as CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.
  • CCDs charge coupled devices
  • CMOSs complementary metal oxide semiconductors
  • infrared sensors and image display devices.
  • the method for producing a cured film of the present invention includes the steps of applying the curable composition of the present invention described above to form a curable composition layer, and heat curing the curable composition layer.
  • the curable composition is preferably applied on a support.
  • the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a glass substrate containing copper.
  • An organic film, an inorganic film, etc. may be formed in these base materials.
  • the material of the organic film include the above-mentioned resins.
  • the base material comprised with resin mentioned above can also be used as a support body.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support.
  • a black matrix may be formed on the support to separate each pixel.
  • the support may be provided with a subbing layer, if necessary, for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate.
  • a glass substrate containing copper it is preferable to use as a support. Conventionally, it has been difficult to form a cured film having good adhesion to a glass substrate containing copper, but the cured film of the present invention is also adhesive to a glass substrate containing copper. The effect of the present invention is more remarkable because the water resistance is excellent and the adhesion to water is also excellent.
  • a method of applying the curable composition to a support known methods can be used. For example, dropping method (drop casting); slit coating method; spraying method; roll coating method; spin coating method (spin coating); cast coating method; slit and spin method; pre-wet method (for example, JP 2009-145395A) Methods described in the publication); Ink jet (for example, on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • the application method in the inkjet is not particularly limited, and for example, the method (in particular, page 115-) disclosed in "Spread and usable inkjet-unlimited possibilities in patents-published in February 2005, resident Betechno Research" Methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. It can be mentioned.
  • the application method of the curable composition the descriptions of International Publication WO 2017/030174 and International Publication WO 2017/018419 can be referred to, and the contents thereof are incorporated herein.
  • the curable composition applied to the support may be dried (prebaked).
  • the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less.
  • the lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more.
  • the pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven or the like.
  • the heating temperature is preferably, for example, 100 to 240.degree. From the viewpoint of film curing, 180 to 230 ° C. is more preferable.
  • the heating time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes.
  • the heat curing treatment can be performed with a hot plate, an oven or the like.
  • the method for producing a cured film of the present invention may further include the step of forming a pattern.
  • the pattern formation method include a pattern formation method using a photolithography method and a pattern formation method using a dry etching method.
  • a pattern formation method using a photolithography method
  • a pattern formation method using a dry etching method When forming a pattern by the photolithographic method, it is preferable to heat-harden a curable composition layer, after forming a pattern.
  • the dry etching method it is preferable to form a pattern, after heat-hardening a curable composition layer.
  • the process of forming a pattern will be described in detail.
  • the pattern formation method in the photolithography method comprises a step of exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern (exposure step), and a curable composition of the unexposed area It is preferable to include the step of developing by removing the layer to form a pattern (developing step). If necessary, a step (post-baking step) may be provided to bake the developed pattern.
  • the curable composition layer is cured by heating to form a cured layer, and then a patterned photoresist layer is formed on the cured layer, and then a patterned photo is formed. It can carry out by methods, such as dry-etching using etching gas with respect to a hardened
  • dry-etching using etching gas with respect to a hardened
  • the description in paragraphs “0010” to “0067” of JP 2013-064993 can be referred to, and the contents thereof are incorporated in the present specification.
  • the near infrared cut filter of the present invention includes the cured film of the present invention.
  • the near infrared cut filter of the present invention preferably has the cured film of the present invention on a support.
  • the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, a glass substrate containing copper, etc., and a glass containing copper Substrates are preferred.
  • the near infrared cut filter of the present invention may further have a dielectric multilayer film, an ultraviolet absorbing layer, etc. in addition to the cured film of the present invention.
  • the near infrared cut filter further includes the dielectric multilayer film, it is easy to obtain a near infrared cut filter having a wide viewing angle and excellent infrared shielding properties.
  • the near infrared cut filter further has an ultraviolet absorbing layer, whereby the near infrared cut filter having excellent ultraviolet shielding properties can be obtained.
  • the ultraviolet absorbing layer for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO 2015/099060 can be referred to, the contents of which are incorporated herein.
  • the dielectric multilayer film the description in paragraphs “0255 to 0259” of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated in the present specification.
  • the near-infrared cut filter of the present invention can be used for various devices such as solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.
  • solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor)
  • CMOS complementary metal oxide semiconductor
  • infrared sensors and image display devices.
  • the solid-state imaging device of the present invention has the cured film of the present invention described above.
  • the configuration of the solid-state imaging device of the present invention is a configuration having the cured film of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. For example, the following configuration may be mentioned.
  • a light shield comprising a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon and the like on the support, light shielding made of tungsten or the like in which only the light receiving portion of the photodiode and the transfer electrodes are opened.
  • a device protection film made of silicon nitride or the like which has a film and is formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode and has the cured film of the present invention on the device protection film It is. Furthermore, on the device protective film, a configuration having a condensing means (for example, a micro lens etc.
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a grid shape by partition walls.
  • the partition walls in this case preferably have a lower refractive index than each pixel.
  • the image display apparatus of the present invention includes the cured film of the present invention.
  • the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
  • organic EL organic electroluminescence
  • the image display device for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)", “Display device (authored by Ibuki Jun, industrial book, Ltd.) Etc.).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”.
  • the image display device may have a white organic EL element. It is preferable that it is a tandem structure as a white organic EL element.
  • JP-A-2003-45676 supervised by Akiyoshi Mikami, "The forefront of organic EL technology development-High luminance, high accuracy, long life, know-how collection", about the tandem structure of organic EL elements, Technical Information Association, It is described on pages 326-328, 2008, etc.
  • the spectrum of the white light emitted by the organic EL element is preferably one having strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm) and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.
  • the infrared sensor of the present invention includes the cured film of the present invention described above.
  • the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
  • an embodiment of the infrared sensor of the present invention will be described using the drawings.
  • reference numeral 110 denotes a solid-state imaging device.
  • An imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. Further, on the near infrared cut filter 111, a color filter 112 is laminated. A microlens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.
  • the near infrared cut filter 111 can be formed using the curable composition of the present invention.
  • the spectral characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) to be used.
  • the color filter 112 is a color filter in which a pixel for transmitting and absorbing light of a specific wavelength in the visible region is formed, and is not particularly limited, and a conventionally known color filter for forming a pixel 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 description in paragraph Nos. 0214 to 0263 of JP-A-2014-043556 can be referred to, the contents of which are incorporated herein.
  • the characteristic of the infrared transmission filter 114 is selected according to the emission wavelength of the infrared LED to be used.
  • a near infrared cut filter (another near infrared cut filter) different from the near infrared cut filter 111 may be further disposed on the planarization layer 116.
  • Other near infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. The details of these may be mentioned above.
  • a dual band pass filter may be used as another near infrared cut filter.
  • the positions of the near infrared cut filter 111 and the color filter 112 may be interchanged.
  • another layer may be disposed between the solid-state imaging device 110 and the near-infrared cut filter 111 and / or between the solid-state imaging device 110 and the infrared-transmissive filter 114.
  • the organic substance layer etc. which were formed using the composition containing a polymeric compound, resin, and a photoinitiator are mentioned.
  • a planarization layer may be formed on the color filter 112.
  • A1 to A18, A20 to A22 compounds of the following structures.
  • (resin) -Resin 1 30 mass% solution of cyclopentanone of resin (The weight average molecular weight 41,400, the numerical value attached to the repeating unit is the number of moles) of the following structure.
  • Resin 2 A 30% by mass solution of cyclopentanone in a resin of the following structure (weight-average molecular weight: 33,100, numerical value added to repeating unit is number of moles).
  • Organic solvent 1 Cyclopentanone
  • Organic solvent 2 3-methoxy-N, N-dimethylpropanamide
  • Organic solvent 3 3-butoxy-N, N-dimethylpropanamide
  • Radically polymerizable compound 1 a mixture of the following compounds (mixture in which the molar ratio of the left compound and the right compound is 7: 3)
  • Radically polymerizable compound 2 mixture of the following compounds (height ratio by high performance liquid chromatography: 46.15: 49.39 :: 4.46)
  • Radically polymerizable compound 3 the following compounds
  • Radically polymerizable compound 4 the following compound (Initiator)
  • Initiator 3 Perbutyl O (manufactured by NOF
  • Silane coupling agent ureidopropyltrimethoxysilane
  • X is, -CF 2 -CF 2 -, - CF 2 -, and -CH 2 -CF 2 - represents either, r is representative of the number of repeating units.
  • Polymerization inhibitor 1 p-methoxyphenol
  • Dispersion liquid 1 The raw material of the following composition is dispersed for 2 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm diameter, and dispersed for 2 hours Liquid 1 was prepared.
  • Dispersant (The resin of the following structure, weight average molecular weight 22, 900, the numerical value attached to the repeating unit of the main chain is the number of moles, and the numerical value written together with the repeating unit of the side chain indicates the repeating number of the repeating unit ) ... 7.2 parts by mass ⁇ Cyclohexanone ... 77. 77 parts by mass
  • Dispersion liquid 2 C. I. Pigment Black 32 60 parts by mass, C.I. I. Pigment Blue 15: 6, 20 parts by mass, C.I. I. Mix 20 parts by mass of Pigment Yellow 139, 80 parts by mass of Solsparse 76500 (manufactured by Nippon Lubrizol Co., Ltd., solid content concentration 50% by mass), and 700 parts by mass of propylene glycol monomethyl ether acetate and mix them with a paint shaker 8 Dispersion was carried out for a time to obtain dispersion liquid 2.
  • Each curable composition is formed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., size 50 mm ⁇ 50 mm, thickness 0.05 mm, copper-containing glass substrate) Then, spin-coating is applied with a Mikasa coater so that the film thickness after film formation is 2.5 ⁇ m, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure Manufactured. The fluorophosphate glass substrate on which a cured film was formed was immersed in water at 95 ° C.
  • the number of peeled squares is 0 4.
  • the number of peeled squares is 1 to 5.
  • 3 The number of peeled squares is 6 to 10.
  • 2 The number of peeled squares is 11 to 30 pieces 1: The number of peeled squares is 31 or more
  • Each curable composition is formed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., size 50 mm ⁇ 50 mm, thickness 0.05 mm, copper-containing glass substrate) Then, spin-coating is applied with a Mikasa coater so that the film thickness after film formation is 2.5 ⁇ m, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure Manufactured. After the fluorophosphate glass substrate on which the cured film is formed is immersed in acetone at 23 ° C.
  • an acceleration voltage of 2.0 kV is used using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corp.)
  • the cross section of the film was observed at an observation magnification of 50000 times, lengths of three arbitrary hole shapes in the long axis direction were measured, and the average value was calculated as the aggregation size.
  • Example 1 As shown in the above table, all of the examples had good water-resistant adhesion and were able to produce a cured film having a small aggregation size.
  • Example 1 even when the initiator of Example 17 described in JP-A-2014-521772 was used instead of the initiator 2, the same effect as that of Example 1 was obtained.
  • 110 solid-state imaging device
  • 111 near infrared cut filter
  • 112 color filter
  • 114 infrared transmission filter
  • 115 microlens
  • 116 flattening layer

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Abstract

Provided is a curable composition which is capable of producing a cured film that exhibits good water-resistant adhesion, while being suppressed in the generation of aggregates derived from a near-infrared absorbing dye. Also provided are: a cured film; a method for producing a cured film; a near-infrared blocking filter; a solid-state imaging element; an image display device; and an infrared sensor. This curable composition contains a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound and a thermal radical polymerization initiator.

Description

硬化性組成物、硬化膜、硬化膜の製造方法、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサCurable composition, cured film, method of producing cured film, near infrared cut filter, solid-state imaging device, image display device, and infrared sensor
　本発明は、硬化性組成物、硬化膜、硬化膜の製造方法、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサに関する。 The present invention relates to a curable composition, a cured film, a method for producing a cured film, a near infrared cut filter, a solid-state imaging device, an image display device, and an infrared sensor.
　ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などには、カラー画像の固体撮像素子である、ＣＣＤ（電荷結合素子）や、ＣＭＯＳ（相補型金属酸化膜半導体）が用いられている。これら固体撮像素子は、その受光部において赤外線に感度を有するシリコンフォトダイオードを使用している。このために、近赤外線カットフィルタを使用して視感度補正を行うことがある。 CCDs (charge coupled devices) and CMOS (complementary metal oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state imaging devices use silicon photodiodes sensitive to infrared light in their light receiving portions. For this reason, a near infrared cut filter may be used to perform luminosity correction.
　近赤外線カットフィルタは、例えば、近赤外線吸収色素を含む硬化性組成物を用いて製造されている（特許文献１参照）。 The near infrared cut filter is manufactured, for example, using a curable composition containing a near infrared absorbing dye (see Patent Document 1).
国際公開ＷＯ２０１４／１９９９３７号公報International Publication WO2014 / 199937
　近年、近赤外線カットフィルタに要求される特性の一つとして、支持体に対する耐水密着性の向上が望まれている。 In recent years, improvement of water-resistant adhesion to a support is desired as one of the characteristics required for near-infrared cut filters.
　また、本発明者の検討によれば、近赤外線吸収色素を含む硬化性組成物を用いて硬化膜を製造した場合、製膜時に近赤外線吸収色素が凝集しやすい傾向にあることが分かった。特に、製膜時に熱が加えられると、近赤外線吸収色素が凝集しやすい傾向にあった。膜中における、近赤外線吸収色素に由来する凝集物のサイズが大きくなると、分光特性にばらつきが生じたり、膜面の平滑性が低下することがある。更には、凝集物のサイズが大きくなると、膜から凝集物が剥落し易くなり、凝集物が存在していた箇所に、凝集物のサイズの孔が生じる恐れがある。 Moreover, according to examination of the present inventor, when a cured film was manufactured using a curable composition containing a near-infrared absorbing dye, it was found that the near-infrared absorbing dye tends to aggregate at the time of film formation. In particular, when heat is applied at the time of film formation, the near infrared absorbing dye tends to aggregate. When the size of the aggregate derived from the near-infrared absorbing dye in the film is increased, the spectral characteristics may vary or the smoothness of the film surface may be reduced. Furthermore, as the size of the aggregate increases, it is likely that the aggregate will fall off from the membrane, and pores of the size of the aggregate may be generated at the location where the aggregate was present.
　よって、本発明の目的は、耐水密着性が良好で、近赤外線吸収色素に由来する凝集物の発生が抑制された硬化膜を製造できる硬化性組成物を提供することにある。また、本発明は、硬化膜、硬化膜の製造方法、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサを提供することにある。 Therefore, an object of the present invention is to provide a curable composition capable of producing a cured film having good water-resistant adhesion and suppressing the generation of aggregates derived from a near-infrared absorbing dye. Another object of the present invention is to provide a cured film, a method for producing the cured film, a near infrared cut filter, a solid-state imaging device, an image display device, and an infrared sensor.
　本発明者の検討によれば、近赤外線吸収色素と、環状エーテル基を有する化合物と、ラジカル重合性化合物と、熱ラジカル重合開始剤とを含む硬化性組成物を用いて得られる硬化膜は、耐水密着性が良好で、近赤外線吸収色素に由来する凝集物が少ないことを見出し本発明を完成するに至った。よって、本発明は以下を提供する。
　＜１＞　近赤外線吸収色素と、環状エーテル基を有する化合物と、ラジカル重合性化合物と、熱ラジカル重合開始剤とを含む硬化性組成物。
　＜２＞　環状エーテル基は、エポキシ基である、＜１＞に記載の硬化性組成物。
　＜３＞　環状エーテル基を有する化合物は、芳香族環を含む化合物である、＜１＞または＜２＞に記載の硬化性組成物。
　＜４＞　環状エーテル基を有する化合物の１００質量部に対して、ラジカル重合性化合物を１～１００質量部含む、＜１＞～＜３＞のいずれか１つに記載の硬化性組成物。
　＜５＞　ラジカル重合性化合物の１００質量部に対して、熱ラジカル重合開始剤を０．０５～２００質量部含む、＜１＞～＜４＞のいずれか１つに記載の硬化性組成物。
　＜６＞　熱ラジカル重合開始剤は、ピナコール化合物およびα－ヒドロキシアセトフェノン化合物から選ばれる少なくとも１種である、＜１＞～＜５＞のいずれか１つに記載の硬化性組成物。
　＜７＞　近赤外線吸収色素は、単環または縮合環の芳香族環を含むπ共役平面を有する化合物である、＜１＞～＜６＞のいずれか１つに記載の硬化性組成物。
　＜８＞　近赤外線吸収色素は、ピロロピロール化合物、スクアリリウム化合物およびシアニン化合物から選ばれる少なくとも１種である、＜１＞～＜６＞のいずれか１つに記載の硬化性組成物。
　＜９＞　＜１＞～＜８＞のいずれか１つに記載の硬化性組成物から得られる硬化膜。
　＜１０＞　支持体上に＜１＞～＜８＞のいずれか１つに記載の硬化性組成物を適用して硬化性組成物層を形成する工程と、
　硬化性組成物層を加熱硬化する工程と、を含む硬化膜の製造方法。
　＜１１＞　支持体が銅を含有するガラス基材である、＜１０＞に記載の硬化膜の製造方法。
　＜１２＞　＜９＞に記載の硬化膜を有する近赤外線カットフィルタ。
　＜１３＞　銅を含有するガラス基材の表面に上記硬化膜を有する、＜１２＞に記載の近赤外線カットフィルタ。
　＜１４＞　＜９＞に記載の硬化膜を有する固体撮像素子。
　＜１５＞　＜９＞に記載の硬化膜を有する画像表示装置。
　＜１６＞　＜９＞に記載の硬化膜を有する赤外線センサ。 According to the study of the inventor of the present invention, a cured film obtained using a curable composition containing a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator is It has been found that the water adhesion is good and the amount of aggregates derived from the near infrared absorbing dye is small, and the present invention has been completed. Accordingly, the present invention provides the following.
<1> A curable composition comprising a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
The curable composition as described in <1> whose <2> cyclic ether group is an epoxy group.
The curable composition as described in <1> or <2> which is a compound which has a <3> cyclic ether group is a compound containing an aromatic ring.
The curable composition as described in any one of <1>-<3> which contains 1-100 mass parts of radically polymerizable compounds with respect to 100 mass parts of compounds which have a <4> cyclic ether group.
The curable composition according to any one of <1> to <4>, containing 0.05 to 200 parts by mass of a thermal radical polymerization initiator with respect to 100 parts by mass of a <5> radically polymerizable compound.
<6> The curable composition according to any one of <1> to <5>, wherein the thermal radical polymerization initiator is at least one selected from a pinacol compound and an α-hydroxyacetophenone compound.
<7> The curable composition according to any one of <1> to <6>, wherein the near-infrared absorbing dye is a compound having a π-conjugated plane including an aromatic ring of a single ring or a condensed ring.
<8> The curable composition according to any one of <1> to <6>, wherein the near infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, squarylium compounds and cyanine compounds.
<9> A cured film obtained from the curable composition according to any one of <1> to <8>.
<10> A step of applying a curable composition according to any one of <1> to <8> onto a support to form a curable composition layer,
Heat curing the curable composition layer, and a method of producing a cured film.
The manufacturing method of the cured film as described in <10> whose <11> support body is a glass base material containing copper.
The near-infrared cut off filter which has a cured film as described in <12><9>.
The near-infrared cut off filter as described in <12> which has the said cured film on the surface of the glass base material containing <13> copper.
The solid-state image sensor which has a cured film as described in <14><9>.
The image display apparatus which has a cured film as described in <15><9>.
The infrared sensor which has a cured film as described in <16><9>.
　本発明によれば、耐水密着性が良好で、近赤外線吸収色素に由来する凝集物の発生が抑制された硬化膜を製造できる硬化性組成物を提供することができる。また、本発明は、硬化膜、硬化膜の製造方法、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサを提供することができる。 According to the present invention, it is possible to provide a curable composition capable of producing a cured film which is excellent in water-resistant adhesion and in which the generation of an aggregate derived from a near infrared absorbing dye is suppressed. Moreover, this invention can provide a cured film, the manufacturing method of a cured film, a near-infrared cut off filter, a solid-state image sensor, an image display apparatus, and an infrared sensor.
赤外線センサの一実施形態を示す概略図である。It is a schematic diagram showing one embodiment of an infrared sensor.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」を用いて表される数値範囲は「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において、「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定でのポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ（内径）×１５．０ｃｍ）を用い、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ（Ｎ－メチルピロリジノン）溶液を用いることによって求めることができる。
　本明細書において、近赤外線とは、波長７００～２，５００ｎｍの光をいう。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において、「工程」との語は、独立した工程を表すだけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 Hereinafter, the contents of the present invention will be described in detail.
In the present specification, a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
In the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Moreover, as light used for exposure, active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like can be mentioned.
In the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acryl” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Allyl "represents both or any of allyl and methallyl, and" (meth) acryloyl "represents both or any of acryloyl and methacryloyl.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement. In the present specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.), and TSKgel Super AWM-H (manufactured by Tosoh Corp.), 6 as a column. It can be determined by using a solution of 10 mmol / L lithium bromide NMP (N-methyl pyrrolidinone) as an eluent, using a .0 mm ID (inner diameter) x 15.0 cm).
In the present specification, near-infrared light refers to light having a wavelength of 700 to 2,500 nm.
As used herein, total solids refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" not only refers to an independent process, but also to the term "process" if the intended function of the process is achieved even if it can not be distinguished clearly from other processes. include.
＜硬化性組成物＞
　本発明の硬化性組成物は、近赤外線吸収色素と、環状エーテル基を有する化合物と、ラジカル重合性化合物と、熱ラジカル重合開始剤とを含むことを特徴とする。
　本発明の硬化性組成物によれば、耐水密着性が良好で、近赤外線吸収色素に由来する凝集物が少ない硬化膜を製造することができる。
　このような効果が得られる理由としては以下によるものであると推測される。すなわち、本発明の硬化性組成物は、ラジカル重合性化合物と熱ラジカル重合開始剤とを含むので、このような硬化性組成物を加熱することで、熱ラジカル重合開始剤から発生したラジカルによってラジカル重合性化合物の重合反応が速やかに進行し、膜を速やかに硬化させることができる。このため、近赤外線吸収色素が膜中の架橋ネットワークなどに速やかに取りこまれると推測される。また、環状エーテル基を有する化合物は、ラジカル重合性化合物に比べて硬化速度が遅いが、環状エーテル基を有する化合物は、近赤外線吸収色素と相互作用し易いと考えられ、近赤外線吸収色素の近傍で環状エーテル基を有する化合物の硬化が進行すると推測される。このため、本発明の硬化性組成物は、加熱時における近赤外線吸収色素の凝集を効果的に抑制でき、近赤外線吸収色素に由来する凝集物が少ない硬化膜を製造することができたと推測される。
　また、環状エーテル基を有する化合物の環状エーテル基は、支持体上の水酸基などと反応し易く、これにより支持体に対して優れた密着性が得られると推測される。また、環状エーテル基を有する化合物は硬化収縮し難い化合物であるため、硬化性組成物に環状エーテル基を有する化合物を含有させたことにより、硬化収縮し難い硬化膜を形成することができたと推測される。また、ラジカル重合性化合物により架橋密度の高い硬化膜を形成することができるので、膜中への水の侵入を効果的に抑制することもできる。このように、本発明によれば、硬化収縮を抑制しつつ、支持体に対する密着性が高い硬化膜を支持体上に形成することができるので、このような硬化膜を水に浸漬しても、支持体と硬化膜との界面に水が浸入することを効果的に抑制でき、そのため、優れた耐水密着性が得られたと推測される。以下、本発明の硬化性組成物の各成分について説明する。 <Curable composition>
The curable composition of the present invention is characterized by containing a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
According to the curable composition of the present invention, it is possible to produce a cured film having good adhesion to water and having few aggregates derived from the near infrared absorbing dye.
The reason why such an effect can be obtained is presumed to be as follows. That is, since the curable composition of the present invention contains a radically polymerizable compound and a thermal radical polymerization initiator, by heating such a curable composition, radicals are generated by radicals generated from the thermal radical polymerization initiator. The polymerization reaction of the polymerizable compound proceeds rapidly, and the film can be rapidly cured. Therefore, it is presumed that the near infrared absorbing dye is rapidly incorporated into the crosslinked network in the membrane. The compound having a cyclic ether group cures slower than the radically polymerizable compound, but the compound having a cyclic ether group is considered to easily interact with the near infrared absorbing dye, and in the vicinity of the near infrared absorbing dye It is inferred that curing of the compound having a cyclic ether group proceeds. For this reason, it is speculated that the curable composition of the present invention was able to effectively suppress the aggregation of the near infrared absorbing dye at the time of heating, and was able to produce a cured film with few aggregates derived from the near infrared absorbing dye. Ru.
Further, it is presumed that the cyclic ether group of the compound having a cyclic ether group easily reacts with a hydroxyl group or the like on the support to thereby obtain excellent adhesion to the support. In addition, since the compound having a cyclic ether group is a compound that is hard to cure and shrink, it is presumed that a cured film that is hard to cure and shrink can be formed by including the compound having a cyclic ether group in the curable composition. Be done. In addition, since a cured film having a high crosslinking density can be formed by the radically polymerizable compound, it is possible to effectively suppress the entry of water into the film. As described above, according to the present invention, a cured film having high adhesion to the support can be formed on the support while suppressing curing shrinkage, so even if such a cured film is immersed in water Then, it is possible to effectively suppress the entry of water into the interface between the support and the cured film, and it is therefore presumed that excellent water-resistant adhesion is obtained. Hereinafter, each component of the curable composition of this invention is demonstrated.
＜＜近赤外線吸収色素＞＞
　本発明の硬化性組成物は、近赤外線吸収色素を含有する。近赤外線吸収色素は、顔料（近赤外線吸収顔料ともいう）であってもよく、染料（近赤外線吸収染料ともいう）であってもよい。また、近赤外線吸収染料と近赤外線吸収顔料とを併用することも好ましい。近赤外線吸収染料と近赤外線吸収顔料とを併用する場合、近赤外線吸収染料と近赤外線吸収顔料との質量比は、近赤外線吸収染料：近赤外線吸収顔料＝９９．９：０．１～０．１：９９．９であることが好ましく、９９．９：０．１～１０：９０であることがより好ましく、９９．９：０．１～２０：８０であることがさらに好ましい。 << Near Infrared Absorbing Dyes >>
The curable composition of the present invention contains a near infrared absorbing dye. The near infrared absorbing dye may be a pigment (also referred to as a near infrared absorbing pigment), or may be a dye (also referred to as a near infrared absorbing dye). It is also preferable to use a near infrared absorbing dye and a near infrared absorbing pigment in combination. When using a near-infrared absorbing dye and a near-infrared absorbing pigment in combination, the mass ratio of the near-infrared absorbing dye to the near-infrared absorbing pigment is as follows: near-infrared absorbing dye: near-infrared absorbing pigment = 99.9: 0.1-0. The ratio is preferably 1: 99.9, more preferably 99.9: 0.1 to 10:90, and still more preferably 99.9: 0.1 to 20:80.
　本発明において、近赤外線吸収染料は、２３℃のシクロペンタノン、シクロヘキサノン、および、ジプロピレングリコールモノメチルエーテルから選ばれる少なくとも１種の溶剤１００ｇに対する溶解度が、１ｇ以上であることが好ましく、２ｇ以上であることがより好ましく、５ｇ以上であることがさらに好ましい。また、近赤外線吸収顔料は、２３℃のシクロペンタノン、シクロヘキサノン、および、ジプロピレングリコールモノメチルエーテルのそれぞれの溶剤１００ｇに対する溶解度が、１ｇ未満であることが好ましく、０．１ｇ以下であることがより好ましく、０．０１ｇ以下であることがさらに好ましい。 In the present invention, the near infrared absorbing dye preferably has a solubility of 1 g or more, preferably 2 g or more, in 100 g of at least one solvent selected from cyclopentanone, cyclohexanone and dipropylene glycol monomethyl ether at 23 ° C. The content is more preferably 5 g or more. The near infrared absorbing pigment preferably has a solubility of 100 g of each of cyclopentanone, cyclohexanone and dipropylene glycol monomethyl ether at 23 ° C. of preferably less than 1 g, and more preferably 0.1 g or less Preferably, it is more preferably 0.01 g or less.
　近赤外線吸収色素は、単環または縮合環の芳香族環を含むπ共役平面を有する化合物であることが好ましい。近赤外線吸収色素のπ共役平面における芳香族環同士の相互作用により、硬化膜の製造時に近赤外線吸収色素のＪ会合体が形成されやすく、近赤外領域の分光特性に優れた硬化膜を製造できる。また、環状エーテル基を有する化合物と相互作用し易く、耐水密着性のより優れた硬化膜を形成し易い。特に環状エーテル基を有する化合物として芳香族環を有する化合物を用いた場合においては、環状エーテル基を有する化合物とより強固に相互作用し易く、耐水密着性を顕著に向上させることができる。 The near infrared absorbing dye is preferably a compound having a π conjugated plane including a single ring or a fused aromatic ring. Due to the interaction between aromatic rings in the π conjugated plane of the near infrared absorbing dye, the J aggregate of the near infrared absorbing dye is easily formed during the production of the cured film, and a cured film having excellent spectral characteristics in the near infrared region is produced. it can. Moreover, it is easy to interact with the compound which has cyclic ether group, and it is easy to form the cured film more excellent in water-resistant adhesiveness. In particular, when a compound having an aromatic ring is used as the compound having a cyclic ether group, the compound more easily interacts with the compound having a cyclic ether group, and the water-resistant adhesion can be remarkably improved.
　近赤外線吸収色素が有するπ共役平面を構成する水素以外の原子数は、６個以上であることが好ましく、１４個以上であることがより好ましく、２０個以上であることがさらに好ましく、２５個以上であることが一層好ましく、３０個以上であることが特に好ましい。上限は、例えば、８０個以下であることが好ましく、５０個以下であることがより好ましい。 The number of atoms other than hydrogen constituting the π conjugated plane possessed by the near infrared absorbing dye is preferably 6 or more, more preferably 14 or more, still more preferably 20 or more, and 25 It is more preferable that it is the above, and it is especially preferable that it is 30 or more. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
　近赤外線吸収色素が有するπ共役平面は、単環または縮合環の芳香族環を２個以上含むことが好ましく、３個以上含むことがより好ましく、４個以上含むことがさらに好ましく、５個以上含むことが特に好ましい。上限は、１００個以下が好ましく、５０個以下がより好ましく、３０個以下がさらに好ましい。前述の芳香族環としては、ベンゼン環、ナフタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、クアテリレン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ピリジン環、キノリン環、イソキノリン環、イミダゾール環、ベンゾイミダゾール環、ピラゾール環、チアゾール環、ベンゾチアゾール環、トリアゾール環、ベンゾトリアゾール環、オキサゾール環、ベンゾオキサゾール環、イミダゾリン環、ピラジン環、キノキサリン環、ピリミジン環、キナゾリン環、ピリダジン環、トリアジン環、ピロール環、インドール環、イソインドール環、カルバゾール環、および、これらの環を有する縮合環が挙げられる。 The π conjugated plane possessed by the near infrared absorbing dye preferably contains two or more, more preferably three or more, and still more preferably four or more, of a single ring or a fused ring aromatic ring. It is particularly preferred to include. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. The above-mentioned aromatic ring includes benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzoimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzooxazole ring, imidazoline ring, pyrazine And rings, quinoxaline rings, pyrimidine rings, quinazoline rings, pyridazine rings, triazine rings, pyrrole rings, indole rings, isoindole rings, carbazole rings, and fused rings having these rings.
　近赤外線吸収色素は、波長７００～１，３００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましく、波長７００～１，０００ｎｍの範囲に極大吸収波長を有する化合物であることがより好ましい。なお、本明細書において、「波長７００～１，３００ｎｍの範囲に極大吸収波長を有する」とは、近赤外線吸収色素の溶液中での吸収スペクトルにおいて、最大の吸光度を示す波長が、波長７００～１，３００ｎｍの範囲内に有ることを意味する。近赤外線吸収色素の溶液中での吸収スペクトルの測定に用いる測定溶媒としては、クロロホルム、メタノール、ジメチルスルホキシド、酢酸エチル、テトラヒドロフランが挙げられる。近赤外線吸収色素がクロロホルムに溶解する化合物である場合は、クロロホルムを測定溶媒として用いる。クロロホルムに溶解しない化合物である場合は、メタノールを用いる。また、クロロホルムおよびメタノールのいずれにも溶解しない場合はジメチルスルホキシドを用いる。 The near infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the range of 700 to 1,300 nm, and more preferably a compound having a maximum absorption wavelength in the range of 700 to 1,000 nm. In the present specification, “having a maximum absorption wavelength in the wavelength range of 700 to 1,300 nm” means that the wavelength showing the maximum absorbance in the absorption spectrum of the near-infrared absorbing dye in the solution is 700 to It means that it exists in the range of 1,300 nm. As a measurement solvent used for the measurement of the absorption spectrum in the solution of a near-infrared absorption pigment, chloroform, methanol, dimethyl sulfoxide, ethyl acetate, tetrahydrofuran are mentioned. When the near infrared absorbing dye is a compound that dissolves in chloroform, chloroform is used as a measurement solvent. If it is a compound which does not dissolve in chloroform, methanol is used. In addition, dimethyl sulfoxide is used when it does not dissolve in either chloroform or methanol.
　近赤外線吸収色素は、波長７００～１，０００ｎｍの範囲に極大吸収波長を有し、かつ、波長５００ｎｍにおける吸光度Ａ1と極大吸収波長における吸光度Ａ2との比率Ａ1／Ａ2が、０．０８以下であることが好ましく、０．０４以下であることがより好ましい。この態様によれば、可視透明性と赤外線遮蔽性に優れた硬化膜を製造しやすい。 Near infrared absorbing dye has an absorption maximum wavelength in a wavelength range of 700 ~ 1,000 nm, and the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength in the wavelength 500 nm, 0. It is preferably 08 or less, more preferably 0.04 or less. According to this aspect, it is easy to manufacture a cured film having excellent visible transparency and infrared shielding properties.
　本発明において、近赤外線吸収色素として、極大吸収波長の異なる少なくとも２種の化合物を用いることも好ましい。この態様によれば、得られる硬化膜の吸収スペクトルの波形が、１種類の近赤外線吸収色素を使用した場合に比べて広がり、幅広い波長範囲の近赤外線を遮蔽することができる。極大吸収波長の異なる少なくとも２種の化合物を用いる場合、波長７００～１，０００ｎｍの範囲に極大吸収波長を有する第１の近赤外線吸収色素と、第１の近赤外線吸収色素の極大吸収波長よりも短波長側であって、波長７００～１，０００ｎｍの範囲に極大吸収波長を有する第２の近赤外線吸収色素とを少なくとも含み、第１の近赤外線吸収色素の極大吸収波長と、第２の近赤外線吸収色素の極大吸収波長との差が１～１５０ｎｍであることが好ましい。 In the present invention, it is also preferable to use at least two kinds of compounds having different maximum absorption wavelengths as the near infrared absorbing dye. According to this aspect, the waveform of the absorption spectrum of the obtained cured film is wider than in the case of using one type of near-infrared absorbing dye, and it is possible to shield near-infrared rays in a wide wavelength range. When at least two compounds having different maximum absorption wavelengths are used, the first near-infrared absorbing dye having the maximum absorption wavelength in the wavelength range of 700 to 1,000 nm and the maximum absorption wavelength of the first near-infrared absorbing dye At least a second near infrared absorbing dye having a maximum absorption wavelength in a wavelength range of 700 to 1,000 nm on the short wavelength side, the maximum absorption wavelength of the first near infrared absorbing dye, and the second near infrared absorption dye; The difference from the maximum absorption wavelength of the infrared absorbing dye is preferably 1 to 150 nm.
　本発明において、近赤外線吸収色素は、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、ジイモニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物およびジベンゾフラノン化合物から選ばれる少なくとも１種が好ましく、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物およびクアテリレン化合物から選ばれる少なくとも１種がより好ましく、ピロロピロール化合物、シアニン化合物およびスクアリリウム化合物から選ばれる少なくとも１種が更に好ましく、ピロロピロール化合物が特に好ましい。ジイモニウム化合物としては、例えば、特表２００８－５２８７０６号公報に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。フタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物、特開２００６－３４３６３１号公報に記載のオキシチタニウムフタロシアニン、特開２０１３－１９５４８０号公報の段落番号００１３～００２９に記載の化合物、特許第６０８１７７１号公報に記載のバナジウムフタロシアニンが挙げられ、これらの内容は本明細書に組み込まれる。ナフタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。また、シアニン化合物、フタロシアニン化合物、ナフタロシアニン化合物、ジイモニウム化合物およびスクアリリウム化合物は、特開２０１０－１１１７５０号公報の段落番号００１０～００８１に記載の化合物を使用してもよく、この内容は本明細書に組み込まれる。また、シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本明細書に組み込まれる。また、近赤外線吸収色素としては、特開２０１６－１４６６１９号公報に記載された化合物を用いることもでき、この内容は本明細書に組み込まれる。また、近赤外線吸収色素は、下記構造の化合物を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000001
 In the present invention, near infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, At least one selected from a pyrromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squalilium compound, a phthalocyanine compound, a naphthalocyanine compound and a quaterrylene compound is more preferable. At least one selected from pyrrolopyrrole compounds, cyanine compounds and squarylium compounds More preferably, pyrrolo-pyrrole compounds are particularly preferred. Examples of diimmonium compounds include the compounds described in JP-A-2008-528706, the contents of which are incorporated herein. As the phthalocyanine compound, for example, a compound described in paragraph 0093 of JP-A-2012-77153, an oxytitanium phthalocyanine described in JP-A-2006-343631, a paragraph number 0013 to 0029 of JP-A-2013-195480. And vanadium phthalocyanine described in Japanese Patent No. 6081771, the contents of which are incorporated herein. As a naphthalocyanine compound, the compound as described in stage number 0093 of Unexamined-Japanese-Patent No. 2012-77153 is mentioned, for example, This content is integrated in this specification. In addition, as the cyanine compound, the phthalocyanine compound, the naphthalocyanine compound, the dimonium compound and the squarylium compound, the compounds described in paragraphs [0010] to [0081] of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated. In addition, cyanine compounds can be referred to, for example, "functional dyes, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein. . Further, as the near infrared absorbing dye, a compound described in JP-A-2016-146619 can also be used, and the contents thereof are incorporated in the present specification. Moreover, it is also preferable to use the compound of the following structure as a near-infrared absorbing dye.
Figure JPOXMLDOC01-appb-C000001
　ピロロピロール化合物としては、式（ＰＰ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000002
　式中、Ｒ1aおよびＲ1bは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ2およびＲ3は、各々独立に水素原子または置換基を表し、Ｒ2およびＲ3は、互いに結合して環を形成してもよく、Ｒ4は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲ4AＲ4B、または金属原子を表し、Ｒ4は、Ｒ1a、Ｒ1bおよびＲ3から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ4AおよびＲ4Bは、各々独立に置換基を表す。Ｒ4AおよびＲ4Bは互いに結合して環を形成していてもよい。式（ＰＰ）の詳細については、特開２００９－２６３６１４号公報の段落番号００１７～００４７、特開２０１１－６８７３１号公報の段落番号００１１～００３６、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
Figure JPOXMLDOC01-appb-C000002
In the formula, R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R 2 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 and R 3 represent R 4 may be combined with each other to form a ring, and each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B , or a metal atom, and R 4 is an R R 4A and R 4B may each independently represent a substituent, which may be covalently bonded or coordinated with at least one selected from 1 a 1 , R 1 b and R 3 . R 4A and R 4B may be bonded to each other to form a ring. About the detail of Formula (PP), Paragraph No. 0017 of the Unexamined-Japanese-Patent No. 2009-263614, Paragraph No. 0011 of the Unexamined-Japanese-Patent No. 2011-68731, Paragraph No. 0010 of the international publication WO2015 / 166873 The contents of which are incorporated herein by reference.
　式（ＰＰ）において、Ｒ1aおよびＲ1bは、各々独立に、アリール基またはヘテロアリール基が好ましく、アリール基がより好ましい。また、Ｒ1aおよびＲ1bが表すアルキル基、アリール基およびヘテロアリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、特開２００９－２６３６１４号公報の段落番号００２０～００２２に記載された置換基や、以下の置換基Ｔが挙げられる。 In formula (PP), R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. In addition, the alkyl group, the aryl group and the heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in Paragraph Nos. 0020 to 0022 of JP 2009-263614 A, and the following substituent T.
（置換基Ｔ）
　アルキル基（好ましくは炭素数１～３０のアルキル基）、アルケニル基（好ましくは炭素数２～３０のアルケニル基）、アルキニル基（好ましくは炭素数２～３０のアルキニル基）、アリール基（好ましくは炭素数６～３０のアリール基）、アミノ基（好ましくは炭素数０～３０のアミノ基）、アルコキシ基（好ましくは炭素数１～３０のアルコキシ基）、アリールオキシ基（好ましくは炭素数６～３０のアリールオキシ基）、ヘテロアリールオキシ基、アシル基（好ましくは炭素数１～３０のアシル基）、アルコキシカルボニル基（好ましくは炭素数２～３０のアルコキシカルボニル基）、アリールオキシカルボニル基（好ましくは炭素数７～３０のアリールオキシカルボニル基）、アシルオキシ基（好ましくは炭素数２～３０のアシルオキシ基）、アシルアミノ基（好ましくは炭素数２～３０のアシルアミノ基）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０のアルコキシカルボニルアミノ基）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０のアリールオキシカルボニルアミノ基）、スルファモイル基（好ましくは炭素数０～３０のスルファモイル基）、カルバモイル基（好ましくは炭素数１～３０のカルバモイル基）、アルキルチオ基（好ましくは炭素数１～３０のアルキルチオ基）、アリールチオ基（好ましくは炭素数６～３０のアリールチオ基）、ヘテロアリールチオ基（好ましくは炭素数１～３０）、アルキルスルホニル基（好ましくは炭素数１～３０）、アリールスルホニル基（好ましくは炭素数６～３０）、ヘテロアリールスルホニル基（好ましくは炭素数１～３０）、アルキルスルフィニル基（好ましくは炭素数１～３０）、アリールスルフィニル基（好ましくは炭素数６～３０）、ヘテロアリールスルフィニル基（好ましくは炭素数１～３０）、ウレイド基（好ましくは炭素数１～３０）、水酸基、カルボキシル基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基、メルカプト基、ハロゲン原子、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基（好ましくは炭素数１～３０）。これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。置換基としては、上述した置換基Ｔで説明した基が挙げられる。 (Substituent T)
An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group, acyl group (preferably having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably having 2 to 30 carbon atoms) Is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acylo group having 2 to 30 carbon atoms). A), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably 7 to carbon atoms) 30) aryloxycarbonylamino group), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably having 1 to 30 carbon atoms) Alkylthio group), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 1 to 30 carbon atoms) Preferably having 6 to 30 carbon atoms, heteroarylsul Group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms) Ureido group (preferably having a carbon number of 1 to 30), hydroxyl group, carboxyl group, sulfo group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, mercapto group, halogen atom, cyano group, alkyl And a sulfino group, an arylsulfino group, a hydrazino group, an imino group and a heteroaryl group (preferably having a carbon number of 1 to 30). When these groups are further substitutable groups, they may further have a substituent. As a substituent, the group demonstrated by the substituent T mentioned above is mentioned.
　Ｒ1a、Ｒ1bで表される基の具体例としては、アルコキシ基を置換基として有するアリール基、水酸基を置換基として有するアリール基、アシルオキシ基を置換基として有するアリール基などが挙げられる。 Specific examples of the group represented by R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, an aryl group having an acyloxy group as a substituent and the like.
　式（ＰＰ）において、Ｒ2およびＲ3は、各々独立に水素原子または置換基を表す。置換基としては上述した置換基Ｔが挙げられる。Ｒ2およびＲ3の少なくとも一方は電子求引性基が好ましい。ハメットの置換基定数σ値（シグマ値）が正の置換基は、電子求引性基として作用する。ここで、ハメット則で求められた置換基定数にはσｐ値とσｍ値がある。これらの値は多くの一般的な成書に見出すことができる。本発明においては、ハメットの置換基定数σ値が０．２以上の置換基を電子求引性基として例示することができる。σ値は、０．２５以上が好ましく、０．３以上がより好ましく、０．３５以上が更に好ましい。上限は特に制限はないが、好ましくは０．８０以下である。電子求引性基の具体例としては、シアノ基（σｐ値＝０．６６）、カルボキシル基（－ＣＯＯＨ：σｐ値＝０．４５）、アルコキシカルボニル基（例えば、－ＣＯＯＭｅ：σｐ値＝０．４５）、アリールオキシカルボニル基（例えば、－ＣＯＯＰｈ：σｐ値＝０．４４）、カルバモイル基（例えば、－ＣＯＮＨ2：σｐ値＝０．３６）、アルキルカルボニル基（例えば、－ＣＯＭｅ：σｐ値＝０．５０）、アリールカルボニル基（例えば、－ＣＯＰｈ：σｐ値＝０．４３）、アルキルスルホニル基（例えば、－ＳＯ2Ｍｅ：σｐ値＝０．７２）、アリールスルホニル基（例えば、－ＳＯ2Ｐｈ：σｐ値＝０．６８）などが挙げられ、シアノ基が好ましい。ここで、Ｍｅはメチル基を、Ｐｈはフェニル基を表す。なお、ハメットの置換基定数σ値については、例えば、特開２０１１－６８７３１号公報の段落番号００１７～００１８を参酌でき、この内容は本明細書に組み込まれる。 In formula (PP), R 2 and R 3 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. At least one of R 2 and R 3 is preferably an electron-withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-withdrawing group. Here, the substituent constants determined by the Hammett rule include σp values and σm values. These values can be found in many general books. In the present invention, a substituent having a Hammett's substituent constant σ value of 0.2 or more can be exemplified as the electron-withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (σ p value = 0.66), a carboxyl group (—COOH: σ p value = 0.45), and an alkoxycarbonyl group (eg, —COOMe: σ p value = 0. 45), an aryloxycarbonyl group (for example, -COOPh: σp value = 0.44), a carbamoyl group (for example, -CONH 2 : σp value = 0.36), an alkylcarbonyl group (for example, -COMe: σp value = 0.50), an arylcarbonyl group (for example, -COPh: σp value = 0.43), an alkylsulfonyl group (for example, -SO 2 Me: σp value = 0.72), an arylsulfonyl group (for example, -SO 2 Ph: σp value = 0.68) and the like, and a cyano group is preferable. Here, Me represents a methyl group, and Ph represents a phenyl group. The Hammett's substituent constant σ value can be referred to, for example, paragraph Nos. 0017 to 0018 of JP-A-2011-68731, the contents of which are incorporated herein.
　式（ＰＰ）において、Ｒ2は電子求引性基（好ましくはシアノ基）を表し、Ｒ3はヘテロアリール基を表すことが好ましい。ヘテロアリール基は、５員環または６員環が好ましい。また、ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。ヘテロアリール基を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。ヘテロ原子としては、例えば、窒素原子、酸素原子、硫黄原子が例示される。ヘテロアリール基は、窒素原子を１個以上有することが好ましい。式（ＰＰ）における２個のＲ2同士は同一であってもよく、異なっていてもよい。また、式（ＰＰ）における２個のＲ3同士は同一であってもよく、異なっていてもよい。 In formula (PP), R 2 preferably represents an electron-withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a fused ring, preferably a single ring or a fused ring having 2 to 8 condensations, and more preferably a single ring or a fused ring having 2 to 4 condensations. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. Two R 2 s in Formula (PP) may be identical to or different from each other. Moreover, two R 3 's in Formula (PP) may be the same or different.
　式（ＰＰ）において、Ｒ4は、水素原子、アルキル基、アリール基、ヘテロアリール基または－ＢＲ4AＲ4Bで表される基であることが好ましく、水素原子、アルキル基、アリール基または－ＢＲ4AＲ4Bで表される基であることがより好ましく、－ＢＲ4AＲ4Bで表される基であることが更に好ましい。Ｒ4AおよびＲ4Bが表す置換基としては、ハロゲン原子、アルキル基、アルコキシ基、アリール基、または、ヘテロアリール基が好ましく、アルキル基、アリール基、または、ヘテロアリール基がより好ましく、アリール基が特に好ましい。これらの基はさらに置換基を有していてもよい。式（ＰＰ）における２個のＲ4同士は同一であってもよく、異なっていてもよい。Ｒ4AおよびＲ4Bは互いに結合して環を形成していてもよい。 In formula (PP), R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR 4A R 4B , and a hydrogen atom, an alkyl group, an aryl group or —BR The group represented by 4A R 4B is more preferably a group represented by -BR 4A R 4B . The substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and an aryl group Particularly preferred. These groups may further have a substituent. Two R 4 's in the formula (PP) may be the same or different. R 4A and R 4B may be bonded to each other to form a ring.
　式（ＰＰ）で表される化合物の具体例としては、下記化合物が挙げられる。以下の構造式中、Ｐｈはフェニル基を表す。また、ピロロピロール化合物としては、特開２００９－２６３６１４号公報の段落番号００１６～００５８に記載の化合物、特開２０１１－６８７３１号公報の段落番号００３７～００５２に記載の化合物、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００３３に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
 The following compounds may be mentioned as specific examples of the compound represented by the formula (PP). In the following structural formulae, Ph represents a phenyl group. As pyrrolopyrrole compounds, compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A, WO 2015/166873 And the compounds described in Paragraph No. 0010 to 0033 of the publication, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
　スクアリリウム化合物としては、下記式（ＳＱ）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000005
　式（ＳＱ）中、Ａ1およびＡ2は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ－１）で表される基を表す；
Figure JPOXMLDOC01-appb-C000006
　式（Ａ－１）中、Ｚ1は、含窒素複素環を形成する非金属原子団を表し、Ｒ2は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。式（ＳＱ）の詳細については、特開２０１１－２０８１０１号公報の段落番号００２０～００４９、特許第６０６５１６９号公報の段落番号００４３～００６２、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００２４～００４０の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As the squarylium compound, a compound represented by the following formula (SQ) is preferable.
Figure JPOXMLDOC01-appb-C000005
In formula (SQ), each of A 1 and A 2 independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);
Figure JPOXMLDOC01-appb-C000006
In formula (A-1), Z 1 represents a nonmetal atomic group forming a nitrogen-containing heterocyclic ring, R 2 represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1. The wavy line represents a connecting hand. The details of the formula (SQ) are described in paragraph Nos. 0020 to 0049 of JP2011-208101A, paragraph Nos. 0043 to 0062 of Patent No. 6065169, and paragraph Nos. 0024 to 0040 of International Publication WO2016 / 181987. The contents of these are incorporated herein by reference.
　なお、式（ＳＱ）においてカチオンは、以下のように非局在化して存在している。
Figure JPOXMLDOC01-appb-C000007
 In the formula (SQ), the cation is present in a delocalized manner as follows.
Figure JPOXMLDOC01-appb-C000007
　スクアリリウム化合物は、下記式（ＳＱ－１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000008
　環Ａおよび環Ｂは、それぞれ独立に芳香族環を表し、
　ＸAおよびＸBはそれぞれ独立に置換基を表し、
　ＧAおよびＧBはそれぞれ独立に置換基を表し、
　ｋＡは０～ｎAの整数を表し、ｋＢは０～ｎBの整数を表し、
　ｎAおよびｎBはそれぞれ環Ａまたは環Ｂに置換可能な最大の整数を表し、
　ＸAとＧA、ＸBとＧB、ＸAとＸBは、互いに結合して環を形成しても良く、ＧAおよびＧBがそれぞれ複数存在する場合は、互いに結合して環構造を形成していても良い。 The squarylium compound is preferably a compound represented by the following formula (SQ-1).
Figure JPOXMLDOC01-appb-C000008
Ring A and ring B each independently represent an aromatic 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 , k B represents an integer of 0 to n B ,
n A and n B respectively represent the largest integers which can be substituted on ring A or ring B,
X A and G A , X B and G B , and X A and X B may bond to each other to form a ring, and when there are a plurality of G A and G B respectively, they may be bonded to each other to form a ring structure May be formed.
　ＧAおよびＧBが表す置換基としては、上述した式（ＰＰ）で説明した置換基Ｔが挙げられる。 The substituent represented by G A and G B, include the substituent T described by the formula (PP) as described above.
　ＸAおよびＸBが表す置換基としては、活性水素を有する基が好ましく、－ＯＨ、－ＳＨ、－ＣＯＯＨ、－ＳＯ3Ｈ、－ＮＲX1ＲX2、－ＮＨＣＯＲX1、－ＣＯＮＲX1ＲX2、－ＮＨＣＯＮＲX1ＲX2、－ＮＨＣＯＯＲX1、－ＮＨＳＯ2ＲX1、－Ｂ（ＯＨ）2および－ＰＯ（ＯＨ）2がより好ましく、－ＯＨ、－ＳＨおよび－ＮＲX1ＲX2が更に好ましい。ＲX1およびＲX1は、それぞれ独立に水素原子または置換基を表す。ＸAおよびＸBが表す置換基としてはアルキル基、アリール基、または、ヘテロアリール基が挙げられ、アルキル基が好ましい。 Examples of the substituent represented by X A and X B, preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2, -NHCOR X1, -CONR X1 R X2, -NHCONR X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 and -PO (OH) 2 are more preferable, and -OH, -SH and -NR X1 R X2 are more preferable. Each of R X1 and R X1 independently represents a hydrogen atom or a substituent. As a substituent which X A and X B represent, an alkyl group, an aryl group, or heteroaryl group is mentioned, An alkyl group is preferable.
　環Ａおよび環Ｂは、それぞれ独立に、芳香族環を表す。芳香族環は単環であってもよく、縮合環であってもよい。芳香族環の具体例としては、ベンゼン環、ナフタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、および、フェナジン環が挙げられ、ベンゼン環またはナフタレン環が好ましい。芳香族環は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述した式（ＰＰ）で説明した置換基Ｔが挙げられる。 Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a single ring or a fused ring. Specific examples of the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene 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, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, tianthrene ring, Men ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring is preferable. The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent T demonstrated by the formula (PP) mentioned above is mentioned.
　ＸAとＧA、ＸBとＧB、ＸAとＸBは、互いに結合して環を形成しても良く、ＧAおよびＧBがそれぞれ複数存在する場合は、互いに結合して環を形成していても良い。環としては、５員環または６員環が好ましい。環は単環であってもよく、縮合環であってもよい。ＸAとＧA、ＸBとＧB、ＸAとＸB、ＧA同士またはＧB同士が結合して環を形成する場合、これらが直接結合して環を形成してもよく、アルキレン基、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＢＲ－およびそれらの組み合わせからなる２価の連結基を介して結合して環を形成してもよい。Ｒは、水素原子または置換基を表す。置換基としては、上述した式（ＰＰ）で説明した置換基Ｔが挙げられ、アルキル基またはアリール基が好ましい。 X A and G A , X B and G B , and X A and X B may bond to each other to form a ring, and when there are a plurality of G A and G B respectively, they may be bonded to each other to form a ring You may form. The ring is preferably a 5- or 6-membered ring. The ring may be a single ring or may be a fused ring. When X A and G A , X B and G B , X A and X B , G A or B B bond together to form a ring, these may be directly bonded to form a ring; The ring may be formed through a divalent linking group consisting of the groups -CO-, -O-, -NH-, -BR- and combinations thereof. R represents a hydrogen atom or a substituent. As a substituent, the substituent T demonstrated by Formula (PP) mentioned above is mentioned, An alkyl group or an aryl group is preferable.
　ｋＡは０～ｎＡの整数を表し、ｋＢは０～ｎＢの整数を表し、ｎAは、環Ａに置換可能な最大の整数を表し、ｎBは、環Ｂに置換可能な最大の整数を表す。ｋＡおよびｋＢは、それぞれ独立に０～４が好ましく、０～２がより好ましく、０～１が特に好ましい。 kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, n A represents a maximum integer replaceable to ring A, n B represents a maximum integer replaceable to ring B Represent. Each of kA and kB is preferably independently 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.
　スクアリリウム化合物は、下記式（ＳＱ－１０）、式（ＳＱ－１１）または式（ＳＱ－１２）で表される化合物であることも好ましい。
式（ＳＱ－１０）
Figure JPOXMLDOC01-appb-C000009
式（ＳＱ－１１）
Figure JPOXMLDOC01-appb-C000010
式（ＳＱ－１２）
Figure JPOXMLDOC01-appb-C000011
 The squarylium compound is also preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12).
Formula (SQ-10)
Figure JPOXMLDOC01-appb-C000009
Formula (SQ-11)
Figure JPOXMLDOC01-appb-C000010
Formula (SQ-12)
Figure JPOXMLDOC01-appb-C000011
　式（ＳＱ－１０）～（ＳＱ－１２）中、Ｘは、独立して、１つ以上の水素原子がハロゲン原子、炭素数１～１２のアルキル基またはアルコキシ基で置換されていてもよい式（１）または式（２）で示される２価の有機基である。
　－（ＣＨ2）n1－　　　・・・（１）
　式（１）中、ｎ１は２または３である。
　－（ＣＨ2）n2－Ｏ－（ＣＨ2）n3－　　　・・・（２）
　式（２）中、ｎ２とｎ３はそれぞれ独立して０～２の整数であり、ｎ２＋ｎ３は１または２である。
　Ｒ1およびＲ2は、それぞれ独立して、アルキル基またはアリール基を表す。アルキル基およびアリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した式（ＰＰ）で説明した置換基Ｔが挙げられる。
　Ｒ3～Ｒ6は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基またはアルコキシ基を表す。
　ｎは２または３である。 In formulas (SQ-10) to (SQ-12), each X is a group of one or more hydrogen atoms optionally substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group. (1) or a divalent organic group represented by the formula (2).
-(CH 2 ) n1-... (1)
In formula (1), n1 is 2 or 3.
- (CH 2) n2 -O- ( CH 2) n3 - ··· (2)
In the formula (2), n2 and n3 are each independently an integer of 0 to 2, and n2 + n3 is 1 or 2.
Each of R 1 and R 2 independently represents an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent or may be unsubstituted. As a substituent, the substituent T demonstrated by the formula (PP) mentioned above is mentioned.
R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
n is 2 or 3.
　スクアリリウム化合物としては、下記構造の化合物が挙げられる。また、特開２０１１－２０８１０１号公報の段落番号００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落番号００６０～００６１に記載の化合物、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００４０に記載の化合物、国際公開ＷＯ２０１３／１３３０９９号公報に記載の化合物、国際公開ＷＯ２０１４／０８８０６３号公報に記載の化合物、特開２０１４－１２６６４２号公報に記載の化合物、特開２０１６－１４６６１９号公報に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、特開２０１７－２５３１１号公報に記載の化合物、国際公開ＷＯ２０１６／１５４７８２号公報に記載の化合物、特許５８８４９５３号公報に記載の化合物、特許６０３６６８９号公報に記載の化合物、特許５８１０６０４号公報に記載の化合物、特開２０１７－０６８１２０号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000012
 As a squarylium compound, the compound of the following structure is mentioned. Further, compounds described in paragraphs 0044 to 0049 of JP2011-208101A, compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, described in paragraph 0040 of International Publication WO2016 / 181987A. Compound, compound described in International Publication WO 2013/133099, compound described in International Publication WO 2014/088063, compound described in Japanese Patent Laid-Open No. 2014-126642, compound described in Japanese Patent Laid-Open No. 2016-146619, The compound described in JP-A-2015-176046, the compound described in JP-A-2017-25311, the compound described in International Publication WO2016 / 154782, the compound described in JP-A-5884953, a JP-A-6036689 Described compounds, Compounds described in 5810604 JP, can be mentioned compounds described in JP-A-2017-068120, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000012
　シアニン化合物は、式（Ｃ）で表される化合物が好ましい。
式（Ｃ）
Figure JPOXMLDOC01-appb-C000013
　式中、Ｚ1およびＺ2は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子団であり、
　Ｒ101およびＲ102は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
　Ｌ1は、奇数個のメチン基を有するメチン鎖を表し、
　ａおよびｂは、それぞれ独立に、０または１であり、
　ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
　式中のＣｙで表される部位がカチオン部である場合、Ｘ1はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ1はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 The cyanine compound is preferably a compound represented by the formula (C).
Formula (C)
Figure JPOXMLDOC01-appb-C000013
In the formula, each of Z 1 and Z 2 independently represents a nonmetallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed.
R 101 and R 102 each independently represent 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,
a and b are each independently 0 or 1;
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X 1 represents an anion, c represents the number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety Where X 1 represents a cation, c represents the number necessary to balance the charge, and c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule It is 0.
　シアニン化合物の具体例としては、以下に示す化合物が挙げられる。また、シアニン化合物としては、特開２００９－１０８２６７号公報の段落番号００４４～００４５に記載の化合物、特開２００２－１９４０４０号公報の段落番号００２６～００３０に記載の化合物、特開２０１５－１７２００４号公報に記載の化合物、特開２０１５－１７２１０２号公報に記載の化合物、特開２００８－８８４２６号公報に記載の化合物、特開２０１７－０３１３９４号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000014
 As specific examples of the cyanine compound, the following compounds may be mentioned. Further, as the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, compounds described in paragraphs 0026 to 0030 of JP 2002-194040 A, JP 2015-172004 A Compounds described in JP-A-2015-172102, compounds described in JP-A-2008-88426, and compounds described in JP-A-2017-031394, the contents of which are incorporated herein by reference. It is incorporated in the specification.
Figure JPOXMLDOC01-appb-C000014
　本発明において、近赤外線吸収色素としては、市販品を用いることもできる。例えば、ＳＤＯ－Ｃ３３（有本化学工業（株）製）、イーエクスカラーＩＲ－１４、イーエクスカラーＩＲ－１０Ａ、イーエクスカラーＴＸ－ＥＸ－８０１Ｂ、イーエクスカラーＴＸ－ＥＸ－８０５Ｋ（（株）日本触媒製）、ＳｈｉｇｅｎｏｘＮＩＡ－８０４１、ＳｈｉｇｅｎｏｘＮＩＡ－８０４２、ＳｈｉｇｅｎｏｘＮＩＡ－８１４、ＳｈｉｇｅｎｏｘＮＩＡ－８２０、ＳｈｉｇｅｎｏｘＮＩＡ－８３９（ハッコーケミカル社製）、ＥｐｏｌｉｔｅＶ－６３、Ｅｐｏｌｉｇｈｔ３８０１、Ｅｐｏｌｉｇｈｔ３０３６（ＥＰＯＬＩＮ社製）、ＰＲＯ－ＪＥＴ８２５ＬＤＩ（富士フイルム（株）製）、ＮＫ－３０２７、ＮＫ－５０６０（（株）林原製）、ＹＫＲ－３０７０（三井化学（株）製）などが挙げられる。 In the present invention, commercially available products can also be used as the near infrared absorbing dye. For example, SDO-C33 (Arimoto Chemical Industries Co., Ltd.), EEX Color IR-14, EEX Color IR-10A, EEX Color TX-EX-801B, EEX Color TX-EX-805K ( A product of Nippon Shokubai), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (Hakoko Chemical Co., Ltd.), Epolite V-63, Epolight 3801, Epolight 3036 (EPOLIN), PRO-JET 825 LDI Film Co., Ltd., NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), and the like.
　本発明で用いられる近赤外線吸収色素は、また、後述する実施例で用いている化合物も好ましい化合物として例示される。
　近赤外線吸収色素の含有量は、硬化性組成物の全固形分に対して３～５０質量％であることが好ましい。上限は、４０質量％以下が好ましく、３５質量％以下がより好ましい。下限は、４質量％以上が好ましく、５質量％以上がより好ましい。近赤外線吸収色素は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。 The near infrared absorbing dye used in the present invention is also exemplified as a preferred compound as a compound used in the examples described later.
The content of the near infrared absorbing dye is preferably 3 to 50% by mass with respect to the total solid content of the curable composition. 40 mass% or less is preferable, and, as for the upper limit, 35 mass% or less is more preferable. 4 mass% or more is preferable, and, as for a lower limit, 5 mass% or more is more preferable. The near infrared absorbing dye may be used alone or in combination of two or more. In the case of 2 or more types, it is preferable that the total amount of them becomes the said range.
＜＜他の近赤外線吸収剤＞＞
　本発明の硬化性組成物は、上述した近赤外線吸収色素以外の近赤外線吸収剤（他の近赤外線吸収剤ともいう）をさらに含んでもよい。他の近赤外線吸収剤としては、無機顔料（無機粒子）が挙げられる。無機顔料の形状は特に制限されず、球状、非球状を問わず、シート状、ワイヤー状、チューブ状であってもよい。無機顔料としては、金属酸化物粒子または金属粒子が好ましい。金属酸化物粒子としては、例えば、酸化インジウムスズ（ＩＴＯ）粒子、酸化アンチモンスズ（ＡＴＯ）粒子、酸化亜鉛（ＺｎＯ）粒子、Ａｌドープ酸化亜鉛（ＡｌドープＺｎＯ）粒子、フッ素ドープ二酸化スズ（ＦドープＳｎＯ2）粒子、ニオブドープ二酸化チタン（ＮｂドープＴｉＯ2）粒子などが挙げられる。金属粒子としては、例えば、銀（Ａｇ）粒子、金（Ａｕ）粒子、銅（Ｃｕ）粒子、ニッケル（Ｎｉ）粒子などが挙げられる。また、無機顔料としては酸化タングステン系化合物を用いることもできる。酸化タングステン系化合物は、セシウム酸化タングステンであることが好ましい。酸化タングステン系化合物の詳細については、特開２０１６－００６４７６号公報の段落番号００８０を参酌でき、この内容は本明細書に組み込まれる。 << Other near infrared absorbers >>
The curable composition of the present invention may further contain a near infrared absorber (also referred to as another near infrared absorber) other than the above-described near infrared absorbing dye. Other near-infrared absorbers include inorganic pigments (inorganic particles). The shape of the inorganic pigment is not particularly limited, and may be spherical, non-spherical, sheet-like, wire-like or tube-like. As the inorganic pigment, metal oxide particles or metal particles are preferable. Examples of metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine-doped tin dioxide (F-doped) SnO 2 ) particles, niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, etc. may be mentioned. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like. Moreover, a tungsten oxide type compound can also be used as an inorganic pigment. The tungsten oxide based compound is preferably cesium tungsten oxide. For details of the tungsten oxide based compound, paragraph 0080 of JP-A-2016-006476 can be referred to, and the contents thereof are incorporated in the present specification.
　本発明の硬化性組成物が他の近赤外線吸収剤を含有する場合、他の近赤外線吸収剤の含有量は、本発明の硬化性組成物の全固形分に対して、０．０１～５０質量％が好ましい。下限は、０．１質量％以上が好ましく、０．５質量％以上がより好ましい。上限は、３０質量％以下が好ましく、１５質量％以下がより好ましい。
　また、上述した近赤外線吸収色素と他の近赤外線吸収剤との合計質量中における他の近赤外線吸収剤の含有量は、１～９９質量％が好ましい。上限は、８０質量％以下が好ましく、５０質量％以下がより好ましく、３０質量％以下がさらに好ましい。
　また、本発明の硬化性組成物は他の近赤外線吸収剤を実質的に含有しないことも好ましい。他の近赤外線吸収剤を実質的に含有しないとは、上述した近赤外線吸収色素と他の近赤外線吸収剤との合計質量中における他の近赤外線吸収剤の含有量が０．５質量％以下であることが好ましく、０．１質量％以下であることがより好ましく、他の近赤外線吸収剤を含有しないことがさらに好ましい。 When the curable composition of the present invention contains another near infrared absorber, the content of the other near infrared absorber is 0.01 to 50 based on the total solid content of the curable composition of the present invention. % By weight is preferred. 0.1 mass% or more is preferable, and, as for a lower limit, 0.5 mass% or more is more preferable. 30 mass% or less is preferable, and, as for the upper limit, 15 mass% or less is more preferable.
In addition, the content of the other near infrared absorber in the total mass of the above-mentioned near infrared absorbing dye and the other near infrared absorber is preferably 1 to 99% by mass. 80 mass% or less is preferable, 50 mass% or less is more preferable, and 30 mass% or less is further more preferable.
Moreover, it is also preferable that the curable composition of this invention does not contain another near-infrared absorber substantially. The content of the other near-infrared absorber in the total mass of the above-mentioned near-infrared absorbing dye and the other near-infrared absorber is 0.5% by mass or less as substantially free of the other near-infrared absorber It is more preferable that it is 0.1 mass% or less, and it is still more preferable that it does not contain other near-infrared absorbers.
＜＜ラジカル重合性化合物＞＞
　本発明の硬化性組成物は、ラジカル重合性化合物を含有する。ラジカル重合性化合物としては、エチレン性不飽和結合を有する基を１個以上有する化合物であることが好ましく、エチレン性不飽和結合を有する基を２個以上有する化合物であることがより好ましく、エチレン性不飽和結合を有する基を３個以上有する化合物であることがさらに好ましい。ラジカル重合性化合物におけるエチレン性不飽和結合を有する基の個数の上限は、たとえば、１５個以下が好ましく、６個以下がより好ましい。エチレン性不飽和結合を有する基としては、ビニル基、スチリル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられ、（メタ）アクリロイル基が好ましい。ラジカル重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。 << Radically Polymerizable Compound >>
The curable composition of the present invention contains a radically polymerizable compound. The radically polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and ethylenic More preferably, it is a compound having three or more groups having unsaturated bonds. The upper limit of the number of groups having an ethylenically unsaturated bond in the radically polymerizable compound is, for example, preferably 15 or less, more preferably 6 or less. As a group which has an ethylenically unsaturated bond, a vinyl group, a styryl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned, A (meth) acryloyl group is preferable. The radically polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
　ラジカル重合性化合物は、モノマー、ポリマーのいずれの形態であってもよいがモノマーが好ましい。モノマータイプのラジカル重合性化合物は、分子量が１００～３，０００であることが好ましい。上限は、２，０００以下がより好ましく、１，５００以下がさらに好ましい。下限は、１５０以上がより好ましく、２５０以上がさらに好ましい。また、ラジカル重合性化合物は、分子量分布を実質的に有さない化合物であることも好ましい。ここで、分子量分布を実質的に有さない化合物としては、化合物の分散度（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））が、１．０～１．５である化合物が好ましく、１．０～１．３がより好ましい。 The radically polymerizable compound may be in the form of a monomer or a polymer, but a monomer is preferred. The monomer type radically polymerizable compound preferably has a molecular weight of 100 to 3,000. The upper limit is more preferably 2,000 or less, further preferably 1,500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more. Moreover, it is also preferable that a radically polymerizable compound is a compound which does not have molecular weight distribution substantially. Here, as the compound substantially having no molecular weight distribution, a compound having a degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 to 1.5 is preferable, 1.0 to 1.3 is more preferable.
　ラジカル重合性化合物の例としては、特開２０１３－２５３２２４号公報の段落番号００３３～００３４の記載を参酌することができ、この内容は本明細書に組み込まれる。ラジカル重合性化合物としては、エチレンオキシ変性ペンタエリスリトールテトラアクリレート（市販品としては、ＮＫエステルＡＴＭ－３５Ｅ；新中村化学工業（株）製）、ジペンタエリスリトールトリアクリレート（市販品としては、ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては、ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては、ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては、ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基が、エチレングリコール残基および／またはプロピレングリコール残基を介して結合している構造の化合物が好ましい。またこれらのオリゴマータイプも使用できる。また、特開２０１３－２５３２２４号公報の段落番号００３４～００３８の記載を参酌することができ、この内容は本明細書に組み込まれる。また、特開２０１２－２０８４９４号公報の段落番号０４７７（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０５８５）に記載の重合性モノマー等が挙げられ、これらの内容は本明細書に組み込まれる。また、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としては、Ｍ－４６０；東亞合成製）、ペンタエリスリトールテトラアクリレート（新中村化学工業（株）製、Ａ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）も好ましい。これらのオリゴマータイプも使用できる。例えば、ＲＰ－１０４０（日本化薬（株）製）などが挙げられる。 As an example of the radically polymerizable compound, the description in paragraphs “0033” to “0034” of JP 2013-253224 A can be referred to, and the contents thereof are incorporated in the present specification. As a radically polymerizable compound, ethyleneoxy modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; Shin-Nakamura Chemical Co., Ltd. product), dipentaerythritol triacrylate (as a commercial product, KAYARAD D- 330; Nippon Kayaku Co., Ltd. product, dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product, dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd. product, A-DPH-12E; Shin Nakamura Chemical Industry Co., Ltd. Co., Ltd.), and these (meta) acrylic Yl group, compounds having a structure linked via an ethylene glycol residue and / or propylene glycol residues is preferred. These oligomer types can also be used. In addition, the description of Paragraph Nos. 0034 to 0038 in JP 2013-253224 A can be referred to, and the contents thereof are incorporated in the present specification. In addition, polymerizable monomers and the like described in paragraph 0477 of JP-A-2012-208494 (paragraph 0585 of corresponding US Patent Application Publication No. 2012/0235099) can be mentioned, and the contents thereof are the same as those of the present specification. Incorporated into In addition, diglycerin EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1, 6 -Hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.
　ラジカル重合性化合物は、カルボキシル基、スルホ基、リン酸基等の酸基を有していてもよい。酸基を有するラジカル重合性化合物の市販品としては、例えば、アロニックスＭ－３０５、Ｍ－５１０、Ｍ－５２０（以上、東亞合成（株）製）などが挙げられる。ラジカル重合性化合物の酸価は、０．１～４０ｍｇＫＯＨ／ｇが好ましい。下限は５ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、３０ｍｇＫＯＨ／ｇ以下がより好ましい。 The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group or a phosphoric acid group. Examples of commercially available products of radically polymerizable compounds having an acid group include Alonics M-305, M-510, M-520 (all manufactured by Toagosei Co., Ltd.). The acid value of the radically polymerizable compound is preferably 0.1 to 40 mg KOH / g. The lower limit is more preferably 5 mg KOH / g or more. The upper limit is more preferably 30 mg KOH / g or less.
　ラジカル重合性化合物は、カプロラクトン構造を有する化合物も好ましい態様である。カプロラクトン構造を有するラジカル重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。カプロラクトン構造を有するラジカル重合性化合物については、特開２０１３－２５３２２４号公報の段落番号００４２～００４５の記載を参酌することができ、この内容は本明細書に組み込まれる。 As the radically polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment. Examples of radically polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like. The description of paragraphs 0042 to 0045 in JP 2013-253224 A can be referred to for a radically polymerizable compound having a caprolactone structure, the contents of which are incorporated herein.
　ラジカル重合性化合物は、アルキレンオキシ基を有する化合物を用いることもできる。アルキレンオキシ基を有するラジカル重合性化合物は、エチレンオキシ基および／またはプロピレンオキシ基を有する化合物であることが好ましく、エチレンオキシ基を有する化合物であることがより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物であることがさらに好ましい。アルキレンオキシ基を有するラジカル重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 The radically polymerizable compound can also be a compound having an alkyleneoxy group. The radically polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. More preferably, they are 3- to 6-functional (meth) acrylate compounds. Commercially available products of radically polymerizable compounds having an alkyleneoxy group include, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) resin having three isobutylene oxy groups. And the like) and KAYARAD TPA-330 which is an acrylate.
　ラジカル重合性化合物としては、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載されたエチレンオキサイド系骨格を有するウレタン化合物も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載された分子内にアミノ構造やスルフィド構造を有するラジカル重合性化合物を用いることも好ましい。また、ラジカル重合性化合物としては、特開２０１７－４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物を用いることもできる。市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ社製）、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株））製などが挙げられる。また、ラジカル重合性化合物としては、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。 As radically polymerizable compounds, urethane acrylates and the like as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765. JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable as urethane compounds having an ethylene oxide skeleton. Further, it is also preferable to use a radically polymerizable compound having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. . Further, as the radically polymerizable compound, compounds described in JP-A-2017-48367, JP-A-6057891, and JP-A-6031807 can also be used. As commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. In addition, it is also preferable to use 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. as the radically polymerizable compound.
　ラジカル重合性化合物の含有量は、硬化性組成物の全固形分に対して、０．１～４０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、３０質量％以下が好ましく、２０質量％以下がより好ましい。
　また、ラジカル重合性化合物の含有量は、環状エーテル基を有する化合物の１００質量部に対して、１～１００質量部であることが好ましい。下限は、３質量％以上が好ましく、１０質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３０質量％以下がより好ましい。ラジカル重合性化合物と環状エーテル基を有する化合物の割合が上記範囲であれば、耐水密着性がより良好で、近赤外線吸収色素に由来する凝集物の発生がより抑制された硬化膜を形成し易い。
　また、ラジカル重合性化合物の含有量は、近赤外線吸収色素の１００質量部に対して、２０～３００質量部であることが好ましい。上限は、２００質量部以下であることが好ましく１５０質量部以下であることがより好ましく、１２０質量部以下であることが更に好ましい。下限は、３０質量部以上であることが好ましく、４０質量部以上であることがより好ましく、６０質量部以上であることが更に好ましい。ラジカル重合性化合物と近赤外線吸収色素との割合が上記範囲であれば、耐水密着性がより良好で、近赤外線吸収色素に由来する凝集物の発生がより抑制された硬化膜を形成し易い。
　本発明の硬化性組成物は、ラジカル重合性化合物を、１種のみ含んでいてもよいし、２種以上含んでいてもよい。ラジカル重合性化合物を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the radically polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. 0.5 mass% or more is preferable, and, as for a lower limit, 1 mass% or more is more preferable. 30 mass% or less is preferable, and, as for the upper limit, 20 mass% or less is more preferable.
Further, the content of the radically polymerizable compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. 3 mass% or more is preferable, and, as for a lower limit, 10 mass% or more is more preferable. 40 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable. If the ratio of the radically polymerizable compound and the compound having a cyclic ether group is in the above range, the water-resistant adhesion is better, and it is easy to form a cured film in which the generation of aggregates derived from the near infrared absorbing dye is further suppressed .
The content of the radically polymerizable compound is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye. The upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less. The lower limit is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 60 parts by mass or more. If the ratio of the radically polymerizable compound and the near infrared absorbing dye is in the above range, the water-resistant adhesion is better, and it is easy to form a cured film in which the generation of aggregates derived from the near infrared absorbing dye is further suppressed.
The curable composition of the present invention may contain only one type of radically polymerizable compound, or may contain two or more types. When two or more radically polymerizable compounds are contained, the total amount thereof is preferably in the above range.
＜＜熱ラジカル重合開始剤＞＞
　本発明の硬化性組成物は熱ラジカル重合開始剤を含有する。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生させてラジカル重合性化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤は、熱および光の作用によってラジカルを発生する化合物であってもよい。 << Thermal radical polymerization initiator >>
The curable composition of the present invention contains a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat to initiate or accelerate the polymerization reaction of the radically polymerizable compound. The thermal radical polymerization initiator may be a compound which generates a radical by the action of heat and light.
　熱ラジカル重合開始剤としては、ピナコール化合物、α－ヒドロキシアセトフェノン化合物、α－アミノアセトフェノン化合物、ベンジルジメチルケタール化合物、有機過酸化物、アゾ化合物などが挙げられ、本発明の効果がより顕著に得られやすいという理由から、ピナコール化合物、α－ヒドロキシアセトフェノン化合物が好ましく、ピナコール化合物がより好ましい。また、本発明においては、熱ラジカル重合開始剤としてピナコール化合物と、ピナコール化合物以外の熱ラジカル重合開始剤（他の熱ラジカル重合開始剤）とを併用することも好ましい。ピナコール化合物と他の熱ラジカル重合開始剤とを併用することで、近赤外線吸収色素由来の凝集物の発生を効果的に抑制できる。さらには、分光特性に優れた硬化膜が得られやすい。ピナコール化合物と併用する他の熱ラジカル重合開始剤としては、α－ヒドロキシアセトフェノン化合物、α－アミノアセトフェノン化合物、ベンジルジメチルケタール化合物、有機過酸化物、アゾ化合物などが挙げられ、α－ヒドロキシアセトフェノン化合物が好ましい。 Examples of thermal radical polymerization initiators include pinacol compounds, α-hydroxyacetophenone compounds, α-aminoacetophenone compounds, benzyl dimethyl ketal compounds, organic peroxides, azo compounds and the like, and the effects of the present invention are more remarkably obtained. Pinacol compounds and α-hydroxyacetophenone compounds are preferable, and pinacol compounds are more preferable because they are easy to use. In the present invention, it is also preferable to use a pinacol compound as a thermal radical polymerization initiator and a thermal radical polymerization initiator (other thermal radical polymerization initiator) other than the pinacol compound in combination. By using the pinacol compound in combination with another thermal radical polymerization initiator, the generation of an aggregate derived from the near infrared absorbing dye can be effectively suppressed. Furthermore, a cured film having excellent spectral characteristics can be easily obtained. Other thermal radical polymerization initiators to be used in combination with pinacol compounds include α-hydroxyacetophenone compounds, α-aminoacetophenone compounds, benzyl dimethyl ketal compounds, organic peroxides, azo compounds, etc. α-hydroxyacetophenone compounds preferable.
　ピナコール化合物としては、ベンゾピナコール化合物であることが好ましい。ピナコール化合物としては、下記式（Ｔ－１）～（Ｔ－３）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000015
 The pinacol compound is preferably a benzopinacol compound. Examples of pinacol compounds include compounds represented by the following formulas (T-1) to (T-3).
Figure JPOXMLDOC01-appb-C000015
　式（Ｔ－１）～（Ｔ－３）中、Ｒｔ1～Ｒｔ4は、それぞれ独立して置換基を表し、ｍ１～ｍ４は、それぞれ独立して０～４の整数を表す。ｍ１が２～４の場合、ｍ１個のＲｔ1は、それぞれ同一であってもよく、異なってもよい。また、ｍ１個のＲｔ1のうち２個のＲｔ1同士が互いに結合して環を形成していてもよい。ｍ２が２～４の場合、ｍ２個のＲｔ2は、それぞれ同一であってもよく、異なってもよい。また、ｍ２個のＲｔ2のうち２個のＲｔ2同士が互いに結合して環を形成していてもよい。ｍ３が２～４の場合、ｍ３個のＲｔ3は、それぞれ同一であってもよく、異なってもよい。また、ｍ３個のＲｔ3のうち２個のＲｔ3同士が互いに結合して環を形成していてもよい。ｍ４が２～４の場合、ｍ４個のＲｔ4は、それぞれ同一であってもよく、異なってもよい。また、ｍ４個のＲｔ4のうち２個のＲｔ4同士が互いに結合して環を形成していてもよい。また、Ｒｔ1とＲｔ2、Ｒｔ1とＲｔ3、Ｒｔ1とＲｔ4、Ｒｔ2とＲｔ3、Ｒｔ2とＲｔ4、Ｒｔ3とＲｔ4は結合して環を形成していてもよい。
　式（Ｔ－１）中、Ｒｔ5およびＲｔ6は、それぞれ独立して、水素原子、アルキル基、アリール基、Ｔｉ（ＲM1）（ＲM2）（ＲM3）、Ｚｒ（ＲM1）（ＲM2）（ＲM3）、Ｓｉ（ＲM1）（ＲM2）（ＲM3）またはＢ（ＲM1）（ＲM2）を表し、ＲM1～ＲM3は、それぞれ独立して置換基を表す。
　式（Ｔ－２）中、Ｍ1は、Ｔｉ（ＲM4）（ＲM5）、Ｚｒ（ＲM4）（ＲM5）、Ｓｉ（ＲM4）（ＲM5）またはＢ（ＲM4）を表し、ＲM4およびＲM5はそれぞれ独立して置換基を表す。
　式（Ｔ－３）中、Ｍ2は、Ｔｉ（ＲM6）、Ｚｒ（ＲM6）、Ｓｉ（ＲM6）またはＢを表し、ＲM6は置換基を表し、Ｌ1は２価の連結基を表す。 In formulas (T-1) to (T-3), Rt 1 to Rt 4 each independently represent a substituent, and m 1 to m 4 each independently represent an integer of 0 to 4. When m1 is 2 to 4, m1 pieces of Rt 1 may be identical to or different from each other. Also, m1 pieces two of the Rt 1 of Rt 1 each other may bond to each other to form a ring. If m2 is 2 ~ 4, m2 amino Rt 2, respectively may be the same or may be different. Further, m2 amino bonded to each other two Rt 2 together of Rt 2 may form a ring. If m3 is 2 ~ 4, m3 amino Rt 3 may each be the same or may be different. Also, m3 or two Rt 3 out of Rt 3 together may be bonded to each other to form a ring. When m4 is 2 to 4, m4 Rt 4 may be identical to or different from each other. In addition, two Rt 4 of m4 Rt 4 may be bonded to each other to form a ring. Further, Rt 1 and Rt 2 , Rt 1 and Rt 3 , Rt 1 and Rt 4 , Rt 2 and Rt 3 , Rt 2 and Rt 4 , and Rt 3 and Rt 4 may form a ring.
In formula (T-1), Rt 5 and Rt 6 each independently represent a hydrogen atom, an alkyl group, an aryl group, Ti (R M1 ) (R M2 ) (R M3 ), Zr (R M1 ) (R M2 ) ( RM3 ), Si ( RM1 ) ( RM2 ) ( RM3 ) or B ( RM1 ) ( RM2 ) is represented, and RM1 to RM3 each independently represent a substituent.
In formula (T-2), M 1 represents Ti ( RM 4 ) ( RM 5 ), Zr ( RM 4 ) ( RM 5 ), Si ( RM 4 ) ( RM 5 ) or B ( RM 4 ), Each of R M4 and R M5 independently represents a substituent.
In formula (T-3), M 2 represents Ti ( RM 6 ), Zr ( RM 6 ), Si ( RM 6 ) or B, RM 6 represents a substituent, and L 1 represents a divalent linking group Represents
　Ｒｔ1～Ｒｔ4、ＲM1～ＲM6が表す置換基としては、アルキル基、アリール基、複素環基、ニトロ基、シアノ基、ハロゲン原子、－ＯＲX1、－ＳＲX1、－ＣＯＲX1、－ＣＯＯＲX1、－ＯＣＯＲX1、－ＮＲX1ＲX2、－ＮＨＣＯＲX1、－ＣＯＮＲX1ＲX2、－ＮＨＣＯＮＲX1ＲX2、－ＮＨＣＯＯＲX1、－ＳＯ2ＲX1、－ＳＯ2ＯＲX1、－ＮＨＳＯ2ＲX1などが挙げられる。ＲX1およびＲX2は、それぞれ独立に、水素原子、アルキル基、アリール基または複素環基を表す。 The substituent represented by Rt 1 to Rt 4 and R M1 to R M6 is an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR X1 , -SR X1 , -COR X1 ,- COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 Etc. Each of R X1 and R X2 independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
　ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられる。
　置換基としてのアルキル基、ＲX1およびＲX2が表すアルキル基、式（Ｔ－１）におけるＲｔ5およびＲｔ6が表すアルキル基の炭素数は、１～２０が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。
　置換基としてのアリール基、ＲX1およびＲX2が表すアリール基、式（Ｔ－１）におけるＲｔ5およびＲｔ6が表すアリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。アリール基は、単環であってもよく、縮合環であってもよい。
　置換基としての複素環基、ならびに、ＲX1およびＲX2が表す複素環基は、５員環または６員環が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。複素環基を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。複素環基を構成するヘテロ原子の数は１～３が好ましい。複素環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。また、複素環基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。 The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The carbon number of the alkyl group as a substituent, the alkyl group represented by R X1 and R X2, and the alkyl group represented by Rt 5 and Rt 6 in the formula (T-1) is preferably 1 to 20. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
The carbon number of the aryl group as a substituent, the aryl group represented by R X1 and R X2, and the aryl group represented by Rt 5 and Rt 6 in the formula (T-1) is preferably 6 to 20, and more preferably 6 to 15 And 6 to 10 are more preferable. The aryl group may be a single ring or a fused ring.
The heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring. The heterocyclic group may be a single ring or may be a fused ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of hydrogen atoms may be substituted by the above-mentioned substituent.
　ｍ１～ｍ４は、それぞれ独立して０～４の整数を表し、０～３が好ましく、０～２がより好ましく、０または１が更に好ましく、０が特に好ましい。 M1 to m4 each independently represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
　Ｌ1が表す２価の連結基としては、アルキレン基、アリーレン基、－ＮＲ’－（Ｒ’は、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、水素原子が好ましい）、－ＳＯ2－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－、－Ｓ－およびこれらを組み合わせてなる基が挙げられる。 As the divalent linking group represented by L 1 , an alkylene group, an arylene group, —NR ′-(R ′ is a hydrogen atom, an alkyl group which may have a substituent, or a substituent, A preferable aryl group is represented, preferably a hydrogen atom), -SO 2- , -CO-, -COO-, -OCO-, -O-, -S- and a combination thereof.
　式（Ｔ－１）において、Ｒｔ5およびＲｔ6の少なくとも一方は水素原子であることが好ましく、Ｒｔ5およびＲｔ6の両方が水素原子であることがより好ましい。 In the formula (T-1), it is preferable that at least one of Rt 5 and Rt 6 is a hydrogen atom, and more preferably both Rt 5 and Rt 6 is a hydrogen atom.
　ピナコール化合物の具体例としては、ベンゾピナコール、１－ヒドロキシ－２－トリメチルシロキシ－１、１、２、２－テトラフェニルエタンなどが挙げられる。また、ピナコール化合物については、特表２０１４－５２１７７２号公報、特表２０１４－５２３９３９号公報、および、特表２０１４－５２１７７２号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of pinacol compounds include benzopinacol, 1-hydroxy-2-trimethylsiloxy-1, 1, 2, 2-tetraphenylethane and the like. Further, with regard to the pinacol compound, the descriptions in JP-A-2014-521772, JP-A-2014-523939, and JP-A-2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.
　α－ヒドロキシアセトフェノン化合物としては、下記式（Ｔ－１１）で表される化合物が挙げられる。
式（Ｔ－１１）
Figure JPOXMLDOC01-appb-C000016
　式中Ｒｔ11は、置換基を表し、Ｒｔ12およびＲｔ13は、それぞれ独立して、水素原子または置換基を表し、Ｒｔ12とＲｔ13が互いに結合して環を形成していてもよく、ｍは０～４の整数を表す。 Examples of the α-hydroxyacetophenone compound include compounds represented by the following formula (T-11).
Formula (T-11)
Figure JPOXMLDOC01-appb-C000016
Wherein Rt 11 represents a substituent, Rt 12 and Rt 13 are each independently, represent a hydrogen atom or a substituent, may form a ring Rt 12 and Rt 13 are mutually, m represents an integer of 0 to 4;
　Ｒｔ11が表す置換基としては、上述した置換基が挙げられ、アルキル基、アルコキシ基が好ましい。アルキル基およびアルコキシ基は、無置換であってもよく、置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。 The substituent Rt 11 represents, and a substituted group mentioned above, an alkyl group, an alkoxy group are preferred. The alkyl group and the alkoxy group may be unsubstituted or may have a substituent. As a substituent, a hydroxy group etc. are mentioned.
　Ｒｔ12およびＲｔ13は、それぞれ独立して、水素原子または置換基を表す。置換基としては、上述した置換基が挙げられ、アルキル基、アリール基が好ましい。また、Ｒｔ12とＲｔ13は互いに結合して環（好ましくは炭素数４～８の環、より好ましくは、炭素数４～８の脂肪族環）を形成していてもよい。 Rt 12 and Rt 13 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituents, and an alkyl group and an aryl group are preferable. Also, Rt 12 and Rt 13 ring bonded to each other (rings preferably 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms) may form.
　α－ヒドロキシアセトフェノン化合物の具体例としては、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オンなどが挙げられる。α－ヒドロキシアセトフェノン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－１８４、ＩＲＧＡＣＵＲＥ－２９５９（以上、ＢＡＳＦ社製）などが挙げられる。 Specific examples of the α-hydroxyacetophenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-l. On etc. are mentioned. Examples of commercially available α-hydroxyacetophenone compounds include IRGACURE-184, IRGACURE-2959 (manufactured by BASF AG), and the like.
　α－アミノアセトフェノン化合物としては、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－１－ブタノン、２－ジメチルアミノ－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノンなどが挙げられる。α－アミノアセトフェノン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、および、ＩＲＧＡＣＵＲＥ－３７９（以上、ＢＡＳＦ社製）などが挙げられる。 As an α-aminoacetophenone compound, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Examples include 1-butanone, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of commercially available α-aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (manufactured by BASF Corporation).
　ベンジルジメチルケタール化合物としては、２，２－ジメトキシ－２－フェニルアセトフェノンなどが挙げられる。市販品としては、ＩＲＧＡＣＵＲＥ－６５１（ＢＡＳＦ社製）などが挙げられる。 Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone and the like. Examples of commercially available products include IRGACURE-651 (manufactured by BASF).
　アゾ化合物としては、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス［Ｎ－（２－プロペニル）２－メチルプロピオンアミド］、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）等が挙げられる。アゾ化合物の市販品としては、Ｖ－７０、Ｖ－６５、Ｖ－６０、Ｖ－５９、Ｖ－４０、Ｖ－３０、Ｖ－５０１、Ｖ－６０１、ＶＥ－０７３、ＶＡ－０８０、ＶＡ－０８６、ＶＦ－０９６、ＶＡｍ－１１０、ＶＡｍ－１１１、ＶＡ－０４４、ＶＡ－０４６Ｂ、ＶＡ－０６０、ＶＡ－０６１、Ｖ－５０、ＶＡ－０５７、ＶＡ－０６７、ＶＲ－１１０（以上、和光純薬工業（株）製）等が挙げられる。
　有機過酸化物としては、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、アセチルアセトンパーオキサイド、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン、２，２－ビス（ｔｅｒｔ－ブチルパーオキシ）ブタン、ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、パラメタンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド、ジクミルパーオキサイド、ビス（ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、２，５－キサノイルパーオキサイド、過酸化こはく酸、過酸化ベンゾイル、２，４－ジクロロベンゾイルパーオキサイド、メタ－トルオイルパーオキサイド、ジイソプロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ジ－２－エトキシエチルパーオキシジカーボネート、ジメトキシイソプロピルパーオキシカーボネート、ジ（３－メチル－３－メトキシブチル）パーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシアセテート、ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシネオデカノエート、ｔｅｒｔ－ブチルパーオキシオクタノエート、ｔｅｒｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシラウレート、３，３’４，４’－テトラ－（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン、３，３’４，４’－テトラ－（ｔ－アミルパーオキシカルボニル）ベンゾフェノン、３，３’４，４’－テトラ－（ｔｅｒｔ－ヘキシルパーオキシカルボニル）ベンゾフェノン、３，３’４，４’－テトラ－（ｔｅｒｔ－オクチルパーオキシカルボニル）ベンゾフェノン、３，３’４，４’－テトラ－（クミルパーオキシカルボニル）ベンゾフェノン、３，３’４，４’－テトラ－（ｐ－イソプロピルクミルパーオキシカルボニル）ベンゾフェノン、カルボニルジ（ｔｅｒｔ－ブチルパーオキシ二水素二フタレート）、カルボニルジ（ｔｅｒｔ－ヘキシルパーオキシ二水素二フタレート）等が挙げられる。有機過酸化物の市販品としては、パーブチルＯ、パーブチルＺ、パーヘキサ２５Ｂ（以上、日油（株）製）等が挙げられる。 As the azo compound, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis ( 2-Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2- Propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like. Commercial products of the azo compound include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, VA-080, VA- 086, VF-096, VAm-110, VAm-111, VA-044, VA-046B, VA-060, VA-061, V-50, VA-057, VA-067, VR-110 (more, Wako Pure) Pharmaceutical Industries Ltd. make) etc. are mentioned.
As the organic peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide Peroxide, paramethan hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide Tert-Butylcumyl peroxide, dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-xanoyl Peroxide, Peroxysuccinic Acid, Benzoyl Peroxide, 2,4-Dichlorobenzoyl Peroxide, Meta-Toluoyl Peroxide, Diisopropyl Peroxy Dicarbonate, Di-2-Ethyl Hexyl Peroxy Dicarbonate, Di-2-Ethoxyethyl Peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butyl Peroxy neodecanoate, tert-butyl peroxyoctanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy laurate, 3,3'4,4'- Tetra- (tert-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (tert-hexylperoxy) Carbonyl) benzophenone, 3,3'4,4'-tetra- (tert-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4, 4'-Tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyl di (tert And -butylperoxydihydrogendiphthalate), carbonyldi (tert-hexylperoxydihydrogendiphthalate) and the like. Examples of commercially available organic peroxides include Perbutyl O, Perbutyl Z, Perhexa 25B (all manufactured by NOF Corporation).
　熱ラジカル重合開始剤の波長３６５ｎｍにおけるモル吸光係数は、１００Ｌ・ｍｏｌ-1・ｃｍ-1以下であることが好ましく、５０Ｌ・ｍｏｌ-1・ｃｍ-1以下であることがより好ましく、１０Ｌ・ｍｏｌ-1・ｃｍ-1以下であることが更に好ましい。熱ラジカル重合開始剤の波長３６５ｎｍにおけるモル吸光係数が１００Ｌ・ｍｏｌ-1・ｃｍ-1以下であれば、硬化性組成物の保管時中において、熱ラジカル重合開始剤からのラジカルの発生を効果的に抑制でき、硬化性組成物の保存安定性が良好である。 The molar absorption coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is preferably 100 L · mol −1 · cm −1 or less, more preferably 50 L · mol −1 · cm −1 or less, and 10 L · mol still more preferably -1 · cm -1 or less. If the molar absorptivity of the thermal radical polymerization initiator at a wavelength of 365 nm is 100 L · mol −1 · cm −1 or less, generation of radicals from the thermal radical polymerization initiator is effective during storage of the curable composition. The storage stability of the curable composition is good.
　なお、本発明において、熱ラジカル重合開始剤の波長３６５ｎｍにおけるモル吸光係数は、熱ラジカル重合開始剤を溶剤に溶解させて、熱ラジカル重合開始剤の５ｍｏｌ％溶液（測定溶液）を調整し、前述の測定溶液の吸光度を測定することで算出した。具体的には、前述の測定溶液を幅１ｃｍのガラスセルに入れ、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製ＵＶ－Ｖｉｓ－ＮＩＲスペクトルメーター（Ｃａｒｙ５０００）を用いて吸光度を測定し、下記式に当てはめて、波長３６５ｎｍにおけるモル吸光係数（Ｌ・ｍｏｌ-1・ｃｍ-1）を算出した。
Figure JPOXMLDOC01-appb-M000017
　上記式においてεはモル吸光係数（Ｌ・ｍｏｌ-1・ｃｍ-1）、Ａは吸光度、ｃは測定溶液の濃度（ｍｏｌ／Ｌ）、ｌは光路長（ｃｍ）を表す。 In the present invention, the molar absorption coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is prepared by dissolving the thermal radical polymerization initiator in a solvent to prepare a 5 mol% solution (measurement solution) of the thermal radical polymerization initiator. It was calculated by measuring the absorbance of the measurement solution of Specifically, the measurement solution described above is placed in a 1 cm wide glass cell, the absorbance is measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies, and the molar ratio at a wavelength of 365 nm is applied according to the following equation. The extinction coefficient (L · mol −1 · cm −1 ) was calculated.
Figure JPOXMLDOC01-appb-M000017
In the above equation, ε is the molar absorption coefficient (L · mol −1 · cm −1 ), A is the absorbance, c is the concentration of the measurement solution (mol / L), and l is the optical path length (cm).
　熱ラジカル重合開始剤のモル吸光係数の測定において、測定溶液の調製に用いる溶剤としては、アセトニトリル、クロロホルムが挙げられる。熱ラジカル重合開始剤がアセトニトリルに溶解する化合物である場合は、アセトニトリルを用いて測定溶液を調製する。熱ラジカル重合開始剤がアセトニトリルに溶解しないが、クロロホルムに溶解する化合物である場合は、クロロホルムを用いて測定溶液を調製する。また、熱ラジカル重合開始剤がアセトニトリルおよびクロロホルムに溶解しないが、ジメチルスルホキシドに溶解する化合物である場合は、ジメチルスルホキシドを用いて測定溶液を調製する。 Acetonitrile and chloroform are mentioned as a solvent used for preparation of a measurement solution in measurement of the molar absorption coefficient of a thermal radical polymerization initiator. When the thermal radical polymerization initiator is a compound that dissolves in acetonitrile, acetonitrile is used to prepare a measurement solution. When the thermal radical polymerization initiator is a compound which is insoluble in acetonitrile but soluble in chloroform, chloroform is used to prepare a measurement solution. When the thermal radical polymerization initiator is a compound which is insoluble in acetonitrile and chloroform but soluble in dimethyl sulfoxide, dimethyl sulfoxide is used to prepare a measurement solution.
　熱ラジカル重合開始剤の熱分解温度は１２０～２７０℃であることが好ましい。熱分解温度の上限は、２５０℃以下であることが好ましく、２２０℃以下であることがより好ましく、１９０℃以下であることがさらに好ましい。熱分解温度の下限は、１２０℃以上であることが好ましく、１５０℃以上であることがより好ましく、１７０℃以上であることがさらに好ましい。熱ラジカル重合開始剤の熱分解温度が１２０℃以上であれば、硬化性組成物の保管時中において、熱ラジカル重合開始剤からのラジカルの発生を効果的に抑制でき、硬化性組成物の保存安定性が良好である。また、熱ラジカル重合開始剤の熱分解温度が２７０℃以下であれば、加熱により速やかにラジカルを発生させることができ、硬化性組成物の硬化性が良好である。 The thermal decomposition temperature of the thermal radical polymerization initiator is preferably 120 to 270.degree. The upper limit of the thermal decomposition temperature is preferably 250 ° C. or less, more preferably 220 ° C. or less, and still more preferably 190 ° C. or less. The lower limit of the thermal decomposition temperature is preferably 120 ° C. or more, more preferably 150 ° C. or more, and still more preferably 170 ° C. or more. If the thermal decomposition temperature of the thermal radical polymerization initiator is 120 ° C. or higher, generation of radicals from the thermal radical polymerization initiator can be effectively suppressed during storage of the curable composition, and storage of the curable composition The stability is good. If the thermal decomposition temperature of the thermal radical polymerization initiator is 270 ° C. or less, radicals can be generated rapidly by heating, and the curability of the curable composition is good.
　なお、本発明において熱ラジカル重合開始剤の熱分解温度は熱重量・示差熱（ＴＧ－ＤＴＡ）測定により測定した値である。 In the present invention, the thermal decomposition temperature of the thermal radical polymerization initiator is a value measured by thermal weight / differential heat (TG-DTA) measurement.
　熱ラジカル重合開始剤の重量１％温度は、９０～２２０℃であることが好ましい。重量１％温度の上限は、２１５℃以下であることが好ましく、２１０℃以下であることがより好ましく、２００℃以下であることがさらに好ましい。重量１％温度の下限は、１００℃以上であることが好ましく、１２０℃以上であることがより好ましく、１５０℃以上であることがさらに好ましい。熱ラジカル重合開始剤の重量１％温度が上記範囲であれば、低温硬化性と組成物の保存安定性を両立させやすい。 The weight percent temperature of the thermal radical polymerization initiator is preferably 90 to 220 ° C. The upper limit of the weight 1% temperature is preferably 215 ° C. or less, more preferably 210 ° C. or less, and still more preferably 200 ° C. or less. The lower limit of the weight 1% temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 150 ° C. or higher. If the temperature by weight of the thermal radical polymerization initiator is in the above-mentioned range, it is easy to achieve both low temperature curability and storage stability of the composition.
　なお、本発明において熱ラジカル重合開始剤の重量１％温度とは、開始剤単体についてＴＧ－ＤＴＡ測定により測定したときの、重量が１％減少する温度である。 In the present invention, the 1% temperature by weight of the thermal radical polymerization initiator is a temperature at which the weight decreases by 1% as measured by TG-DTA measurement for the initiator alone.
　熱ラジカル重合開始剤の含有量は、硬化性組成物の全固形分に対し０．１～１０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、５質量％以下がより好ましい。
　また、熱ラジカル重合開始剤の含有量は、ラジカル重合性化合物の１００質量部に対して、０．０５～２００質量部であることが好ましい。下限は、１質量部以上が好ましく、１０質量部以上がより好ましく、５０質量部以上であってもよく、８０質量部以上であってもよく、１００質量部を超えてもよい。上限は、１５０質量部以下が好ましく、１２０質量部以下がより好ましい。熱ラジカル重合開始剤とラジカル重合性化合物との割合が上記範囲であれば、耐水密着性がより良好で、近赤外線吸収色素に由来する凝集物の発生がより抑制された硬化膜を形成し易い。
　また、熱ラジカル重合開始剤として、ピナコール化合物と、α－ヒドロキシアセトフェノン化合物とを併用する場合、ピナコール化合物の１００質量部に対してα－ヒドロキシアセトフェノン化合物の含有量が１～７０質量部であることが好ましく、３～６０質量部であることがより好ましく、５～５０質量部であることがさらに好ましい。
　本発明の硬化性組成物は、熱ラジカル重合開始剤を、１種のみ含んでいてもよいし、２種以上含んでいてもよい。熱ラジカル重合開始剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
　また、本発明では、光ラジカル重合開始剤を実質的に含まない構成とすることもできる。実質的に含まないとは、例えば、光ラジカル重合開始剤の含有量が、熱ラジカル重合開始剤の含有量の１質量％以下であることをいう。 The content of the thermal radical polymerization initiator is preferably 0.1 to 10% by mass with respect to the total solid content of the curable composition. 0.5 mass% or more is preferable, and, as for a lower limit, 1 mass% or more is more preferable. The upper limit is more preferably 5% by mass or less.
Further, the content of the thermal radical polymerization initiator is preferably 0.05 to 200 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. 1 mass part or more is preferable, 10 mass parts or more are more preferable, 50 mass parts or more may be sufficient, 80 mass parts or more may be sufficient, and a lower limit may exceed 100 mass parts. The upper limit is preferably 150 parts by mass or less, and more preferably 120 parts by mass or less. If the ratio between the thermal radical polymerization initiator and the radically polymerizable compound is in the above range, the water-resistant adhesion is better, and it is easy to form a cured film in which the generation of aggregates derived from the near-infrared absorbing dye is further suppressed .
When the pinacol compound and the α-hydroxyacetophenone compound are used in combination as the thermal radical polymerization initiator, the content of the α-hydroxyacetophenone compound is 1 to 70 parts by mass with respect to 100 parts by mass of the pinacol compound. Is preferable, 3 to 60 parts by mass is more preferable, and 5 to 50 parts by mass is more preferable.
The curable composition of the present invention may contain only one type of thermal radical polymerization initiator, or may contain two or more types. When 2 or more types of thermal radical polymerization initiators are included, it is preferable that the total amount of them becomes the said range.
Further, in the present invention, it may be configured not to substantially contain the photo radical polymerization initiator. The term "substantially free" means that, for example, the content of the photo radical polymerization initiator is 1% by mass or less of the content of the thermal radical polymerization initiator.
＜＜環状エーテル基を有する化合物＞＞
　本発明の硬化性組成物は、環状エーテル基を有する化合物を含有する。環状エーテル基としては、エポキシ基、オキセタニル基が挙げられ、エポキシ基が好ましい。環状エーテル基を有する化合物は、１分子内に環状エーテル基を２個以上有する化合物であることが好ましい。環状エーテル基を有する化合物における環状エーテル基の数の上限は、１００個以下であることが好ましく、１０個以下であることがより好ましく、５個以下であることが更に好ましい。 << Compound Having Cyclic Ether Group >>
The curable composition of the present invention contains a compound having a cyclic ether group. As a cyclic ether group, an epoxy group and oxetanyl group are mentioned, and an epoxy group is preferable. The compound having a cyclic ether group is preferably a compound having two or more cyclic ether groups in one molecule. The upper limit of the number of cyclic ether groups in the compound having cyclic ether groups is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less.
　環状エーテル基を有する化合物の環状エーテル基当量（環状エーテル基を有する化合物の分子量／環状エーテル基を有する化合物中の環状エーテル基の数）は、５０～４００ｇ／ｍｏｌであることが好ましい。環状エーテル基当量の下限は、１００ｇ／ｍｏｌ以上であることが好ましく、１５０ｇ／ｍｏｌ以上であることがより好ましい。上限は、３５０ｇ／ｍｏｌ以下であることが好ましく、３００ｇ／ｍｏｌ以下であることがより好ましい。
　また、環状エーテル基を有する化合物がエポキシ基を有する化合物である場合、エポキシ基当量（エポキシ基を有する化合物の分子量／エポキシ基を有する化合物中のエポキシ基の数）は、５０～４００ｇ／ｍｏｌであることが好ましい。エポキシ基当量の下限は、１００ｇ／ｍｏｌ以上であることが好ましく、１５０ｇ／ｍｏｌ以上であることがより好ましい。上限は、３５０ｇ／ｍｏｌ以下であることが好ましく、３００ｇ／ｍｏｌ以下であることがより好ましい。 The cyclic ether group equivalent of the compound having a cyclic ether group (molecular weight of the compound having a cyclic ether group / number of cyclic ether groups in the compound having a cyclic ether group) is preferably 50 to 400 g / mol. The lower limit of the cyclic ether group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more. The upper limit is preferably 350 g / mol or less, more preferably 300 g / mol or less.
When the compound having a cyclic ether group is a compound having an epoxy group, the epoxy group equivalent (molecular weight of the compound having an epoxy group / number of epoxy groups in the compound having an epoxy group) is 50 to 400 g / mol Is preferred. The lower limit of the epoxy group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more. The upper limit is preferably 350 g / mol or less, more preferably 300 g / mol or less.
　環状エーテル基を有する化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）であってもよい。環状エーテル基を有する化合物の分子量（ポリマーの場合は、重量平均分子量）は、２００～１０００００が好ましく、５００～５００００がより好ましい。分子量（ポリマーの場合は、重量平均分子量）の上限は、３０００以下が好ましく、２０００以下がより好ましく、１５００以下が更に好ましい。 The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more) It is also good. The molecular weight (weight average molecular weight in the case of a polymer) of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.
　本発明で用いられる環状エーテル基を有する化合物は、繰り返し単位を有する化合物であることが好ましい。環状エーテル基を有する化合物は、繰り返し単位を有する化合物である場合、環状エーテル基は繰り返し単位の側鎖に有していてもよく、主鎖末端に有していてもよい。なかでも、支持体に対して面吸着して、より優れた耐水密着性が得られやすいという理由から側鎖に環状エーテル基を有する化合物であることが好ましい。 The compound having a cyclic ether group used in the present invention is preferably a compound having a repeating unit. When the compound having a cyclic ether group is a compound having a repeating unit, the cyclic ether group may be on the side chain of the repeating unit or may be on the main chain terminal. Among them, compounds having a cyclic ether group in a side chain are preferable because they are surface-adsorbed to a support to easily obtain more excellent water adhesion.
　環状エーテル基を有する化合物は、芳香族環および／または脂肪族環を有する構造の化合物であることが好ましく、芳香族環を有する構造の化合物であることが更に好ましい。環状エーテル基を有する化合物として芳香族環を有する化合物を用いた場合、近赤外線吸収色素と相互作用し易く、耐水密着性のより優れた硬化膜を形成し易い。 The compound having a cyclic ether group is preferably a compound having a structure having an aromatic ring and / or an aliphatic ring, and more preferably a compound having a structure having an aromatic ring. When a compound having an aromatic ring is used as the compound having a cyclic ether group, the compound easily interacts with a near infrared absorbing dye and easily forms a cured film having more excellent water resistance.
　芳香族環としては、芳香族炭化水素環であることが好ましい。また、芳香族環は、単環であってもよく、縮合環であってもよい。芳香族環の具体例としては、ベンゼン環、ナフタレン環などが挙げられ、近赤外線吸収色素との相溶性が高まり、優れた耐水密着性が得られやすいという理由からナフタレン環を少なくとも含むことが好ましい。
　環状エーテル基を有する化合物が芳香族環を含む場合、芳香族環の数としては、１個以上であることが好ましく、近赤外線吸収色素との相溶性が高まり、優れた耐水密着性が得られやすいという理由から２個以上であることがより好ましい。上限は、５個以下が好ましく、４個以下がより好ましい。また、環状エーテル基を有する化合物が繰り返し単位を有する化合物である場合、一つの繰り返し単位における芳香族環の数は、１～１０個が好ましい。上限は、７個以下が好ましく、５個以下がより好ましい。下限は、２個以上が好ましい。なお、環状エーテル基を有する化合物における芳香族環の数とは、単環の芳香族環の数と、縮合環を構成する環の数の合計値である。例えば、環状エーテル基を有する化合物における芳香族環としてナフタレン環を有する化合物の場合、この環状エーテル基を有する化合物の芳香族環の数は２個である。環状エーテル基を有する化合物における芳香族環としてベンゼン環とナフタレン環を有する化合物の場合、この環状エーテル基を有する化合物の芳香族環の数は３個である。 The aromatic ring is preferably an aromatic hydrocarbon ring. The aromatic ring may be a single ring or a fused ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring and the like, and it is preferable to include at least a naphthalene ring because the compatibility with the near infrared absorbing dye is enhanced and the excellent water adhesion is easily obtained .
When the compound having a cyclic ether group contains an aromatic ring, the number of aromatic rings is preferably one or more, and the compatibility with the near infrared absorbing dye is enhanced, and excellent water-resistant adhesion is obtained. It is more preferable that it is 2 or more from the reason of being easy. The upper limit is preferably 5 or less, more preferably 4 or less. When the compound having a cyclic ether group is a compound having a repeating unit, the number of aromatic rings in one repeating unit is preferably 1 to 10. Seven or less are preferable and, as for the upper limit, five or less are more preferable. The lower limit is preferably 2 or more. The number of aromatic rings in the compound having a cyclic ether group is a total value of the number of monocyclic aromatic rings and the number of rings constituting a fused ring. For example, in the case of a compound having a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having this cyclic ether group is two. In the case of a compound having a benzene ring and a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having a cyclic ether group is three.
　環状エーテル基を有する化合物が、芳香族環および／または脂肪族環を有する構造の化合物である場合、環状エーテル基は、単結合または連結基を介して、芳香族環および／または脂肪族環に結合していることが好ましい。連結基としては、アルキレン基、アリーレン基、－ＮＲ’－（Ｒ’は、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、水素原子が好ましい）、－ＳＯ2－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－、－Ｓ－およびこれらを組み合わせてなる基が挙げられる。 When the compound having a cyclic ether group is a compound having a structure having an aromatic ring and / or an aliphatic ring, the cyclic ether group may be bonded to an aromatic ring and / or an aliphatic ring via a single bond or a linking group. It is preferred that they be linked. As a linking group, an alkylene group, an arylene group, -NR'- (R 'represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, hydrogen Atoms are preferable), -SO 2- , -CO-, -COO-, -OCO-, -O-, -S- and a group formed by combining these.
　環状エーテル基を有する化合物は、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。環状エーテル基を有する化合物の市販品としては、例えば、ナフタレン変性エポキシ樹脂として、ＥＰＩＣＬＯＮ　ＨＰ５０００、ＥＰＩＣＬＯＮ　ＨＰ４０３２Ｄ（以上、ＤＩＣ（株）製）などが挙げられる。アルキルジフェノール型エポキシ樹脂として、ＥＰＩＣＬＯＮ　８２０（ＤＩＣ（株）製）などが挙げられる。ビスフェノールＡ型エポキシ樹脂として、ｊＥＲ８２５、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１０５５、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８６０、ＥＰＩＣＬＯＮ１０５０、ＥＰＩＣＬＯＮ１０５１、ＥＰＩＣＬＯＮ１０５５（以上、ＤＩＣ（株）製）等が挙げられる。ビスフェノールＦ型エポキシ樹脂として、ｊＥＲ８０６、ｊＥＲ８０７、ｊＥＲ４００４、ｊＥＲ４００５、ｊＥＲ４００７、ｊＥＲ４０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８３０、ＥＰＩＣＬＯＮ８３５（以上、ＤＩＣ（株）製）、ＬＣＥ－２１、ＲＥ－６０２Ｓ（以上、日本化薬（株）製）等が挙げられる。フェノールノボラック型エポキシ樹脂として、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ１５７Ｓ６５（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ　Ｎ－７４０、ＥＰＩＣＬＯＮ　Ｎ－７７０、ＥＰＩＣＬＯＮ　Ｎ－７７５（以上、ＤＩＣ（株）製）等が挙げられる。クレゾールノボラック型エポキシ樹脂として、ＥＰＩＣＬＯＮ　Ｎ－６６０、ＥＰＩＣＬＯＮ　Ｎ－６６５、ＥＰＩＣＬＯＮ　Ｎ－６７０、ＥＰＩＣＬＯＮ　Ｎ－６７３、ＥＰＩＣＬＯＮ　Ｎ－６８０、ＥＰＩＣＬＯＮ　Ｎ－６９０、ＥＰＩＣＬＯＮ　Ｎ－６９５（以上、ＤＩＣ（株）製）、ＥＯＣＮ－１０２０（日本化薬（株）製）等が挙げられる。脂肪族エポキシ樹脂として、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０８０Ｓ、同ＥＰ－４０８５Ｓ、同ＥＰ－４０８８Ｓ（以上、（株）ＡＤＥＫＡ製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、ＥＨＰＥ３１５０、ＥＰＯＬＥＡＤ　ＰＢ　３６００、ＥＰＯＬＥＡＤ　ＰＢ　４７００（以上、（株）ダイセル製）、デナコール　ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ（以上、ナガセケムテックス（株）製）等が挙げられる。また、オキセタニル基を有する化合物として、ＯＸＴ－１０１、ＯＸＴ－１２１、ＯＸＴ－２１２、ＯＸＴ－２２１（以上、東亞合成（株）製）、ＯＸＥ－１０、ＯＸＥ－３０（以上、大阪有機化学工業（株）製）などが挙げられる。 Compounds having a cyclic ether group are described in paragraph Nos. 0034 to 0036 of JP2013-011869A, paragraph Nos. 0147 to 0156 of JP2014-043556A, and paragraph Nos. 0085 to 0092 of JP2014-089408A. The compounds described can also be used. The contents of these are incorporated herein. As a commercial item of the compound which has a cyclic ether group, EPICLON HP5000, EPICLON HP4032D (above, DIC Corporation make) etc. are mentioned as a naphthalene modified epoxy resin, for example. EPICLON 820 (made by DIC Corporation) etc. are mentioned as an alkyl diphenol type epoxy resin. As bisphenol A type epoxy resin, jER825, jER827, jER 828, jER1001, jER1002, jER1003, jER1005, jER1005, jER1009, jER1010 (above, Mitsubishi Chemical Co., Ltd. product), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, DIC) Manufactured by Co., Ltd., and the like. As bisphenol F-type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (above, DIC Corporation), LCE-21, RE-602S (above) Above, Nippon Kayaku Co., Ltd. product etc. are mentioned. As phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (above, Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. It can be mentioned. EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation) as cresol novolac epoxy resins And EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. As aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all, made by ADEKA), Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (all manufactured by Daicel Co., Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Co., Ltd.), and the like. Further, as a compound having an oxetanyl group, OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd.), OXE-10, OXE-30 (all, Osaka Organic Chemical Industry Co., Ltd.) and the like.
　環状エーテル基を有する化合物の含有量は、硬化性組成物の全固形分に対し、１～４５質量％が好ましい。下限は、２質量％以上が好ましく、３質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３０質量％以下がより好ましい。
　また、環状エーテル基を有する化合物の含有量は、近赤外線吸収色素の１００質量部に対して、５～５００質量部であることが好ましい。上限は、４００質量部以下であることが好ましく、３５０質量部以下であることがより好ましく、３００質量部以下であることが更に好ましい。下限は、１０質量部以上であることが好ましく、２０質量部以上であることがより好ましい。環状エーテル基を有する化合物と近赤外線吸収色素との割合が上記範囲であれば、耐水密着性がより良好で、近赤外線吸収色素に由来する凝集物の発生がより抑制された硬化膜を形成し易い。
　本発明の硬化性組成物は、環状エーテル基を有する化合物を、１種のみ含んでいてもよいし、２種以上含んでいてもよい。環状エーテル基を有する化合物を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the compound having a cyclic ether group is preferably 1 to 45% by mass with respect to the total solid content of the curable composition. 2 mass% or more is preferable, and, as for a lower limit, 3 mass% or more is more preferable. 40 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable.
In addition, the content of the compound having a cyclic ether group is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the near infrared absorbing dye. The upper limit is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and still more preferably 300 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. If the ratio of the compound having a cyclic ether group to the near infrared absorbing dye is in the above range, the cured film is formed with better water resistance and more suppressed generation of aggregates derived from the near infrared absorbing dye. easy.
The curable composition of the present invention may contain only one type of compound having a cyclic ether group, or may contain two or more types. When two or more compounds having a cyclic ether group are contained, the total amount thereof is preferably in the above range.
＜＜光ラジカル重合開始剤＞＞
　本発明の硬化性組成物は、さらに光ラジカル重合開始剤を含有することができる。光ラジカル重合開始剤としては、紫外線領域から可視領域の光線に対してラジカルを発生させる化合物が好ましい。 << photo radical polymerization initiator >>
The curable composition of the present invention can further contain a radical photopolymerization initiator. As a radical photopolymerization initiator, a compound which generates radicals for light in the ultraviolet region to the visible region is preferable.
　光ラジカル重合開始剤としては、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－アミノアセトフェノン化合物、α－ヒドロキシアセトフェノン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物が挙げられる。 As a radical photopolymerization initiator, trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-aminoacetophenone compounds, α-hydroxyacetophenone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, oniums The compounds include benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds.
　光ラジカル重合開始剤は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物であることがより好ましい。また、光ラジカル重合開始剤は、３６５ｎｍおよび４０５ｎｍの吸光度が高い化合物が好ましい。光ラジカル重合開始剤の波長３６５ｎｍにおけるモル吸光係数は、５Ｌ・ｍｏｌ-1・ｃｍ-1を超えることが好ましく、１０Ｌ・ｍｏｌ-1・ｃｍ-1を超えることがより好ましく、１５Ｌ・ｍｏｌ-1・ｃｍ-1を超えることが更に好ましく、５０Ｌ・ｍｏｌ-1・ｃｍ-1を超えることが更に一層好ましく、１００Ｌ・ｍｏｌ-1・ｃｍ-1を超えることが特に好ましい。 The photo radical polymerization initiator is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. The photo radical polymerization initiator is preferably a compound having a high absorbance at 365 nm and 405 nm. The molar absorption coefficient of the radical photopolymerization initiator at a wavelength of 365 nm is preferably more than 5 L · mol −1 · cm −1 , more preferably more than 10 L · mol −1 · cm −1 , and 15 L · mol −1 - more preferably of greater than cm -1, even more preferably greater than 50L · mol -1 · cm -1, and particularly preferably more than 100L · mol -1 · cm -1.
　本発明の硬化性組成物が光ラジカル重合開始剤を含有する場合、光ラジカル重合開始剤の含有量は、硬化性組成物の全固形分に対し２０質量％以下が好ましく、１５質量％がよリ好ましく、１０質量％が更に好ましい。下限は、例えば０．５質量％以上が好ましく、１質量％以上がより好ましい。光ラジカル重合開始剤は１種単独であってもよいし、２種以上を併用してもよい。光ラジカル重合開始剤を２種以上併用する場合は、合計量が上記範囲となることが好ましい。 When the curable composition of the present invention contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator is preferably 20% by mass or less, preferably 15% by mass, based on the total solid content of the curable composition. 10 mass% is more preferable. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The photo radical polymerization initiator may be used alone or in combination of two or more. When two or more types of photo radical polymerization initiators are used in combination, the total amount is preferably in the above range.
＜＜樹脂＞＞
　本発明の硬化性組成物は、上述した環状エーテル基を有する化合物、ラジカル重合性化合物以外の成分として、樹脂を含有することができる。樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。 << Resin >>
The curable composition of the present invention can contain a resin as a component other than the above-described compound having a cyclic ether group and the radically polymerizable compound. The resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder. In addition, resin used mainly for disperse | distributing particle | grains, such as a pigment, is also called a dispersing agent. However, such application of the resin is an example, and the resin can also be used for purposes other than such application.
　樹脂の重量平均分子量（Ｍｗ）は、２,０００～２,０００,０００が好ましい。上限は、１,０００,０００以下が好ましく、５００,０００以下がより好ましい。下限は、３,０００以上が好ましく、５,０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. 3,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.
　樹脂としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。環状オレフィン樹脂としては、耐熱性向上の観点からノルボルネン樹脂が好ましく用いることができる。ノルボルネン樹脂の市販品としては、例えば、ＪＳＲ（株）製のＡＲＴＯＮシリーズ（例えば、ＡＲＴＯＮ　Ｆ４５２０）などが挙げられる。また、樹脂は、国際公開ＷＯ２０１６／０８８６４５号公報の実施例に記載された樹脂、特開２０１７－５７２６５号公報に記載された樹脂、特開２０１７－３２６８５号公報に記載された樹脂、特開２０１７－０７５２４８号公報に記載された樹脂、特開２０１７－０６６２４０号公報に記載された樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。 As the resin, (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin And polyolefin resins, cyclic olefin resins, polyester resins and styrene resins. One of these resins may be used alone, or two or more thereof may be mixed and used. As cyclic olefin resin, norbornene resin can be preferably used from a viewpoint of heat resistance improvement. Examples of commercially available products of norbornene resin include ARTON series (for example, ARTON F 4520) manufactured by JSR Corporation. Further, as the resin, a resin described in an example of International Publication WO 2016/088645, a resin described in JP-A-2017-57265, a resin described in JP-A-2017-32685, JP-A-2017 It is also possible to use the resin described in Japanese Patent Application Laid-Open No. 0-75248 and the resin described in JP-A-2017-066240, the contents of which are incorporated herein.
　本発明で用いる樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂として用いることもできる。 The resin used in the present invention may have an acid group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable. These acid groups may be of only one type, or of two or more types. The resin having an acid group can also be used as an alkali-soluble resin.
　酸基を有する樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。具体例としては、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシ基を有するポリマーに酸無水物を付加させた樹脂が挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等、ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。また他のモノマーは、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマー、例えば、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等を用いることもできる。なお、これらの（メタ）アクリル酸と共重合可能な他のモノマーは１種のみであってもよいし、２種以上であってもよい。 As a resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples thereof include alkali-soluble polymers such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, novolac resin, etc. A phenolic resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxy group are mentioned. In particular, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenyl maleimide, N-cyclohexyl maleimide and the like can also be used. These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.
　酸基を有する樹脂は、さらに重合性基を有していてもよい。重合性基としては、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。市販品としては、ダイヤナールＮＲシリーズ（三菱レイヨン（株）製）、Ｐｈｏｔｏｍｅｒ６１７３（カルボキシル基含有ポリウレタンアクリレートオリゴマー、Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業株式会社製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれも（株）ダイセル製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー（株）製）、アクリキュアーＲＤ－Ｆ８(（株）日本触媒製)などが挙げられる。 The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. Commercially available products include Dianal NR series (Mitsubishi Rayon Co., Ltd.), Photomer 6173 (Carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all are Osaka organic) Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all from Daicel Co., Ltd.), Ebecryl 3800 (Daicel UBC Co., Ltd.), Acrycure RD-F8 (Co., Ltd.) Nippon Catalyst Co., Ltd. and the like.
　酸基を有する樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体なども好ましく用いることができる。 Resin having an acid group is benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) A multicomponent copolymer consisting of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, those obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-1420654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene Macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.
　酸基を有する樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分に由来する繰り返し単位を含むポリマーであることも好ましい。 The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that it is a polymer containing a repeating unit derived from a component.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（ＥＤ１）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000019
　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Figure JPOXMLDOC01-appb-C000019
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.
　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 As a specific example of the ether dimer, for example, paragraph “0317” of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification. The ether dimer may be only one type, or two or more types.
　酸基を有する樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000020
　式（Ｘ）において、Ｒ1は、水素原子またはメチル基を表し、Ｒ2は炭素数２～１０のアルキレン基を表し、Ｒ3は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000020
In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring. Represents an alkyl group of n represents an integer of 1 to 15.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。例えば、アクリベースＦＦ－４２６（藤倉化成（株）製）などが挙げられる。 The resin having an acid group is described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding US patent application publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408. No. 0076-0099 can be referred to, and the contents thereof are incorporated herein. Moreover, the resin which has an acidic radical can also use a commercial item. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) and the like can be mentioned.
　酸基を有する樹脂の酸価は、３０～２００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１２０ｍｇＫＯＨ／ｇ以下がより好ましい。 The acid value of the resin having an acid group is preferably 30 to 200 mg KOH / g. The lower limit is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more. 150 mgKOH / g or less is preferable and 120 mgKOH / g or less of an upper limit is more preferable.
　酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。以下の構造式中、Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000021
 As resin which has an acidic radical, resin of the following structure etc. are mentioned, for example. In the following structural formulae, Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000021
　本発明の硬化性組成物は、樹脂として、式（Ａ３－１）～（Ａ３－７）で表される繰り返し単位を有する樹脂を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000022
　式中、Ｒ5は水素原子またはアルキル基を表し、Ｌ4～Ｌ7は各々独立に単結合または２価の連結基を表し、Ｒ10～Ｒ13は各々独立にアルキル基またはアリール基を表す。Ｒ14およびＲ15は、各々独立に水素原子または置換基を表す。 In the curable composition of the present invention, it is also preferable to use, as a resin, a resin having repeating units represented by formulas (A3-1) to (A3-7).
Figure JPOXMLDOC01-appb-C000022
In the formula, R 5 represents a hydrogen atom or an alkyl group, L 4 to L 7 each independently represent a single bond or a divalent linking group, and R 10 to R 13 each independently represent an alkyl group or an aryl group . Each of R 14 and R 15 independently represents a hydrogen atom or a substituent.
　Ｒ5は、水素原子またはアルキル基を表す。アルキル基の炭素数は、１～５が好ましく、１～３がさらに好ましく、１が特に好ましい。Ｒ5は、水素原子またはメチル基が好ましい。 R 5 represents a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R 5 is preferably a hydrogen atom or a methyl group.
　Ｌ4～Ｌ7は、各々独立に単結合または２価の連結基を表す。２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ2－、－ＮＲ10－（Ｒ10は水素原子あるいはアルキル基を表し、水素原子が好ましい）
、または、これらの組み合わせからなる基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。アルキレン基は、置換基を有していてもよいが、無置換が好ましい。アルキレン基は、直鎖、分岐、環状のいずれであってもよい。また、環状のアルキレン基は、単環、多環のいずれであってもよい。アリーレン基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましい。 L 4 to L 7 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , and -NR 10- (R 10 is a hydrogen atom or Represents an alkyl group, preferably a hydrogen atom)
Or a group consisting of a combination of these. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. The cyclic alkylene group may be either monocyclic or polycyclic. The carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
　Ｒ10～Ｒ13が表すアルキル基は、直鎖状、分岐状または環状のいずれでもよく、環状が好ましい。アルキル基は置換基を有していてもよく、無置換であってもよい。アルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０がさらに好ましい。Ｒ10～Ｒ13が表すアリール基の炭素数は６～１８が好ましく、６～１２がより好ましく、６がさらに好ましい。Ｒ10は、環状のアルキル基またはアリール基が好ましい。Ｒ11、Ｒ12は、直鎖状または分岐状のアルキル基が好ましい。Ｒ13は、直鎖状のアルキル基、分岐状のアルキル基、または、アリール基が好ましい。 The alkyl group represented by R 10 to R 13 may be linear, branched or cyclic, preferably cyclic. The alkyl group may have a substituent or may be unsubstituted. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The carbon number of the aryl group represented by R 10 to R 13 is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. R 10 is preferably a cyclic alkyl group or an aryl group. R 11 and R 12 are preferably linear or branched alkyl groups. R 13 is preferably a linear alkyl group, a branched alkyl group or an aryl group.
　Ｒ14およびＲ15が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アラルキル基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、－ＮＲa1Ｒa2、－ＣＯＲa3、－ＣＯＯＲa4、－ＯＣＯＲa5、－ＮＨＣＯＲa6、－ＣＯＮＲa7Ｒa8、－ＮＨＣＯＮＲa9Ｒa10、－ＮＨＣＯＯＲa11、－ＳＯ2Ｒa12、－ＳＯ2ＯＲa13、－ＮＨＳＯ2Ｒa14または－ＳＯ2ＮＲa15Ｒa16が挙げられる。Ｒa1～Ｒa16は、各々独立に水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、または、ヘテロアリール基を表す。なかでも、Ｒ14およびＲ15の少なくとも一方は、シアノ基または－ＣＯＯＲa4を表すことが好ましい。Ｒa4は、水素原子、アルキル基またはアリール基を表すことが好ましい。 The substituent represented by R 14 and R 15 is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group , Alkylthio group, arylthio group, heteroarylthio group, -NR a1 R a2 , -COR a3 , -COOR a4 , -OCOR a5 , -NHCOR a6 , -CONR a7 R a8 , -NHCONR a9 R a10 , -NHCOOR a11 , And -SO 2 R a12 , -SO 2 OR a13 , -NHSO 2 R a14 or -SO 2 NR a15 R a16 . Each of R a1 to R a16 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Among them, at least one of R 14 and R 15 preferably represents a cyano group or -COOR a4 . R a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.
　式（Ａ３－７）で表される繰り返し単位を有する樹脂の市販品としては、ＡＲＴＯＮ　Ｆ４５２０（ＪＳＲ（株）製）などが挙げられる。また、式（Ａ３－７）で表される繰り返し単位を有する樹脂の詳細については、特開２０１１－１０００８４号公報の段落番号００５３～００７５、０１２７～０１３０の記載を参酌でき、この内容は本明細書に組み込まれる。 Examples of commercially available resins having a repeating unit represented by the formula (A3-7) include ARTON F 4520 (manufactured by JSR Corporation). In addition, for details of the resin having a repeating unit represented by the formula (A3-7), the descriptions in paragraphs “0053” to “0075” and “0127 to 0130” of JP 2011-100084 A can be referred to, and the contents thereof are described in this specification. Incorporated into the book.
　本発明の硬化性組成物は、分散剤としての樹脂を含むこともできる。特に、顔料を用いた場合、分散剤を含むことが好ましい。分散剤は、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。 The curable composition of the present invention can also contain a resin as a dispersant. In particular, when a pigment is used, it is preferable to include a dispersant. The dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. Resins consisting only of groups are more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mg KOH / g, more preferably 50 to 105 mg KOH / g, and still more preferably 60 to 105 mg KOH / g. Moreover, a basic dispersing agent (basic resin) represents resin whose quantity of a basic group is larger than the quantity of an acidic radical. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50% by mole, where the total amount of the amount of acid groups and the amount of basic groups is 100% by mole. The basic group possessed by the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、酸基を有する繰り返し単位を含むことが好ましい。分散剤として用いる樹脂が酸基を有する繰り返し単位を含むことにより、フォトリソグラフィ法によりパターン形成する際、画素の下地に発生する残渣をより低減することができる。 The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersing agent contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixel when forming a pattern by photolithography.
　分散剤として用いる樹脂は、グラフト共重合体であることも好ましい。グラフト共重合体は、グラフト鎖によって溶剤との親和性を有するために、顔料の分散性、および、経時後の分散安定性に優れる。グラフト共重合体の詳細は、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。また、グラフト共重合体の具体例は、下記の樹脂が挙げられる。以下の樹脂は酸基を有する樹脂（アルカリ可溶性樹脂）でもある。また、グラフト共重合体としては特開２０１２－２５５１２８号公報の段落番号００７２～００９４に記載の樹脂が挙げられ、この内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000023
 It is also preferable that the resin used as the dispersant is a graft copolymer. The graft copolymer is excellent in the dispersibility of the pigment and the dispersion stability after aging since it has an affinity to a solvent by the graft chain. The details of the graft copolymer can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Moreover, the following resin is mentioned as a specific example of a graft copolymer. The following resin is also a resin having an acid group (alkali soluble resin). Further, examples of the graft copolymer include the resins described in Paragraph Nos. 0072 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000023
　また、本発明において、樹脂（分散剤）は、主鎖および側鎖の少なくとも一方に窒素原子を含むオリゴイミン系分散剤を用いることも好ましい。オリゴイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する構造単位と、原子数４０～１０，０００の側鎖Ｙを含む側鎖とを有し、かつ主鎖および側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子とは、塩基性を呈する窒素原子であれば特に制限はない。オリゴイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。オリゴイミン系分散剤の具体例としては、例えば、以下が挙げられる。以下の樹脂は酸基を有する樹脂（アルカリ可溶性樹脂）でもある。また、オリゴイミン系分散剤としては、特開２０１２－２５５１２８号公報の段落番号０１６８～０１７４に記載の樹脂を用いることができる。
Figure JPOXMLDOC01-appb-C000024
 In the present invention, it is also preferable to use, as the resin (dispersant), an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine dispersant comprises a structural unit having a partial structure X having a functional group having a pKa of 14 or less and a side chain containing a side chain Y having an atom number of 40 to 10,000, and having a main chain and a side chain The resin which has a basic nitrogen atom in at least one side is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. With regard to the oligoimine dispersant, the description in paragraphs [0102] to [0166] of JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. Specific examples of the oligoimine dispersant include the following. The following resin is also a resin having an acid group (alkali soluble resin). Further, as the oligoimine dispersant, the resins described in paragraph Nos. 0168 to 0174 of JP 2012-255128 A can be used.
Figure JPOXMLDOC01-appb-C000024
　分散剤は、市販品としても入手可能であり、そのような具体例としては、Ｄｉｓｐｅｒｂｙｋ－１１１（ＢＹＫＣｈｅｍｉｅ社製）、ソルスパース７６５００（日本ルーブリゾール（株）製）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。また、上述した酸基を有する樹脂などを分散剤として用いることもできる。 The dispersant is also available as a commercial product, and as such specific examples, Disperbyk-111 (manufactured by BYK Chemie), Solsparse 76500 (manufactured by Nippon Lubrizol Co., Ltd.) and the like can be mentioned. In addition, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein. Moreover, the resin etc. which have an acidic radical mentioned above can also be used as a dispersing agent.
　本発明の硬化性組成物において、樹脂の含有量は、本発明の硬化性組成物の全固形分に対し、１～６０質量％が好ましい。下限は、５質量％以上が好ましく、７質量％以上がより好ましい。上限は、５０質量％以下が好ましく、３０質量％以下がより好ましい。 In the curable composition of the present invention, the content of the resin is preferably 1 to 60% by mass with respect to the total solid content of the curable composition of the present invention. 5 mass% or more is preferable, and, as for a lower limit, 7 mass% or more is more preferable. 50 mass% or less is preferable, and, as for the upper limit, 30 mass% or less is more preferable.
　また、樹脂として分散剤を含有する場合、分散剤の含有量は、硬化性組成物の全固形分に対して、０．１～４０質量％が好ましい。上限は、２０質量％以下が好ましく、１０質量％以下がさらに好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がさらに好ましい。また、分散剤の含有量は、顔料１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下が好ましく、６０質量部以下がより好ましい。下限は、２．５質量部以上が好ましく、５質量部以上がより好ましい。 When a dispersant is contained as a resin, the content of the dispersant is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. 0.5 mass% or more is preferable, and, as for a minimum, 1 mass% or more is more preferable. The content of the dispersant is preferably 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, and more preferably 60 parts by mass or less. 2.5 mass parts or more are preferable, and 5 mass parts or more are more preferable for a minimum.
＜＜有彩色着色剤＞＞
　本発明の硬化性組成物は、有彩色着色剤を含有することができる。本発明において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、波長４００ｎｍ以上６５０ｎｍ未満の範囲に吸収を有する着色剤が好ましい。 << Achromatic coloring agent >>
The curable composition of the present invention can contain a chromatic coloring agent. In the present invention, a chromatic coloring agent means a coloring agent other than a white coloring agent and a black coloring agent. The chromatic coloring agent is preferably a coloring agent having absorption in the wavelength range of 400 nm to less than 650 nm.
　有彩色着色剤は、顔料であってもよく、染料であってもよい。顔料は、有機顔料であることが好ましい。有機顔料としては、以下に示すものが挙られる。
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等（以上、青色顔料）、
　これら有機顔料は、単独若しくは種々組合せて用いることができる。 The chromatic coloring agent may be a pigment or a dye. The pigment is preferably an organic pigment. Examples of the organic pigment include the following.
Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 35, 53, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42 etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64, 66, 79, 80 (the above, blue pigment),
These organic pigments can be used alone or in various combinations.
　染料としては特に制限はなく、公知の染料が使用できる。化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が使用できる。また、これらの染料の多量体を用いてもよい。また、特開２０１５－０２８１４４号公報、特開２０１５－３４９６６号公報に記載の染料を用いることもできる。 The dye is not particularly limited, and known dyes can be used. The chemical structure includes pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used. In addition, multimers of these dyes may be used. Further, dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
　本発明の硬化性組成物が、有彩色着色剤を含有する場合、有彩色着色剤の含有量は、本発明の硬化性組成物の全固形分に対して０．１～７０質量％が好ましい。下限は、０．５質量％以上が好ましく、１．０質量％以上がより好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましい。また、有彩色着色剤と近赤外線吸収色素との合計量は、本発明の硬化性組成物の全固形分に対して１～８０質量％が好ましい。下限は、５質量％以上が好ましく、１０質量％以上がより好ましい。上限は、７０質量％以下が好ましく、６０質量％以下がより好ましい。本発明の硬化性組成物が、有彩色着色剤を２種以上含む場合、それらの合計量が上記範囲内であることが好ましい。
　また、本発明の硬化性組成物は、有彩色着色剤を実質的に含有しないことも好ましい。有彩色着色剤を実質的に含有しないとは、有彩色着色剤の含有量が、硬化性組成物の全固形分に対して０．０５質量％以下であることが好ましく、０．０１質量％以下であることがより好ましく、有彩色着色剤を含有しないことがさらに好ましい。 When the curable composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the curable composition of the present invention. . 0.5 mass% or more is preferable, and, as for a lower limit, 1.0 mass% or more is more preferable. 60 mass% or less is preferable, and, as for the upper limit, 50 mass% or less is more preferable. The total amount of the chromatic coloring agent and the near-infrared absorbing dye is preferably 1 to 80% by mass with respect to the total solid content of the curable composition of the present invention. 5 mass% or more is preferable, and, as for a lower limit, 10 mass% or more is more preferable. 70 mass% or less is preferable, and, as for the upper limit, 60 mass% or less is more preferable. When the curable composition of the present invention contains two or more types of chromatic coloring agents, the total amount thereof is preferably within the above range.
It is also preferable that the curable composition of the present invention contains substantially no chromatic coloring agent. The phrase "containing substantially no chromatic colorant" means that the content of the chromatic colorant is preferably 0.05% by mass or less, based on the total solid content of the curable composition, 0.01% by mass It is more preferable that it is the following and it is still more preferable that it does not contain a chromatic coloring agent.
＜＜赤外線を透過させて可視光を遮光する色材＞＞
　本発明の硬化性組成物は、赤外線を透過させて可視光を遮光する色材（以下、可視光を遮光する色材ともいう）を含有することもできる。
　本発明において、可視光を遮光する色材は、紫色から赤色の波長領域の光を吸収する色材であることが好ましい。また、本発明において、可視光を遮光する色材は、波長４５０～６５０ｎｍの波長領域の光を遮光する色材であることが好ましい。また、可視光を遮光する色材は、波長９００～１３００ｎｍの光を透過する色材であることが好ましい。
　本発明において、可視光を遮光する色材は、以下の（Ａ）および（Ｂ）の少なくとも一方の要件を満たすことが好ましい。
（Ａ）：２種類以上の有彩色着色剤を含み、２種以上の有彩色着色剤の組み合わせで黒色を形成している。
（Ｂ）：有機系黒色着色剤を含む。 << Colorant that transmits infrared rays and blocks visible light >>
The curable composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter, also referred to as a coloring material that blocks visible light).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the violet to red wavelength range. Further, in the present invention, the coloring material for blocking visible light is preferably a coloring material for blocking light in a wavelength range of 450 to 650 nm. Further, it is preferable that the coloring material that blocks visible light is a coloring material that transmits light with a wavelength of 900 to 1300 nm.
In the present invention, it is preferable that the coloring material that blocks visible light satisfy at least one of the following requirements (A) and (B).
(A): A black color is formed by a combination of two or more chromatic colorants, including two or more chromatic colorants.
(B): Contains an organic black colorant.
　有彩色着色剤としては、上述したものが挙げられる。有機系黒色着色剤としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報、国際公開ＷＯ２０１４／２０８３４８号公報、特表２０１５－５２５２６０号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。アゾメチン化合物としては、特開平１－１７０６０１号公報、特開平２－３４６６４号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。 As the chromatic coloring agent, those mentioned above can be mentioned. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds and the like, with bisbenzofuranone compounds and perylene compounds being preferred. As the bisbenzofuranone compounds, those described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication WO 2014/208348, JP-A-2015-525260, etc. The compound is mentioned, for example, it is available as "Irgaphor Black" made by BASF. As perylene compounds, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-32664 and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika.
　２種以上の有彩色着色剤の組み合わせで黒色を形成する場合の、有彩色着色剤の組み合わせとしては、例えば以下が挙げられる。
（１）黄色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（２）黄色着色剤、青色着色剤および赤色着色剤を含有する態様。
（３）黄色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（４）黄色着色剤および紫色着色剤を含有する態様。
（５）緑色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（６）紫色着色剤およびオレンジ色着色剤を含有する態様。
（７）緑色着色剤、紫色着色剤および赤色着色剤を含有する態様。
（８）緑色着色剤および赤色着色剤を含有する態様。 Examples of combinations of chromatic colorants in the case of forming a black color by the combination of two or more chromatic colorants include the following.
(1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant and a red colorant.
(2) An embodiment containing a yellow colorant, a blue colorant and a red colorant.
(3) An embodiment containing a yellow colorant, a purple colorant and a red colorant.
(4) An embodiment containing a yellow colorant and a purple colorant.
(5) An embodiment containing a green coloring agent, a blue coloring agent, a purple coloring agent and a red coloring agent.
(6) An embodiment containing a purple colorant and an orange colorant.
(7) An embodiment containing a green colorant, a purple colorant and a red colorant.
(8) An embodiment containing a green colorant and a red colorant.
　本発明の硬化性組成物が、可視光を遮光する色材を含有する場合、可視光を遮光する色材の含有量は、硬化性組成物の全固形分に対して６０質量％以下が好ましく、５０質量％以下がより好ましく、３０質量％以下がさらに好ましく、２０質量％以下がより一層好ましく、１５質量％以下が特に好ましい。下限は、例えば、０．１質量％以上とすることができ、０．５質量％以上とすることもできる。
　また、本発明の硬化性組成物は、可視光を遮光する色材を実質的に含有しないことも好ましい。可視光を遮光する色材を実質的に含有しないとは、可視光を遮光する色材の含有量が、硬化性組成物の全固形分に対して０．０５質量％以下であることが好ましく、０．０１質量％以下であることがより好ましく、可視光を遮光する色材を含有しないことがさらに好ましい。 When the curable composition of the present invention contains a coloring material that blocks visible light, the content of the coloring material that blocks visible light is preferably 60% by mass or less based on the total solid content of the curable composition. 50 mass% or less is more preferable, 30 mass% or less is more preferable, 20 mass% or less is still more preferable, and 15 mass% or less is especially preferable. The lower limit may be, for example, 0.1% by mass or more and may be 0.5% by mass or more.
Moreover, it is also preferable that the curable composition of this invention does not contain the coloring material which shades visible light substantially. The content of the coloring material for blocking visible light is preferably 0.05% by mass or less based on the total solid content of the curable composition that substantially no coloring material for blocking visible light is contained. It is more preferable that it is 0.01 mass% or less, and it is further more preferable not to contain the coloring material which shields visible light.
＜＜顔料誘導体＞＞
　本発明の硬化性組成物は、さらに顔料誘導体を含有することができる。顔料誘導体としては、色素骨格に、酸基および塩基性基から選ばれる少なくとも１種の基が結合した化合物が挙げられる。顔料誘導体としては、式（Ｂ１）で表される化合物が好ましい。 << pigment derivative >>
The curable composition of the present invention can further contain a pigment derivative. The pigment derivative includes a compound in which at least one group selected from an acid group and a basic group is bonded to a dye skeleton. As a pigment derivative, the compound represented by Formula (B1) is preferable.
Figure JPOXMLDOC01-appb-C000025
　式（Ｂ１）中、Ｐは色素骨格を表し、Ｌは単結合または連結基を表し、Ｘは酸基または塩基性基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。
Figure JPOXMLDOC01-appb-C000025
In formula (B1), P represents a dye skeleton, L represents a single bond or a linking group, X represents an acid group or a basic group, m represents an integer of 1 or more, n represents an integer of 1 or more In the case where m is 2 or more, the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.
　Ｐが表す色素骨格としては、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、キナクリドン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、ベンゾイソインドール色素骨格、チアジンインジゴ色素骨格、アゾ色素骨格、キノフタロン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、ジオキサジン色素骨格、ペリレン色素骨格、ペリノン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾチアゾール色素骨格、ベンゾイミダゾール色素骨格およびベンゾオキサゾール色素骨格から選ばれる少なくとも１種が好ましく、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、キナクリドン色素骨格およびベンゾイミダゾロン色素骨格から選ばれる少なくとも１種が更に好ましく、ピロロピロール色素骨格が特に好ましい。 The dye skeleton represented by P includes pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, thiazine indigo dye skeleton, azo dye skeleton, quinophthalone Dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzoimidazole dye skeleton, and at least one selected from benzoimidazole dye skeleton And at least one selected from pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton and benzimidazolone dye skeleton is more preferable, and pyrrolopyrrole dye skeleton is more preferable. Element skeleton is particularly preferred.
　Ｌが表す連結基としては、炭化水素基、複素環基、－ＮＲ－、－ＳＯ2－、－Ｓ－、－Ｏ－、－ＣＯ－もしくはこれらの組み合わせからなる基が挙げられる。Ｒは水素原子、アルキル基またはアリール基を表す。 The linking group represented by L includes a group consisting of a hydrocarbon group, a heterocyclic group, -NR-, -SO 2- , -S-, -O-, -CO- or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.
　Ｘが表す酸基としては、カルボキシル基、スルホ基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基等が挙げられる。カルボン酸アミド基としては、－ＮＨＣＯＲX1で表される基が好ましい。スルホン酸アミド基としては、－ＮＨＳＯ2ＲX2で表される基が好ましい。イミド酸基としては、－ＳＯ2ＮＨＳＯ2ＲX3、－ＣＯＮＨＳＯ2ＲX4、－ＣＯＮＨＣＯＲX5または－ＳＯ2ＮＨＣＯＲX6で表される基が好ましい。ＲX1～ＲX6は、それぞれ独立に、炭化水素基または複素環基を表す。ＲX1～ＲX6が表す、炭化水素基および複素環基は、さらに置換基を有してもよい。さらなる置換基としては、上述した式（ＰＰ）で説明した置換基Ｔが挙げられ、ハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。Ｘが表す塩基性基としてはアミノ基が挙げられる。Ｘが表す塩構造としては、上述した酸基または塩基性基の塩が挙げられる。 Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group. As the carboxamide group, a group represented by -NHCOR X1 is preferable. The sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 . The imide group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 . Each of R X1 to R X6 independently represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group which R X1 to R X6 represent may further have a substituent. As the further substituent, the substituent T described in the above-mentioned formula (PP) can be mentioned, and a halogen atom is preferable, and a fluorine atom is more preferable. An amino group is mentioned as a basic group which X represents. As a salt structure which X represents, the salt of the acid group or basic group mentioned above is mentioned.
　顔料誘導体としては、下記構造の化合物が挙げられる。また、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平１－２１７０７７号公報、特開平３－９９６１号公報、特開平３－２６７６７号公報、特開平３－１５３７８０号公報、特開平３－４５６６２号公報、特開平４－２８５６６９号公報、特開平６－１４５５４６号公報、特開平６－２１２０８８号公報、特開平６－２４０１５８号公報、特開平１０－３００６３号公報、特開平１０－１９５３２６号公報、国際公開ＷＯ２０１１／０２４８９６号公報の段落番号００８６～００９８、国際公開ＷＯ２０１２／１０２３９９号公報の段落番号００６３～００９４等に記載の化合物、特許第５２９９１５１号公報に記載の化合物を用いることもでき、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000026
 As a pigment derivative, the compound of the following structure is mentioned. Further, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, JP-A-3-153780. Patent Publication Nos. Hei 3-45662, Hei 4-285669, Hei 6-145546, Hei 6-212088, Hei 6-240158, Hei 10-30063, Compounds described in JP-A-10-195326, International Publication WO 2011/024896, paragraphs 0086 to 0098, International Publication WO 2012/102399, paragraphs 0063 to 0094, etc., Patent 5299151 Can also be used, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000026
　本発明の硬化性組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料１００質量部に対し、１～５０質量部が好ましい。下限値は、３質量部以上が好ましく、５質量部以上がより好ましい。上限値は、４０質量部以下が好ましく、３０質量部以下がより好ましい。顔料誘導体の含有量が上記範囲であれば、顔料の分散性を高めて、顔料の凝集を効率よく抑制できる。顔料誘導体は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 When the curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. 3 mass parts or more are preferable, and 5 mass parts or more of a lower limit are more preferable. 40 mass parts or less are preferable, and 30 mass parts or less are more preferable. When the content of the pigment derivative is in the above range, the dispersibility of the pigment can be enhanced, and the aggregation of the pigment can be efficiently suppressed. A pigment derivative may use only 1 type and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes said range.
＜＜溶剤＞＞
　本発明の硬化性組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤の例としては、例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類などが挙げられる。これらの詳細については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテートなどが挙げられる。また、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドも溶解性向上の観点から好ましい。本発明において有機溶剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。ただし溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << solvent >>
The curable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Examples of the organic solvent include, for example, esters, ethers, ketones, aromatic hydrocarbons and the like. For details of these, reference can be made to paragraph No. 0223 of International Publication WO 2015/166779, the content of which is incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of solubility improvement. In the present invention, the organic solvent may be used singly or in combination of two or more. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, or 10 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない溶剤を用いることが好ましい。溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 In the present invention, it is preferable to use a solvent having a low metal content. The metal content of the solvent is preferably, for example, 10 parts by weight (pps) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 As a method of removing impurities such as metal from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned. As a filter hole diameter of a filter used for filtration, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　溶剤には、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.
　本発明において、有機溶剤は、過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
　溶剤の含有量は、硬化性組成物の全量に対し、１０～９０質量％であることが好ましく、２０～８０質量％であることがより好ましく、２５～７５質量％であることが更に好ましい。溶剤を２種類以上用いる場合は、それらの合計量が上記範囲となることが好ましい。また、環境面等の理由により、硬化性組成物は、溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）を含有しないことが好ましい場合もある。 The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass, with respect to the total amount of the curable composition. When two or more solvents are used, the total amount thereof is preferably in the above range. Further, in some cases, it is preferable that the curable composition does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent because of environmental reasons and the like.
　溶剤の含有量は、硬化性組成物の全量に対し、１０～９７質量％であることが好ましい。下限は、３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることがさらに好ましく、６０質量％以上であることがより一層好ましく、７０質量％以上であることが特に好ましい。上限は、９６質量％以下であることが好ましく、９５質量％以下であることがより好ましい。 The content of the solvent is preferably 10 to 97% by mass with respect to the total amount of the curable composition. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and 70% by mass It is particularly preferable to be the above. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less.
＜＜重合禁止剤＞＞
　本発明の硬化性組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。重合禁止剤の含有量は、硬化性組成物の全固形分に対して、０．００１～５質量％が好ましい。 << polymerization inhibitor >>
The curable composition of the present invention can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts and the like). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass with respect to the total solid content of the curable composition.
＜＜シランカップリング剤＞＞
　本発明の硬化性組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応および縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、スチリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。シランカップリング剤は、ウレア基を有するシランカップリング剤が好ましい。 << Silane coupling agent >>
The curable composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Moreover, as functional groups other than a hydrolysable group, a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, for example And the like, and (meth) acryloyl group and epoxy group are preferable. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604, the contents of which are It is incorporated in the specification. The silane coupling agent is preferably a silane coupling agent having a urea group.
　シランカップリング剤の含有量は、硬化性組成物の全固形分に対して、０．０１～１５．０質量％が好ましく、０．０５～１０．０質量％がより好ましい。シランカップリング剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass, with respect to the total solid content of the curable composition. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably in the above range.
＜＜界面活性剤＞＞
　本発明の硬化性組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤は、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。 << Surfactant >>
The curable composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The surfactant can be referred to in paragraphs [0238 to 0245] of International Publication WO 2015/166779, the content of which is incorporated herein.
　本発明において、界面活性剤は、フッ素系界面活性剤であることが好ましい。本発明の硬化性組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。 In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the curable composition of the present invention, the liquid properties (in particular, the fluidity) can be further improved, and the liquid saving property can be further improved. In addition, a film with small thickness unevenness can also be formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.
　フッ素系界面活性剤として具体的には、特開２０１４－４１３１８号公報の段落番号００６０～００６４（対応する国際公開２０１４／１７６６９号公報の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 Specific examples of the fluorine-based surfactant include the surfactants described in paragraph Nos. 0060 to 0064 of JP-A-2014-41318 (paragraph Nos. 0060 to 0064 of corresponding international publication 2014/17669) and the like, and the like. Examples thereof include the surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, the contents of which are incorporated herein. As commercially available products of fluorine-based surfactants, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, R304, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Corporation), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, made by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, made by OMNOVA Corporation), etc. may be mentioned. .
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造で、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられる。 Further, the fluorine-based surfactant is a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied to volatilize the fluorine atom is also preferable. It can be used. As such a fluorochemical surfactant, Megafuck DS series (Chemical Chemical Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS -21 can be mentioned.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000027
　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (meth) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorinated surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000027
The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of repeating units is mol%.
　本発明においてフッ素系界面活性剤としては、フッ素原子および硬化性基を有する化合物（以下、含フッ素硬化性化合物ともいう）を用いることが好ましい。このような界面活性剤を用いることで、得られる膜の耐熱性をより向上できる。更には優れた耐溶剤性が得られる。含フッ素硬化性化合物を用いることで優れた耐溶剤性が得られる理由としては次によるものであると推測する。含フッ素硬化性化合物は表面自由エネルギーが低いため、例えば、基板などの支持体上に組成物を塗布して形成される塗膜においては、支持体とは反対側の塗膜表面近傍に含フッ素硬化性化合物が偏在しやすい。含フッ素硬化性化合物がこのように偏在した状態で本発明の硬化性組成物を硬化することで、基板から遠い側の表面に含フッ素硬化性化合物の硬化物の割合が多い領域が形成される。このような領域が存在することにより、膜を溶剤に浸漬させても、近赤外線吸収色素が膜表面から浸み出しにくくなり、優れた耐溶剤性が得られる。 In the present invention, as the fluorine-based surfactant, it is preferable to use a compound having a fluorine atom and a curable group (hereinafter, also referred to as a fluorine-containing curable compound). By using such a surfactant, the heat resistance of the resulting film can be further improved. Furthermore, excellent solvent resistance can be obtained. It is speculated that the reason why excellent solvent resistance can be obtained by using a fluorine-containing curable compound is as follows. Since a fluorine-containing curable compound has a low surface free energy, for example, in a coating film formed by applying a composition on a support such as a substrate, the fluorine-containing compound is present in the vicinity of the coating film surface opposite to the support The curable compound is likely to be unevenly distributed. By curing the curable composition of the present invention in such a state where the fluorine-containing curable compound is unevenly distributed, a region having a large proportion of the cured product of the fluorine-containing curable compound is formed on the surface far from the substrate. . Due to the presence of such a region, even if the film is immersed in a solvent, the near infrared absorbing dye is unlikely to leak from the film surface, and excellent solvent resistance can be obtained.
　含フッ素硬化性化合物が有する硬化性基としては、（メタ）アクリロイルオキシ基、エポキシ基およびオキセタニル基が挙げられ、（メタ）アクリロイルオキシ基が好ましい。 As a curable group which a fluorine-containing curable compound has, a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group are mentioned, A (meth) acryloyloxy group is preferable.
　含フッ素硬化性化合物は、フッ素原子で置換されたアルキレン基、フッ素原子で置換されたアルキル基、及び、フッ素原子で置換されたアリール基からなる群から選択される少なくとも１つを有することが好ましい。
　フッ素原子で置換されたアルキレン基としては、少なくとも１つの水素原子がフッ素原子で置換された直鎖状、分岐状又は環状のアルキレン基であることが好ましい。
　フッ素原子で置換されたアルキル基としては、少なくとも１つの水素原子がフッ素原子で置換された直鎖状、分岐状又は環状のアルキル基であることが好ましい。
　フッ素原子で置換されたアルキレン基及びフッ素原子で置換されたアルキル基中の炭素数は、１～２０であることが好ましく、１～１０であることがより好ましく、１～５であることがさらに好ましい。
　フッ素原子で置換されたアリール基は、アリール基がフッ素原子で直接に置換されているか、トリフルオロメチル基で置換されていることが好ましい。
　フッ素原子で置換されたアルキレン基、フッ素原子で置換されたアルキル基、及び、フッ素原子で置換されたアリール基は、フッ素原子以外の置換基をさらに有していてもよい。これらの具体例としては、例えば、特開２０１１－１０００８９号公報の段落０２６６～０２７２を参酌することができ、この内容は本明細書に組み込まれる。 The fluorine-containing curable compound preferably has at least one selected from the group consisting of a fluorine atom-substituted alkylene group, a fluorine atom-substituted alkyl group, and a fluorine atom-substituted aryl group. .
The fluorine atom-substituted alkylene group is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
The fluorine atom-substituted alkyl group is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
The carbon number in the fluorine atom-substituted alkylene group and the fluorine atom-substituted alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. preferable.
The aryl group substituted with a fluorine atom is preferably such that the aryl group is directly substituted with a fluorine atom or substituted with a trifluoromethyl group.
The fluorine atom-substituted alkylene group, the fluorine atom-substituted alkyl group, and the fluorine atom-substituted aryl group may further have a substituent other than a fluorine atom. As specific examples of these, for example, paragraphs 0266 to 0272 of JP-A-2011-100089 can be referred to, and the contents thereof are incorporated in the present specification.
　含フッ素硬化性化合物は、フルオロエーテル基と硬化性基とを含む化合物であることが好ましい。フルオロエーテル基としては、フッ素原子で置換されたアルキレン基と酸素原子とが連結した基Ｘ（式（Ｘ）で表される基）が挙げられる。フルオロエーテル基は、パーフルオロアルキレンエーテル基であることが好ましい。なお、パーフルオロアルキレンエーテル基とは、下記式（Ｘ）におけるＬAがパーフルオロアルキレン基であることを意味する。パーフルオロアルキレン基とは、アルキレン基中の水素原子がすべてフッ素原子で置換された基を意味する。
　式（Ｘ）　　－（ＬA－Ｏ）ｎ－　上記ＬAは、フッ素原子で置換されたアルキレン基を表す。フッ素原子で置換されたアルキレン基の炭素数は、１～２０であることが好ましく、１～１０であることがより好ましく、１～５であることがさらに好ましい。フッ素原子で置換されたアルキレン基は直鎖状であっても、分岐状であってもよい。ｎは１以上の整数を表し、１～５０が好ましく、１～２０がより好ましい。なお、ｎが２以上の場合、複数の－（ＬA－Ｏ）－中のＬAは同一であってもよく、異なっていてもよい。 The fluorine-containing curable compound is preferably a compound containing a fluoroether group and a curable group. As a fluoroether group, group X (group represented by Formula (X)) which the alkylene group substituted by the fluorine atom and the oxygen atom connected is mentioned. The fluoroether group is preferably a perfluoroalkylene ether group. Note that the perfluoroalkylene ether groups, which means that L A in formula (X) is a perfluoroalkylene group. The perfluoroalkylene group means a group in which all hydrogen atoms in the alkylene group are substituted with a fluorine atom.
Formula (X)-(L A -O) n-The above L A represents an alkylene group substituted by a fluorine atom. The carbon number of the fluorine atom-substituted alkylene group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. The fluorine atom-substituted alkylene group may be linear or branched. n represents an integer of 1 or more, preferably 1 to 50, and more preferably 1 to 20. When n is 2 or more, a plurality of - (L A -O) - L A medium may be the same or different.
　含フッ素硬化性化合物は、モノマーであってもよく、ポリマーであってもよいが、ポリマーであることが好ましい。 The fluorine-containing curable compound may be a monomer or a polymer, but is preferably a polymer.
　含フッ素硬化性化合物がポリマーである場合、ポリマーは、フルオロエーテル基を有する繰り返し単位と、硬化性基を有する繰り返し単位とを有するポリマーであることが好ましい。また、下記式（Ｂ１）で表される繰り返し単位と、下記式（Ｂ２）で表される繰り返し単位及び式（Ｂ３）で表される繰り返し単位の少なくとも一方とを有するポリマーであることが好ましく、下記式（Ｂ１）で表される繰り返し単位と、下記式（Ｂ３）で表される繰り返し単位とを有するポリマーであることがより好ましい。 When the fluorine-containing curable compound is a polymer, the polymer is preferably a polymer having a repeating unit having a fluoroether group and a repeating unit having a curable group. The polymer is preferably a polymer having a repeating unit represented by the following formula (B1), at least one of a repeating unit represented by the following formula (B2) and a repeating unit represented by the formula (B3), It is more preferable that it is a polymer which has a repeating unit represented by a following formula (B1), and a repeating unit represented by a following formula (B3).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（Ｂ１）～（Ｂ３）中、Ｒ1～Ｒ11は、それぞれ独立に、水素原子、アルキル基、又は、ハロゲン原子を表す。Ｌ1～Ｌ4は、それぞれ独立に、単結合又は２価の連結基を表す。Ｘ1は、（メタ）アクリロイルオキシ基、エポキシ基、又はオキセタニル基を表し、Ｘ2はフッ素原子で置換されたアルキル基またはフッ素原子で置換されたアリール基を表し、Ｘ3は式（Ｘ）で表される基を表す。 In the formulas (B1) to (B3), R 1 to R 11 each independently represent a hydrogen atom, an alkyl group or a halogen atom. L 1 to L 4 each independently represent a single bond or a divalent linking group. X 1 represents a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group, X 2 represents a fluorine atom-substituted alkyl group or a fluorine atom-substituted aryl group, and X 3 represents a group of formula (X) Represents a group represented by
　式（Ｂ１）～（Ｂ３）中、Ｒ1～Ｒ11は、それぞれ独立に、水素原子又はアルキル基であることが好ましい。Ｒ1～Ｒ11がアルキル基を表す場合、炭素数１～３のアルキル基が好ましい。Ｒ1～Ｒ11がハロゲン原子を表す場合、フッ素原子が好ましい。
　式（Ｂ１）～（Ｂ３）中、Ｌ1～Ｌ4が２価の連結基を表す場合、２価の連結基としては、ハロゲン原子が置換していてもよいアルキレン基、ハロゲン原子が置換していてもよいアリーレン基、－ＮＲ12－、－ＣＯＮＲ12－、－ＣＯ－、－ＣＯ2－、－ＳＯ2ＮＲ12－、－Ｏ－、－Ｓ－、－ＳＯ2－、又は、これらの組み合わせが挙げられる。なかでも、炭素数２～１０のハロゲン原子が置換していてもよいアルキレン基及び炭素数６～１２のハロゲン原子が置換していてもよいアリーレン基からなる群から選択される少なくとも１種、又は、これらの基と－ＮＲ12－、－ＣＯＮＲ12－、－ＣＯ－、－ＣＯ2－、－ＳＯ2ＮＲ12－、－Ｏ－、－Ｓ－、及び－ＳＯ2－からなる群から選択される少なくとも１種の基との組み合わせからなる基が好ましく、炭素数２～１０のハロゲン原子が置換していてもよいアルキレン基、－ＣＯ2－、－Ｏ－、－ＣＯ－、－ＣＯＮＲ12－、又は、これらの基の組み合わせからなる基がより好ましい。ここで、上記Ｒ12は、水素原子又はメチル基を表す。 In formulas (B1) to (B3), R 1 to R 11 are preferably each independently a hydrogen atom or an alkyl group. When R 1 to R 11 represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable. When R 1 to R 11 represent a halogen atom, a fluorine atom is preferred.
In formulas (B1) to (B3), when L 1 to L 4 represent a divalent linking group, as the divalent linking group, an alkylene group which may be substituted by a halogen atom, or a halogen atom is substituted which may be an arylene group, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, - SO 2 NR 12 -, - O -, - S -, - SO 2 -, or, of A combination is mentioned. Among them, at least one selected from the group consisting of an alkylene group which may be substituted by a C 2-10 halogen atom and an arylene group which may be substituted a C 6-12 halogen atom, or these groups and -NR 12 -, - CONR 12 - , - CO -, - CO 2 -, - SO 2 NR 12 -, - O -, - S-, and -SO 2 - is selected from the group consisting of that at least one group is preferably a combination of a group, an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon atoms, -CO 2 -, - O - , - CO -, - CONR 12 - Or a group consisting of a combination of these groups is more preferred. Here, the above R 12 represents a hydrogen atom or a methyl group.
　上記式（Ｂ１）で表される繰り返し単位の含有量は、含フッ素硬化性化合物中の全繰り返し単位に対して、３０～９５モル％であることが好ましく、４５～９０モル％であることがより好ましい。
　上記式（Ｂ２）で表される繰り返し単位及び式（Ｂ３）で表される繰り返し単位の合計含有量は、含フッ素硬化性化合物中の全繰り返し単位に対して、５～７０モル％であることが好ましく、１０～６０モル％であることがより好ましい。なお、式（Ｂ２）で表される繰り返し単位が含まれず、式（Ｂ３）で表される繰り返し単位が含まれる場合は、式（Ｂ２）で表される繰り返し単位の含有量は０モル％として、式（Ｂ３）で表される繰り返し単位の含有量が上記範囲であることが好ましい。 The content of the repeating unit represented by the above formula (B1) is preferably 30 to 95 mol%, more preferably 45 to 90 mol%, based on all repeating units in the fluorine-containing curable compound. More preferable.
The total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) is 5 to 70 mol% with respect to all the repeating units in the fluorine-containing curable compound. Is preferable, and 10 to 60 mol% is more preferable. In addition, when the repeating unit represented by Formula (B2) is not contained but the repeating unit represented by Formula (B3) is included, content of the repeating unit represented by Formula (B2) is 0 mol%. The content of the repeating unit represented by the formula (B3) is preferably in the above range.
　また、含フッ素硬化性化合物は、上記式（Ｂ１）～（Ｂ３）で表される繰り返し単位以外の他の繰り返し単位を有していてもよい。他の繰り返し単位の含有量は、含フッ素硬化性化合物中の全繰り返し単位に対して、１０モル％以下であることが好ましく、１モル％以下であることがより好ましい。 Further, the fluorine-containing curable compound may have another repeating unit other than the repeating units represented by the above formulas (B1) to (B3). The content of the other repeating units is preferably 10 mol% or less, and more preferably 1 mol% or less, based on all the repeating units in the fluorine-containing curable compound.
　含フッ素硬化性化合物がポリマーである場合、重量平均分子量が５，０００～１００，０００であることが好ましく、７，０００～５０，０００であることがより好ましい。また、分散度（重量平均分子量／数平均分子量）は、１．８０～３．００であることが好ましく、２．００～２．９０であることがより好ましい。 When the fluorine-containing curable compound is a polymer, the weight average molecular weight is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. The degree of dispersion (weight-average molecular weight / number-average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.
　含フッ素硬化性化合物の市販品としては、例えば、ＤＩＣ社製のメガファックＲＳ－７２－Ｋ、メガファックＲＳ－７５、メガファックＲＳ－７６－Ｅ、メガファックＲＳ－７６－ＮＳ、メガファックＲＳ－７７等を利用することができる。含フッ素硬化性化合物は、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。また、含フッ素硬化性化合物として（Ｂ１－１）で表される繰り返し単位と、式（Ｂ３－１）で表される繰り返し単位とを有するポリマーを用いることもできる。式（Ｂ３－１）中、Ｘは、フルオロメチレン基またはフルオロエチレン基を表し、ｒは繰り返し単位数を表す。
Figure JPOXMLDOC01-appb-C000029
 As a commercial item of the fluorine-containing curable compound, for example, Megafuck RS-72-K, Megafuck RS-75, Megafuck RS-76-E, Megafuck RS-76-NS, Megafuck RS manufactured by DIC Corporation. -77 mag can be used. As the fluorine-containing curable compound, compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965 and compounds described in paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can be used. It can also be used. Further, a polymer having a repeating unit represented by (B1-1) and a repeating unit represented by formula (B3-1) can also be used as the fluorine-containing curable compound. In formula (B3-1), X represents a fluoromethylene group or a fluoroethylene group, and r represents the number of repeating units.
Figure JPOXMLDOC01-appb-C000029
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレートおよびプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 As nonionic surfactants, glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronics 304, 701, 704, 901, 904, 150R1 (BA). Made by F company, Solsparse 20000 (made by Nippon Lubrisol Ltd.), NCW-101, NCW-1001, NCW-1002 (made by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), and the like.
　界面活性剤の含有量は、本発明の硬化性組成物の全固形分に対して、０．００１質量％～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。界面活性剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 The content of the surfactant is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% to 3.0% by mass, with respect to the total solid content of the curable composition of the present invention. The surfactant may be only one type, or two or more types. In the case of two or more types, the total amount is preferably in the above range.
＜＜紫外線吸収剤＞＞
　本発明の硬化性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノブタジエン化合物、メチルジベンゾイル化合物、クマリン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－６８８１４号公報の段落番号０３１７～０３３４の記載を参酌でき、これらの内容は本明細書に組み込まれる。共役ジエン化合物の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としてはミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）を用いてもよい。
　紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、０．０１～１０質量％が好ましく、０．０１～５質量％がより好ましい。本発明において、紫外線吸収剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 << UV Absorbent >>
The curable composition of the present invention can contain an ultraviolet absorber. As the ultraviolet light absorber, conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds and the like can be used. The details of these can be referred to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, the contents of which are incorporated herein. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). In addition, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) made by Miyoshi Yushi may be used.
The content of the UV 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. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
＜＜その他成分＞＞
　本発明の硬化性組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱重合禁止剤、可塑剤、密着促進剤およびその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、潜在酸化防止剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分は、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、この内容は本明細書に組み込まれる。また、酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。酸化防止剤としては、分子量５００以上のフェノール化合物、分子量５００以上の亜リン酸エステル化合物または分子量５００以上のチオエーテル化合物がより好ましい。これらは２種以上を混合して使用してもよい。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。特に、フェノール性水酸基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、および亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）からなる群から選ばれる少なくとも１種の化合物が挙げられる。これらは、市販品として入手できる。例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（（株）ＡＤＥＫＡ）などが挙げられる。また、酸化防止剤として、国際公開ＷＯ１７／００６６００号公報に記載された多官能ヒンダードアミン酸化防止剤を用いることもできる。酸化防止剤の含有量は、硬化性組成物の全固形分に対して、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。
　潜在酸化防止剤とは、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物であることが好ましい。潜在酸化防止剤としては国際公開ＷＯ２０１４／０２１０２３号公報、国際公開ＷＯ２０１７／０３０００５号公報、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。 << Other ingredients >>
The curable composition of the present invention may contain, if necessary, a sensitizer, a curing accelerator, a filler, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter and other auxiliary agents (eg, conductive particles, fillers) Defoamer, flame retardant, leveling agent, peeling accelerator, antioxidant, latent antioxidant, perfume, surface tension regulator, chain transfer agent, etc.). These components can be referred to the description of paragraph Nos. 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074, the contents of which are incorporated herein. Moreover, a phenol compound, a phosphorous acid ester compound, a thioether compound etc. are mentioned as antioxidant. As the antioxidant, a phenolic compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. You may mix and use these 2 or more types. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. In particular, compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group are preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, a phosphorus antioxidant can also be used conveniently for antioxidant. As a phosphorus antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl And at least one compound selected from the group consisting of oxy] ethyl] amine and ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl). These are commercially available. For example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, Adekastab AO-330 ADEKA) and the like. Moreover, the polyfunctional hindered amine antioxidant described in International Publication WO17 / 006600 can also be used as an antioxidant. The content of the antioxidant is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass, with respect to the total solid content of the curable composition. One type of antioxidant may be sufficient, and 2 or more types may be sufficient as it. In the case of two or more types, the total amount is preferably in the above range.
A latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C., or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Thus, it is preferable that the compound is a compound which functions as an antioxidant by eliminating the protective group. Examples of the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. Examples of commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like.
　本発明の硬化性組成物の粘度（２３℃）は、例えば、塗布により膜を形成する場合、１～１００ｍＰａ・ｓであることが好ましい。下限は、２ｍＰａ・ｓ以上がより好ましく、３ｍＰａ・ｓ以上がさらに好ましい。上限は、５０ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下がさらに好ましく、１５ｍＰａ・ｓ以下が特に好ましい。 The viscosity (23 ° C.) of the curable composition of the present invention is preferably, for example, 1 to 100 mPa · s when a film is formed by coating. The lower limit is preferably 2 mPa · s or more, more preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, still more preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
　本発明の硬化性組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 There is no limitation in particular as a storage container of the curable composition of this invention, A well-known storage container can be used. In addition, as a container, for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use. As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.
　本発明の硬化性組成物の用途は、特に限定されない。例えば、近赤外線カットフィルタなどの形成に好ましく用いることができる。また、本発明の硬化性組成物において、さらに、可視光を遮光する色材を含有させることで、特定の波長以上の近赤外線のみを透過可能な赤外線透過フィルタを形成することもできる。 The application of the curable composition of the present invention is not particularly limited. For example, it can be preferably used for forming a near infrared cut filter or the like. Moreover, the curable composition of this invention WHEREIN: Furthermore, the infrared rays permeable filter which can permeate | transmit only the near infrared rays more than a specific wavelength can also be formed by containing the color material which shields visible light.
＜硬化性組成物の調製方法＞
　本発明の硬化性組成物は、前述の成分を混合して調製できる。硬化性組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して硬化性組成物を調製してもよいし、必要に応じては、各成分を適宜配合した２つ以上の溶液または分散液をあらかじめ調製し、使用時（塗布時）にこれらを混合して硬化性組成物として調製してもよい。 <Method of Preparing Curable Composition>
The curable composition of the present invention can be prepared by mixing the above-mentioned components. In the preparation of the curable composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare a curable composition, and if necessary, two or more solutions containing each component as appropriate The dispersion may be prepared in advance and mixed at the time of use (at the time of application) to prepare a curable composition.
　また、本発明の硬化性組成物が顔料などの粒子を含む場合は、粒子を分散させるプロセスを含むことが好ましい。粒子を分散させるプロセスにおいて、粒子の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における粒子の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、粒子を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセスおよび分散機を好適に使用出来る。また粒子を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 When the curable composition of the present invention contains particles such as pigments, it is preferable to include a process of dispersing the particles. In the process of dispersing the particles, mechanical force used to disperse the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverizing of particles in a sand mill (bead mill), it is preferable to use a bead having a small diameter, treatment under conditions in which the pulverizing efficiency is enhanced by increasing the packing ratio of beads, or the like. Moreover, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverizing treatment. In addition, the process of dispersing particles and the dispersing machine are the dispersion technology and industrial application centering on "Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005" and "suspension (solid / liquid dispersion system)" The process and the dispersing machine described in Paragraph No. 0022 of JP-A-2015-157893, published on October 10, 1978, can be preferably used. In the process of dispersing the particles, the particles may be subjected to a refinement process in a salt milling step. The materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
　硬化性組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、硬化性組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。
　フィルタの孔径は、０．０１～７．０μｍ程度が適しており、好ましくは０．０１～３．０μｍ程度であり、さらに好ましくは０．０５～０．５μｍ程度である。フィルタの孔径が上記範囲であれば、微細な異物を確実に除去できる。また、ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。具体的には、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）のフィルタカートリッジが挙げられる。 In the preparation of the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign substances and reducing defects. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. For example, a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP) Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore diameter of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore diameter of the filter is in the above range, fine foreign particles can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, filter cartridges of SBP type series (SBP 008 and the like), TPR type series (TPR 002, TPR 005 and the like), and SHPX type series (SHPX 003 and the like) manufactured by Loki Techno, Inc. can be mentioned.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。
　また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）または株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
　第２のフィルタは、第１のフィルタと同様の素材等で形成されたものを使用することができる。
　また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using filters, different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
Moreover, you may combine the filter of a different hole diameter within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it is possible to select from various filters provided by Nippon Pall Co., Ltd. (DFA 4201 NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. can do.
The second filter can be made of the same material as the first filter.
In addition, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.
＜硬化膜＞
　本発明の硬化膜は、上述した本発明の硬化性組成物から得られるものである。本発明の硬化膜は、近赤外線カットフィルタとして好ましく用いることができる。また、熱線遮蔽フィルタや赤外線透過フィルタとして用いることもできる。本発明の硬化膜は、支持体上に積層して用いてもよく、支持体から剥離して用いてもよい。本発明の硬化膜は、パターンを有していてもよく、パターンを有さない膜（平坦膜）であってもよい。 <Cured film>
The cured film of the present invention is obtained from the above-mentioned curable composition of the present invention. The cured film of the present invention can be preferably used as a near infrared cut filter. Moreover, it can also be used as a heat ray blocking filter or an infrared rays transmission filter. The cured film of the present invention may be used by being laminated on a support, or may be used by peeling it from the support. The cured film of the present invention may have a pattern or may be a film having no pattern (flat film).
　本発明の硬化膜の厚さは、目的に応じて適宜調整できる。硬化膜の厚さは、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 The thickness of the cured film of the present invention can be appropriately adjusted according to the purpose. 20 micrometers or less are preferable, as for the thickness of a cured film, 10 micrometers or less are more preferable, and 5 micrometers or less are more preferable. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.
　本発明の硬化膜は、波長７００～１３００ｎｍの範囲に極大吸収波長を有することが好ましく、波長７００～１０００ｎｍの範囲に極大吸収波長を有することがより好ましく、波長７２０～９８０ｎｍの範囲に極大吸収波長を有することがさらに好ましく、波長７４０～９６０ｎｍの範囲に極大吸収波長を有することが特に好ましい。 The cured film of the present invention preferably has a maximum absorption wavelength in the range of 700 to 1300 nm, more preferably a maximum absorption wavelength in the range of 700 to 1000 nm, and a maximum absorption wavelength in the range of 720 to 980 nm. It is more preferable that the light absorption wavelength is in the range of 740 to 960 nm.
　本発明の硬化膜を近赤外線カットフィルタとして用いる場合は、本発明の硬化膜は以下の（１）～（４）のうちの少なくとも１つの条件を満たすことが好ましく、（１）～（４）のすべての条件を満たすことがさらに好ましい。
（１）波長４００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、８５％以上がさらに好ましく、９０％以上が特に好ましい。
（２）波長５００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。
（３）波長６００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。
（４）波長６５０ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が特に好ましい。 When the cured film of the present invention is used as a near infrared cut filter, the cured film of the present invention preferably satisfies at least one of the following (1) to (4), and (1) to (4) It is further preferred that all the conditions of
(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.
(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
　本発明の硬化膜は、有彩色着色剤を含むカラーフィルタと組み合わせて用いることもできる。カラーフィルタは、有彩色着色剤を含む着色組成物を用いて製造できる。有彩色着色剤としては、本発明の硬化性組成物に含んでもよいものとして挙げた有彩色着色剤が挙げられる。また、本発明の硬化膜に有彩色着色剤を含有させて、近赤外線カットフィルタとカラーフィルタとしての機能を備えたフィルタとしてもよい。 The cured film of the present invention can also be used in combination with a color filter containing a chromatic coloring agent. A color filter can be manufactured using a coloring composition containing a chromatic coloring agent. The chromatic coloring agents include the chromatic coloring agents mentioned as those which may be contained in the curable composition of the present invention. In addition, the cured film of the present invention may contain a chromatic coloring agent to provide a near infrared cut filter and a filter having a function as a color filter.
　本発明の硬化膜を、カラーフィルタと組み合わせて用いる場合、本発明の硬化膜の光路上にカラーフィルタが配置されていることが好ましい。例えば、本発明の硬化膜とカラーフィルタとを積層して積層体として用いることができる。積層体においては、本発明の硬化膜とカラーフィルタとは、両者が厚み方向で隣接していてもよく、隣接していなくてもよい。本発明の硬化膜とカラーフィルタとが厚み方向で隣接していない場合は、カラーフィルタが形成された支持体とは別の支持体に、本発明の硬化膜が形成されていてもよく、本発明の硬化膜とカラーフィルタとの間に、固体撮像素子を構成する他の部材（例えば、マイクロレンズ、平坦化層など）が介在していてもよい。 When using the cured film of this invention in combination with a color filter, it is preferable that the color filter is arrange | positioned on the optical path of the cured film of this invention. For example, the cured film of the present invention and a color filter can be laminated and used as a laminate. In the laminate, the cured film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the cured film of the present invention and the color filter are not adjacent in the thickness direction, the cured film of the present invention may be formed on a support other than the support on which the color filter is formed. Between the cured film of the invention and the color filter, another member (for example, a microlens, a planarizing layer, etc.) constituting the solid-state imaging device may be interposed.
　なお、本発明において、近赤外線カットフィルタとは、可視領域の波長の光（可視光）を透過させ、近赤外領域の波長の光（近赤外線）の少なくとも一部を遮光するフィルタを意味する。近赤外線カットフィルタは、可視領域の波長の光をすべて透過するものであってもよく、可視領域の波長の光のうち、特定の波長領域の光を透過させ、特定の波長領域の光を遮光するものであってもよい。また、本発明において、カラーフィルタとは、可視領域の波長の光のうち、特定の波長領域の光を透過させ、特定の波長領域の光を遮光するフィルタを意味する。また、本発明において、赤外線透過フィルタとは、可視光を遮光し、近赤外線の少なくとも一部を透過させるフィルタを意味する。 In the present invention, the near-infrared cut filter means a filter that transmits light in the visible region (visible light) and blocks at least part of light in the near-infrared region (near infrared). . The near infrared cut filter may transmit all light of wavelengths in the visible region, and among light of wavelengths in the visible region, transmits light of a specific wavelength region and blocks light of a specific wavelength region It may be Further, in the present invention, the color filter means a filter that transmits light in a specific wavelength range and blocks light in a specific wavelength range, out of light of wavelengths in the visible range. Further, in the present invention, the infrared transmission filter means a filter that shields visible light and transmits at least a part of near infrared light.
　本発明の硬化膜は、銅を含有するガラスとの密着性および耐水密着性に優れるため、銅を含有するガラスに積層して用いることが好ましい。銅を含有するガラスとしては、銅を含有する燐酸塩ガラス、銅を含有する弗燐酸塩ガラスなどが挙げられる。銅を含有するガラスにおける銅の含有量としては、０．１～２０質量％であることが好ましく、０．３～１７質量％であることがより好ましく、０．５～１５質量％であることが更に好ましい。 The cured film of the present invention is preferably used by being laminated on a glass containing copper since it is excellent in adhesion to a glass containing copper and water-resistant adhesion. Examples of copper-containing glass include copper-containing phosphate glass and copper-containing fluorophosphate glass. The content of copper in the glass containing copper is preferably 0.1 to 20% by mass, more preferably 0.3 to 17% by mass, and 0.5 to 15% by mass Is more preferred.
　銅を含有するガラスは、波長７００～１１００ｎｍの範囲に極大吸収波長を有することが好ましい。下限は８００ｎｍ以上であることが好ましく、９００ｎｍ以上であることがより好ましい。上限は１０５０ｎｍ以下であることが好ましく、１０００ｎｍ以下であることがより好ましい。 The copper-containing glass preferably has a maximum absorption wavelength in the wavelength range of 700 to 1100 nm. The lower limit is preferably 800 nm or more, and more preferably 900 nm or more. The upper limit is preferably 1050 nm or less, more preferably 1000 nm or less.
　銅を含有するガラスの具体例としては、以下が挙げられる。
　（１）質量％で、Ｐ2Ｏ5　４６～７０％、ＡｌＦ3　０．２～２０％、ΣＲＦ（Ｒ＝Ｌｉ、Ｎａ、Ｋ）０～２５％、ΣＲ’Ｆ2（Ｒ’＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ）　１～５０％からなり、Ｆ　０．５～３２％、Ｏ　２６～５４％を含む基礎ガラス１００質量部に対し、外掛け表示でＣｕＯ　０．５～７質量部を含むガラス。
　（２）質量％で、Ｐ2Ｏ5　２５～６０％、Ａｌ2Ｏ3　１～１３％、ＭｇＯ　１～１０％、ＣａＯ　１～１６％、ＢａＯ　１～２６％、ＳｒＯ　０～１６％、ＺｎＯ　０～１６％、Ｌｉ2Ｏ　０～１３％、Ｎａ2Ｏ　０～１０％、Ｋ2Ｏ　０～１１％、ＣｕＯ　１～７％、ΣＲＯ（Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）　１５～４０％、ΣＲ’2Ｏ（Ｒ’＝Ｌｉ、Ｎａ、Ｋ）　３～１８％（ただし、３９％モル量までのＯ2-イオンがＦで置換されている）からなるガラス。
　（３）質量％で、Ｐ2Ｏ5　５～４５％、ＡｌＦ3　１～３５％、ΣＲＦ（Ｒ＝Ｌｉ、Ｎａ、Ｋ）　０～４０％、ΣＲ’Ｆ2（Ｒ’＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、Ｚｎ）　１０～７５％、Ｒ”Ｆm（Ｒ”＝Ｌａ、Ｙ、Ｃｄ、Ｓｉ、Ｂ、Ｚｒ、Ｔａ、ｍはＲ”の原子価に相当する数）　０～１５％（ただし、弗化物総合計量の７０％までを酸化物に置換可能）、およびＣｕＯ　０．２～１５％を含むガラス。
　（４）カチオン％で、Ｐ5+　１１～４３％、Ａｌ3+　１～２９％、ΣＲカチオン（Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、Ｚｎ）　１４～５０％、ΣＲ’カチオン（Ｒ’＝Ｌｉ、Ｎａ、Ｋ）　０～４３％、ΣＲ”カチオン（Ｒ”＝Ｌａ、Ｙ、Ｇｄ、Ｓｉ、Ｂ、Ｚｒ、Ｔａ）　０～８％、およびＣｕ2+　０．５～１３％を含み、さらにアニオン％でＦ-　１７～８０％含有するガラス。
　（５）カチオン％で、Ｐ5+　２３～４１％、Ａｌ3+　４～１６％、Ｌｉ+　１１～４０％、Ｎａ+　３～１３％、ΣＲカチオン（Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ）　１２～５３％、およびＣｕ2+　２．６～４．７％を含み、さらにアニオン％でＦ-　２５～４８％、およびＯ2-　５２～７５％を含むガラス。
　（６）質量％で、Ｐ2Ｏ5　７０～８５％、Ａｌ2Ｏ3　８～１７％、Ｂ2Ｏ3　１～１０％、Ｌｉ2Ｏ　０～３％、Ｎａ2Ｏ　０～５％、Ｋ2Ｏ　０～５％、ただし、ΣＲ2Ｏ（Ｒ＝Ｌｉ、Ｎａ、Ｋ）　０．１～５％、ＳｉＯ2　０～３％からなる基礎ガラス１００質量部に対し、外割でＣｕＯを０．１～５質量部含むガラス。 The following is mentioned as a specific example of the glass containing copper.
(1) In mass%, 46 to 70% of P 2 O 5 , 0.2 to 20% of AlF 3 , 0 to 25% of RFRF (R = Li, Na, K), RR′F 2 (R ′ = Mg, Ca, Sr, Ba, Pb) 0.5 to 7 parts by mass of CuO in an external display with respect to 100 parts by mass of the base glass containing 1 to 50% of F, 0.5 to 32% of F, and 26 to 54% of O Containing glass.
(2) 25 to 60% of P 2 O 5, 1 to 13% of Al 2 O 3 , 1 to 10% of MgO, 1 to 16% of CaO, 1 to 26% of BaO 1 to 26%, SrO 0 to 16%, ZnO by mass% 0 to 16%, Li 2 O 0 to 13%, Na 2 O 0 to 10%, K 2 O 0 to 11%, CuO 1 to 7%, RORO (R = Mg, Ca, Sr, Ba) 15 to 40 %, RR ′ 2 O (R ′ = Li, Na, K) 3-18% (however, up to 39% molar amount of O 2− ions are replaced by F).
(3) 5 to 45% of P 2 O 5 , 1 to 35% of AlF 3 , 0 to 40% of RFRF (R = Li, Na, K), ΣR′F 2 (R ′ = Mg, Ca, in mass%) Sr, Ba, Pb, Zn) 10 to 75%, R′′F m (R ′ ′ = La, Y, Cd, Si, B, Zr, Ta, m is a number corresponding to the valence of R ′ ′) 0 to 15 % (But up to 70% of the total fluoride weight can be replaced by oxides), and glass containing 0.2 to 15% of CuO.
(4) P5 + 11 to 43%, Al 3 + 1 to 29%, RR cation (R = Mg, Ca, Sr, Ba, Pb, Zn) 14 to 50%, カ チ オ ン R 'cation (R '= Li, Na, K) 0 to 43%, ΣR ′ ′ cation (R ′ ′ = La, Y, Gd, Si, B, Zr, Ta) 0 to 8%, and Cu 2+ 0.5 to 13% Glass further containing F - 17 to 80% as anion%.
(5) In cation%, P 5+ 23 to 41%, Al 3 + 4 to 16%, Li + 11 to 40%, Na + 3 to 13%, ΣR cation (R = Mg, Ca, Sr, Ba, Zn) 12 ~ 53%, and Cu 2+ comprises 2.6 to 4.7%, further anionic% in F - 25 ~ 48%, and O 2- 52 ~ 75% glass containing.
(6) mass%, P 2 O 5 70 ~ 85%, Al 2 O 3 8 ~ 17%, B 2 O 3 1 ~ 10%, Li 2 O 0 ~ 3%, Na 2 O 0 ~ 5%, CuO is externally added to 100 parts by mass of a base glass consisting of 0 to 5% K 2 O, where ΣR 2 O (R = Li, Na, K) 0.1 to 5%, and SiO 2 0 to 3% Glass containing 0.1 to 5 parts by mass.
　銅を含有するガラスは、市販品を用いることもできる。銅を含有するガラスの市販品としては、ＮＦ－５０（ＡＧＣテクノグラス（株）製）等が挙げられる。 A commercial product can also be used for the glass containing copper. Commercially available products of copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.) and the like.
　本発明の硬化膜は、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や、赤外線センサ、画像表示装置などの各種装置に用いることができる。 The cured film of the present invention can be used for various devices such as solid-state imaging devices such as CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.
＜硬化膜の製造方法＞
　次に、本発明の硬化膜の製造方法について説明する。本発明の硬化膜の製造方法は、上述した本発明の硬化性組成物を適用して硬化性組成物層を形成する工程と、硬化性組成物層を加熱硬化する工程と、を含む。 <Method for producing cured film>
Next, the manufacturing method of the cured film of this invention is demonstrated. The method for producing a cured film of the present invention includes the steps of applying the curable composition of the present invention described above to form a curable composition layer, and heat curing the curable composition layer.
　硬化膜の製造方法において、硬化性組成物は支持体上に適用することが好ましい。支持体としては、シリコン、無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラスなどの材質で構成された基材、銅を含有するガラス基材などが挙げられる。これらの基材には、有機膜や無機膜などが形成されていてもよい。有機膜の材料としては、例えば上述した樹脂が挙げられる。また、支持体としては、上述した樹脂で構成された基材を用いることもできる。また、支持体には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、支持体には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、支持体には、必要により、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層が設けられていてもよい。本発明においては、支持体として銅を含有するガラス基材を用いることが好ましい。従来は、銅を含有するガラス基材に対して密着性の良い硬化膜を形成することは困難であったが、本発明の硬化膜は、銅を含有するガラス基材に対しても密着性が良好で、更には耐水密着性にも優れるので、本発明の効果がより顕著である。 In the method for producing a cured film, the curable composition is preferably applied on a support. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a glass substrate containing copper. An organic film, an inorganic film, etc. may be formed in these base materials. Examples of the material of the organic film include the above-mentioned resins. Moreover, the base material comprised with resin mentioned above can also be used as a support body. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In addition, a black matrix may be formed on the support to separate each pixel. In addition, the support may be provided with a subbing layer, if necessary, for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate. In the present invention, it is preferable to use a glass substrate containing copper as a support. Conventionally, it has been difficult to form a cured film having good adhesion to a glass substrate containing copper, but the cured film of the present invention is also adhesive to a glass substrate containing copper. The effect of the present invention is more remarkable because the water resistance is excellent and the adhesion to water is also excellent.
　支持体への硬化性組成物の適用方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、硬化性組成物の適用方法については、国際公開ＷＯ２０１７／０３０１７４号公報、国際公開ＷＯ２０１７／０１８４１９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 As a method of applying the curable composition to a support, known methods can be used. For example, dropping method (drop casting); slit coating method; spraying method; roll coating method; spin coating method (spin coating); cast coating method; slit and spin method; pre-wet method (for example, JP 2009-145395A) Methods described in the publication); Ink jet (for example, on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. The application method in the inkjet is not particularly limited, and for example, the method (in particular, page 115-) disclosed in "Spread and usable inkjet-unlimited possibilities in patents-published in February 2005, resident Betechno Research" Methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. It can be mentioned. In addition, regarding the application method of the curable composition, the descriptions of International Publication WO 2017/030174 and International Publication WO 2017/018419 can be referred to, and the contents thereof are incorporated herein.
　支持体に適用した硬化性組成物に対し、乾燥（プリベーク）を行ってもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下がさらに好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０秒～３０００秒が好ましく、４０～２５００秒がより好ましく、８０～２２０秒がさらに好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。 The curable composition applied to the support may be dried (prebaked). When prebaking is performed, the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less. The lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more. The pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven or the like.
　硬化性組成物層を加熱硬化する工程において、加熱温度としては、例えば１００～２４０℃が好ましい。膜硬化の観点から、１８０～２３０℃がより好ましい。加熱時間としては、２～１０分が好ましく、４～８分がより好ましい。加熱硬化処理は、ホットプレート、オーブン等で行うことができる。 In the step of heat curing the curable composition layer, the heating temperature is preferably, for example, 100 to 240.degree. From the viewpoint of film curing, 180 to 230 ° C. is more preferable. The heating time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes. The heat curing treatment can be performed with a hot plate, an oven or the like.
　本発明の硬化膜の製造方法においては、さらにパターンを形成する工程を含んでいてもよい。パターン形成方法としては、フォトリソグラフィ法を用いたパターン形成方法や、ドライエッチング法を用いたパターン形成方法が挙げられる。フォトリソグラフィ法でパターンを形成する場合、パターンを形成した後、硬化性組成物層の加熱硬化を行うことが好ましい。また、ドライエッチング法でパターンを形成する場合、硬化性組成物層の加熱硬化を行った後、パターンを形成することが好ましい。なお、本発明の硬化膜を平坦膜として用いる場合には、パターンを形成する工程を行わなくてもよい。以下、パターンを形成する工程について詳細に説明する。 The method for producing a cured film of the present invention may further include the step of forming a pattern. Examples of the pattern formation method include a pattern formation method using a photolithography method and a pattern formation method using a dry etching method. When forming a pattern by the photolithographic method, it is preferable to heat-harden a curable composition layer, after forming a pattern. Moreover, when forming a pattern by the dry etching method, it is preferable to form a pattern, after heat-hardening a curable composition layer. In addition, when using the cured film of this invention as a flat film, it is not necessary to perform the process of forming a pattern. Hereinafter, the process of forming a pattern will be described in detail.
（フォトリソグラフィ法でパターン形成する場合）
　フォトリソグラフィ法でのパターン形成方法は、本発明の硬化性組成物を適用して形成した硬化性組成物層に対しパターン状に露光する工程（露光工程）と、未露光部の硬化性組成物層を除去することにより現像してパターンを形成する工程（現像工程）と、を含むことが好ましい。必要に応じて、現像されたパターンをベークする工程（ポストベーク工程）を設けてもよい。 (When forming a pattern by photolithography)
The pattern formation method in the photolithography method comprises a step of exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern (exposure step), and a curable composition of the unexposed area It is preferable to include the step of developing by removing the layer to form a pattern (developing step). If necessary, a step (post-baking step) may be provided to bake the developed pattern.
（ドライエッチング法でパターン形成する場合）
　ドライエッチング法でのパターン形成は、硬化性組成物層を加熱硬化して硬化物層を形成し、次いで、この硬化物層上にパターニングされたフォトレジスト層を形成し、次いで、パターニングされたフォトレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングするなどの方法で行うことができる。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 (When patterning by dry etching)
In the dry etching method, the curable composition layer is cured by heating to form a cured layer, and then a patterned photoresist layer is formed on the cured layer, and then a patterned photo is formed. It can carry out by methods, such as dry-etching using etching gas with respect to a hardened | cured material layer, using a resist layer as a mask. For the pattern formation by the dry etching method, the description in paragraphs “0010” to “0067” of JP 2013-064993 can be referred to, and the contents thereof are incorporated in the present specification.
＜近赤外線カットフィルタ＞
　次に、本発明の近赤外線カットフィルタについて説明する。本発明の近赤外線カットフィルタは、本発明の硬化膜を含む。本発明の近赤外線カットフィルタは、支持体上に本発明の硬化膜を有することが好ましい。支持体としては、シリコン、無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラスなどの材質で構成された基材、銅を含有するガラス基材などが挙げられ、銅を含有するガラス基材が好ましい。 <Near infrared cut filter>
Next, the near infrared cut filter of the present invention will be described. The near infrared cut filter of the present invention includes the cured film of the present invention. The near infrared cut filter of the present invention preferably has the cured film of the present invention on a support. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, a glass substrate containing copper, etc., and a glass containing copper Substrates are preferred.
　本発明の近赤外線カットフィルタは、本発明の硬化膜の他に、さらに、誘電体多層膜、紫外線吸収層などを有していてもよい。近赤外線カットフィルタが、さらに、誘電体多層膜を有することで、視野角が広く、赤外線遮蔽性に優れた近赤外線カットフィルタが得られやすい。また、近赤外線カットフィルタが、さらに、紫外線吸収層を有することで、紫外線遮蔽性に優れた近赤外線カットフィルタとすることができる。紫外線吸収層としては、例えば、国際公開ＷＯ２０１５／０９９０６０号公報の段落番号００４０～００７０、０１１９～０１４５に記載の吸収層を参酌でき、この内容は本明細書に組み込まれる。誘電体多層膜としては、特開２０１４－４１３１８号公報の段落番号０２５５～０２５９の記載を参酌でき、この内容は本明細書に組み込まれる。 The near infrared cut filter of the present invention may further have a dielectric multilayer film, an ultraviolet absorbing layer, etc. in addition to the cured film of the present invention. When the near infrared cut filter further includes the dielectric multilayer film, it is easy to obtain a near infrared cut filter having a wide viewing angle and excellent infrared shielding properties. In addition, the near infrared cut filter further has an ultraviolet absorbing layer, whereby the near infrared cut filter having excellent ultraviolet shielding properties can be obtained. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO 2015/099060 can be referred to, the contents of which are incorporated herein. As the dielectric multilayer film, the description in paragraphs “0255 to 0259” of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated in the present specification.
　本発明の近赤外線カットフィルタは、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や、赤外線センサ、画像表示装置などの各種装置に用いることができる。 The near-infrared cut filter of the present invention can be used for various devices such as solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.
＜固体撮像素子＞
　本発明の固体撮像素子は、上述した本発明の硬化膜を有する。本発明の固体撮像素子の構成としては、本発明の硬化膜を有する構成であり、固体撮像素子として機能する構成であれば特に限定はない。例えば、以下のような構成が挙げられる。 <Solid-state imaging device>
The solid-state imaging device of the present invention has the cured film of the present invention described above. The configuration of the solid-state imaging device of the present invention is a configuration having the cured film of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. For example, the following configuration may be mentioned.
　支持体上に、固体撮像素子の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、本発明の硬化膜を有する構成である。さらに、デバイス保護膜上であって、本発明の硬化膜の下（支持体に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、本発明の硬化膜上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各画素を形成する膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各画素よりも低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。 A light shield comprising a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon and the like on the support, light shielding made of tungsten or the like in which only the light receiving portion of the photodiode and the transfer electrodes are opened. A device protection film made of silicon nitride or the like which has a film and is formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode and has the cured film of the present invention on the device protection film It is. Furthermore, on the device protective film, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) under the cured film of the present invention (closer to the support), or on the cured film of the present invention It may be a configuration having a condensing means. In addition, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a grid shape by partition walls. The partition walls in this case preferably have a lower refractive index than each pixel. As an example of an imaging device having such a structure, devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.
＜画像表示装置＞
　本発明の画像表示装置は、本発明の硬化膜を含む。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス（有機ＥＬ）表示装置などが挙げられる。画像表示装置の定義や詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。画像表示装置は、白色有機ＥＬ素子を有するものであってもよい。白色有機ＥＬ素子としては、タンデム構造であることが好ましい。有機ＥＬ素子のタンデム構造については、特開２００３－４５６７６号公報、三上明義監修、「有機ＥＬ技術開発の最前線－高輝度・高精度・長寿命化・ノウハウ集－」、技術情報協会、３２６－３２８ページ、２００８年などに記載されている。有機ＥＬ素子が発光する白色光のスペクトルは、青色領域（４３０ｎｍ－４８５ｎｍ）、緑色領域（５３０ｎｍ－５８０ｎｍ）および黄色領域（５８０ｎｍ－６２０ｎｍ）に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加えさらに赤色領域（６５０ｎｍ－７００ｎｍ）に極大発光ピークを有するものがより好ましい。 <Image display device>
The image display apparatus of the present invention includes the cured film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition and details of the image display device, for example, "Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)", "Display device (authored by Ibuki Jun, industrial book, Ltd.) Etc.). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”. There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology." The image display device may have a white organic EL element. It is preferable that it is a tandem structure as a white organic EL element. JP-A-2003-45676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development-High luminance, high accuracy, long life, know-how collection", about the tandem structure of organic EL elements, Technical Information Association, It is described on pages 326-328, 2008, etc. The spectrum of the white light emitted by the organic EL element is preferably one having strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm) and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.
＜赤外線センサ＞
　本発明の赤外線センサは、上述した本発明の硬化膜を含む。赤外線センサの構成としては、赤外線センサとして機能する構成であれば特に限定はない。以下、本発明の赤外線センサの一実施形態について、図面を用いて説明する。 <Infrared sensor>
The infrared sensor of the present invention includes the cured film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described using the drawings.
　図１において、符号１１０は、固体撮像素子である。固体撮像素子１１０上に設けられている撮像領域は、近赤外線カットフィルタ１１１と、赤外線透過フィルタ１１４とを有する。また、近赤外線カットフィルタ１１１上には、カラーフィルタ１１２が積層している。カラーフィルタ１１２および赤外線透過フィルタ１１４の入射光ｈν側には、マイクロレンズ１１５が配置されている。マイクロレンズ１１５を覆うように平坦化層１１６が形成されている。 In FIG. 1, reference numeral 110 denotes a solid-state imaging device. An imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. Further, on the near infrared cut filter 111, a color filter 112 is laminated. A microlens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.
　近赤外線カットフィルタ１１１は本発明の硬化性組成物を用いて形成することができる。近赤外線カットフィルタ１１１の分光特性は、使用する赤外発光ダイオード（赤外ＬＥＤ）の発光波長に応じて選択される。 The near infrared cut filter 111 can be formed using the curable composition of the present invention. The spectral characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) to be used.
　カラーフィルタ１１２は、可視領域における特定波長の光を透過および吸収する画素が形成されたカラーフィルタであって、特に限定はなく、従来公知の画素形成用のカラーフィルタを用いることができる。例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタなどが用いられる。例えば、特開２０１４－０４３５５６号公報の段落番号０２１４～０２６３の記載を参酌することができ、この内容は本明細書に組み込まれる。 The color filter 112 is a color filter in which a pixel for transmitting and absorbing light of a specific wavelength in the visible region is formed, and is not particularly limited, and a conventionally known color filter for forming a pixel can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraph Nos. 0214 to 0263 of JP-A-2014-043556 can be referred to, the contents of which are incorporated herein.
　赤外線透過フィルタ１１４は、使用する赤外ＬＥＤの発光波長に応じてその特性が選択される。 The characteristic of the infrared transmission filter 114 is selected according to the emission wavelength of the infrared LED to be used.
　図１に示す赤外線センサにおいて、平坦化層１１６上には、近赤外線カットフィルタ１１１とは別の近赤外線カットフィルタ（他の近赤外線カットフィルタ）がさらに配置されていてもよい。他の近赤外線カットフィルタとしては、銅を含有する層および／または誘電体多層膜を有するものなどが挙げられる。これらの詳細については、上述したものが挙げられる。また、他の近赤外線カットフィルタとしては、デュアルバンドパスフィルタを用いてもよい。また、図１に示す赤外線センサにおいて、近赤外線カットフィルタ１１１とカラーフィルタ１１２の位置が入れ替わっても良い。また、固体撮像素子１１０と近赤外線カットフィルタ１１１との間、および／または、固体撮像素子１１０と赤外線透過フィルタ１１４との間に他の層が配置されていてもよい。他の層としては、重合性化合物、樹脂および光重合開始剤とを含む組成物を用いて形成された有機物層などが挙げられる。また、カラーフィルタ１１２上に平坦化層が形成されていてもよい。 In the infrared sensor shown in FIG. 1, a near infrared cut filter (another near infrared cut filter) different from the near infrared cut filter 111 may be further disposed on the planarization layer 116. Other near infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. The details of these may be mentioned above. In addition, as another near infrared cut filter, a dual band pass filter may be used. Further, in the infrared sensor shown in FIG. 1, the positions of the near infrared cut filter 111 and the color filter 112 may be interchanged. In addition, another layer may be disposed between the solid-state imaging device 110 and the near-infrared cut filter 111 and / or between the solid-state imaging device 110 and the infrared-transmissive filter 114. As another layer, the organic substance layer etc. which were formed using the composition containing a polymeric compound, resin, and a photoinitiator are mentioned. In addition, a planarization layer may be formed on the color filter 112.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」および「％」は、質量基準である。また、構造式中におけるＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references. In the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
＜組成物の調製＞
　下記の表に示す原料を、下記の表に示す割合（質量部）で混合および撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、各組成物を調製した。
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
 <Preparation of composition>
The raw materials shown in the following table are mixed and stirred in the proportions (parts by mass) shown in the following table, and then filtered with a nylon filter (made by Nippon Pall Co., Ltd.) having a pore diameter of 0.45 μm to obtain each composition Prepared.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
　上記表に記載の原料は以下の通りである。 The raw materials described in the above table are as follows.
　（近赤外線吸収色素）
　Ａ１～Ａ１８、Ａ２０～Ａ２２：下記構造の化合物。
　Ａ１９：ＮＫ－５０６０（（株）林原製、シアニン化合物）
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
 (Near-infrared absorbing dye)
A1 to A18, A20 to A22: compounds of the following structures.
A19: NK-5060 (manufactured by Hayashibara, cyanine compound)
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
　（樹脂）
・樹脂１：下記構造の樹脂（重量平均分子量４１，４００、繰り返し単位に付記した数値はモル数である）のシクロペンタノン３０質量％溶液。
Figure JPOXMLDOC01-appb-C000038
・樹脂２：下記構造の樹脂（重量平均分子量３３１００、繰り返し単位に付記した数値はモル数である）のシクロペンタノン３０質量％溶液。
Figure JPOXMLDOC01-appb-C000039
 (resin)
-Resin 1: 30 mass% solution of cyclopentanone of resin (The weight average molecular weight 41,400, the numerical value attached to the repeating unit is the number of moles) of the following structure.
Figure JPOXMLDOC01-appb-C000038
Resin 2: A 30% by mass solution of cyclopentanone in a resin of the following structure (weight-average molecular weight: 33,100, numerical value added to repeating unit is number of moles).
Figure JPOXMLDOC01-appb-C000039
　（有機溶剤）
・有機溶剤１：シクロペンタノン
・有機溶剤２：３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド
・有機溶剤３：３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド (Organic solvent)
Organic solvent 1: Cyclopentanone Organic solvent 2: 3-methoxy-N, N-dimethylpropanamide Organic solvent 3: 3-butoxy-N, N-dimethylpropanamide
　（環状エーテル基を有する化合物）
・環状エーテル基を有する化合物１：ＥＰＩＣＬＯＮ　ＨＰ５０００（ＤＩＣ（株）製、ナフタレン変性エポキシ樹脂、一つの繰り返し単位における芳香族環の数＝３個、エポキシ基価＝２４５～２６０ｇ／ｍｏｌ）
・環状エーテル基を有する化合物２：ＥＰＩＣＬＯＮ　ＨＰ４０３２Ｄ（ＤＩＣ（株）製、ナフタレン変性エポキシ樹脂、一つの繰り返し単位における芳香族環の数＝２個、エポキシ基価＝１３６～１４８ｇ／ｍｏｌ）
・環状エーテル基を有する化合物３：ＥＰＩＣＬＯＮ　ＨＰ８２０（ＤＩＣ（株）製、アルキルジフェノール型エポキシ樹脂、一つの繰り返し単位における芳香族環の数＝２個、エポキシ基価＝２００～２５０ｇ／ｍｏｌ）
・環状エーテル基を有する化合物４：ＥＰＯＬＥＡＤ　ＰＢ　４７００（（株）ダイセル製、ブタジエン型エポキシ樹脂、芳香族環の数＝０個、エポキシ基価＝１５２～１７８ｇ／ｍｏｌ）
・環状エーテル基を有する化合物５：ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製、クレゾールノボラック型エポキシ樹脂、一つの繰り返し単位における芳香族環の数＝１個、エポキシ基価＝２０９～２１９ｇ／ｍｏｌ）
・環状エーテル基を有する化合物６：ＥＨ３１５０（（株）ダイセル製、シクロヘキサノン型樹脂、芳香族環の数＝０個、エポキシ基価＝１７０～１９０ｇ／ｍｏｌ） (Compound having a cyclic ether group)
· Compound 1 having cyclic ether group: EPICLON HP 5000 (manufactured by DIC Corporation, naphthalene-modified epoxy resin, number of aromatic rings in one repeating unit = 3, epoxy group value = 245 to 260 g / mol)
· Compound 2 having cyclic ether group: EPICLON HP4032D (manufactured by DIC Corporation, naphthalene-modified epoxy resin, number of aromatic rings in one repeating unit = 2, epoxy group value = 136 to 148 g / mol)
・ Compound 3 having a cyclic ether group: EPICLON HP 820 (manufactured by DIC Corporation, alkyldiphenol type epoxy resin, number of aromatic rings in one repeating unit = 2, epoxy group value = 200 to 250 g / mol)
· Compound 4 having a cyclic ether group: EPOLEAD PB 4700 (manufactured by Daicel, butadiene type epoxy resin, number of aromatic rings = 0, epoxy group value = 152 to 178 g / mol)
· Compound 5 having a cyclic ether group: EPICLON N-695 (made by DIC Corporation, cresol novolac epoxy resin, number of aromatic rings in one repeating unit = 1, epoxy group value = 209 to 219 g / mol)
· Compound having cyclic ether group 6: EH 3150 (manufactured by Daicel, cyclohexanone type resin, number of aromatic rings = 0, epoxy group value = 170 to 190 g / mol)
　（ラジカル重合性化合物）
　ラジカル重合性化合物１：下記化合物の混合物（左側化合物と右側化合物とのモル比が７：３の混合物）
Figure JPOXMLDOC01-appb-C000040
 (Radical polymerizable compound)
Radically polymerizable compound 1: a mixture of the following compounds (mixture in which the molar ratio of the left compound and the right compound is 7: 3)
Figure JPOXMLDOC01-appb-C000040
ラジカル重合性化合物２：下記化合物の混合物（高速液体クロマトグラフィーでの高さ比：４６．１５：４９．３９：：４．４６）
Figure JPOXMLDOC01-appb-C000041
ラジカル重合性化合物３：下記化合物
Figure JPOXMLDOC01-appb-C000042
ラジカル重合性化合物４：下記化合物
Figure JPOXMLDOC01-appb-C000043
　（開始剤）
・開始剤１：ＩＲＧＡＣＵＲＥ－１８４（ＢＡＳＦ社製、α－ヒドロキシアセトフェノン化合物、波長３６５ｎｍにおけるモル吸光係数＝１９．５Ｌ・ｍｏｌ-1・ｃｍ-1、熱分解温度＝１５１℃、熱ラジカル重合開始剤）
・開始剤２：下記構造の化合物（ピナコール化合物、波長３６５ｎｍにおけるモル吸光係数＝１０Ｌ・ｍｏｌ-1・ｃｍ-1以下、熱分解温度＝１８２℃、熱ラジカル重合開始剤）
Figure JPOXMLDOC01-appb-C000044
・開始剤３：パーブチルＯ（日油（株）製、有機過酸化物、波長３６５ｎｍにおけるモル吸光係数＝５Ｌ・ｍｏｌ-1・ｃｍ-1以下、熱分解温度＝１０５℃、熱ラジカル重合開始剤）
・開始剤４：Ｖ－６０１（和光純薬工業（株）製、アゾ化合物、波長３６５ｎｍにおけるモル吸光係数＝６Ｌ・ｍｏｌ-1・ｃｍ-1以下、熱分解温度＝９０℃、熱ラジカル重合開始剤）
・開始剤５：ＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製、オキシム化合物、光ラジカル重合開始剤） Radically polymerizable compound 2: mixture of the following compounds (height ratio by high performance liquid chromatography: 46.15: 49.39 :: 4.46)
Figure JPOXMLDOC01-appb-C000041
Radically polymerizable compound 3: the following compounds
Figure JPOXMLDOC01-appb-C000042
Radically polymerizable compound 4: the following compound
Figure JPOXMLDOC01-appb-C000043
(Initiator)
Initiator 1: IRGACURE-184 (manufactured by BASF, α-hydroxyacetophenone compound, molar absorption coefficient at a wavelength of 365 nm = 19.5 L · mol −1 · cm −1 , thermal decomposition temperature = 151 ° C., thermal radical polymerization initiator )
-Initiator 2: compound of the following structure (pinacol compound, molar absorption coefficient at a wavelength of 365 nm = 10 L · mol -1 · cm -1 or less, thermal decomposition temperature = 182 ° C, thermal radical polymerization initiator)
Figure JPOXMLDOC01-appb-C000044
Initiator 3: Perbutyl O (manufactured by NOF Corporation, organic peroxide, molar extinction coefficient at a wavelength of 365 nm = 5 L · mol −1 · cm −1 or less, thermal decomposition temperature = 105 ° C., thermal radical polymerization initiator )
Initiator 4: V-601 (manufactured by Wako Pure Chemical Industries, Ltd., azo compound, molar absorptivity at wavelength of 365 nm = 6 L · mol −1 · cm −1 or less, thermal decomposition temperature = 90 ° C., thermal radical polymerization initiation Agent)
-Initiator 5: IRGACURE-OXE01 (manufactured by BASF, oxime compound, photo radical polymerization initiator)
・シランカップリング剤：ウレイドプロピルトリメトキシシラン Silane coupling agent: ureidopropyltrimethoxysilane
・界面活性剤：下記式（Ｂ１－１）で表される繰り返し単位と、下記式（Ｂ３－１）で表される繰り返し単位とを有するポリマー（重量平均分子量＝７，４００ｇ／ｍｏｌ、Ｂ１－１：Ｂ３－１＝９２．５：７．５（モル比））のプロピレングリコールモノメチルエーテル アセテート（ＰＧＭＥＡ）３０質量％溶液。下記式（Ｂ３－１）中、Ｘは、－ＣＦ2－ＣＦ2－、－ＣＦ2－、及び－ＣＨ2－ＣＦ2－のいずれかを表し、ｒは繰り返し単位数を表す。Ｘについては、－ＣＦ2－ＣＦ2－と、－ＣＦ2－と、－ＣＨ2－ＣＦ2－との個数の割合が、－ＣＦ2－ＣＦ2－：－ＣＦ2－：－ＣＨ2－ＣＦ2－＝４．２：１．９：１．０である。
Figure JPOXMLDOC01-appb-C000045
 Surfactant: Polymer having a repeating unit represented by the following formula (B1-1) and a repeating unit represented by the following formula (B3-1) (weight-average molecular weight = 7,400 g / mol, B1- 1: 30% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) in a ratio of 1: B3-1 = 92.5: 7.5 (molar ratio). In the following formula (B3-1), X is, -CF 2 -CF 2 -, - CF 2 -, and -CH 2 -CF 2 - represents either, r is representative of the number of repeating units. For X, -CF 2 -CF 2 - and, -CF 2 - and, -CH 2 -CF 2 - ratio of the number of is, -CF 2 -CF 2 -: - CF 2 -: - CH 2 - CF 2 − = 4.2: 1.9: 1.0.
Figure JPOXMLDOC01-appb-C000045
・重合禁止剤１：ｐ－メトキシフェノール Polymerization inhibitor 1: p-methoxyphenol
（分散液１）
　下記組成の原料を、０．３ｍｍ径のジルコニアビーズを使用して、ビーズミル（減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製））で、２時間かけて分散し、分散液１を調製した。
　－分散液１の組成－
・下記構造の近赤外線吸収色素（平均一次粒子径２００ｎｍ）・・・１１．６質量部
Figure JPOXMLDOC01-appb-C000046
・下記構造の顔料誘導体・・・・３．５質量部
Figure JPOXMLDOC01-appb-C000047
・分散剤（下記構造の樹脂、重量平均分子量２２，９００、主鎖の繰り返し単位に付記した数値はモル数であり、側鎖の繰り返し単位に併記される数値は、繰り返し単位の繰り返し数を示す。）・・・７．２質量部
Figure JPOXMLDOC01-appb-C000048
・シクロヘキサノン　　・・・７７．７７質量部 (Dispersion liquid 1)
The raw material of the following composition is dispersed for 2 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm diameter, and dispersed for 2 hours Liquid 1 was prepared.
-Composition of Dispersion 1-
・ Near-infrared absorbing dye of the following structure (average primary particle diameter 200 nm) ・ ・ ・ 11.6 parts by mass
Figure JPOXMLDOC01-appb-C000046
・ Pigment derivative of the following structure ··· 3.5 mass parts
Figure JPOXMLDOC01-appb-C000047
· Dispersant (The resin of the following structure, weight average molecular weight 22, 900, the numerical value attached to the repeating unit of the main chain is the number of moles, and the numerical value written together with the repeating unit of the side chain indicates the repeating number of the repeating unit ) ... 7.2 parts by mass
Figure JPOXMLDOC01-appb-C000048
· Cyclohexanone ... 77. 77 parts by mass
（分散液２）
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ３２の６０質量部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６の２０質量部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１３９の２０質量部、ソルスパース７６５００（日本ルーブリゾール（株）製、固形分濃度５０質量％）の８０質量部、およびプロピレングリコールモノメチルエーテルアセテートの７００質量部を混合し、ペイントシェーカーを用いて８時間分散して、分散液２を得た。 (Dispersion liquid 2)
C. I. Pigment Black 32 60 parts by mass, C.I. I. Pigment Blue 15: 6, 20 parts by mass, C.I. I. Mix 20 parts by mass of Pigment Yellow 139, 80 parts by mass of Solsparse 76500 (manufactured by Nippon Lubrizol Co., Ltd., solid content concentration 50% by mass), and 700 parts by mass of propylene glycol monomethyl ether acetate and mix them with a paint shaker 8 Dispersion was carried out for a time to obtain dispersion liquid 2.
＜耐水密着性の評価＞
　各硬化性組成物を、弗燐酸塩ガラス基材（製品名：ＮＦ－５０、ＡＧＣテクノグラス社製、大きさ５０ｍｍ×５０ｍｍ、厚さ０．０５ｍｍ、銅を含有するガラス基材である）上に、製膜後の膜厚が２．５μｍとなるようにミカサコーターにてスピンコート塗布し、ホットプレートを用いて１００℃で１２０秒間乾燥し、次いで、２２０℃で５分間加熱して硬化膜を製造した。
　硬化膜が形成された弗燐酸塩ガラス基材を、９５℃の水に１時間浸漬後、１ｍｍ×１ｍｍの１００個の升目にクロスカットし、ニチバン製の植物系セロテープ（登録商標）Ｎｏ．４０５を用いてテープ剥離試験を行い、以下の基準で耐水密着性を評価した。
　５：剥がれた升目の数が０個である
　４：剥がれた升目の数が１～５個である
　３：剥がれた升目の数が６～１０個である
　２：剥がれた升目の数が１１～３０個である
　１：剥がれた升目の数が３１個以上である <Evaluation of water tightness>
Each curable composition is formed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., size 50 mm × 50 mm, thickness 0.05 mm, copper-containing glass substrate) Then, spin-coating is applied with a Mikasa coater so that the film thickness after film formation is 2.5 μm, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure Manufactured.
The fluorophosphate glass substrate on which a cured film was formed was immersed in water at 95 ° C. for 1 hour, and then cross-cut into 100 squares of 1 mm × 1 mm, and Nichiban vegetable cellotape (registered trademark) No. A tape peel test was conducted using No. 405, and the water-resistant adhesion was evaluated according to the following criteria.
5: The number of peeled squares is 0 4. The number of peeled squares is 1 to 5. 3: The number of peeled squares is 6 to 10. 2: The number of peeled squares is 11 to 30 pieces 1: The number of peeled squares is 31 or more
＜凝集サイズの評価＞
　各硬化性組成物を、弗燐酸塩ガラス基材（製品名：ＮＦ－５０、ＡＧＣテクノグラス社製、大きさ５０ｍｍ×５０ｍｍ、厚さ０．０５ｍｍ、銅を含有するガラス基材である）上に、製膜後の膜厚が２．５μｍとなるようにミカサコーターにてスピンコート塗布し、ホットプレートを用いて１００℃で１２０秒間乾燥し、次いで、２２０℃で５分間加熱して硬化膜を製造した。
　硬化膜が形成された弗燐酸塩ガラス基材を、２３℃のアセトン中に５分間浸漬した後に、超高分解能走査型電子顕微鏡（（株）日立ハイテクノロジーズ製）を用い、加速電圧２．０ｋＶ、観測倍率５００００倍にて膜断面の観察を行い、任意の３か所の穴空き形状の長軸方向の長さを測定し、その平均値を凝集サイズとして算出した。 <Evaluation of aggregation size>
Each curable composition is formed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., size 50 mm × 50 mm, thickness 0.05 mm, copper-containing glass substrate) Then, spin-coating is applied with a Mikasa coater so that the film thickness after film formation is 2.5 μm, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure Manufactured.
After the fluorophosphate glass substrate on which the cured film is formed is immersed in acetone at 23 ° C. for 5 minutes, an acceleration voltage of 2.0 kV is used using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corp.) The cross section of the film was observed at an observation magnification of 50000 times, lengths of three arbitrary hole shapes in the long axis direction were measured, and the average value was calculated as the aggregation size.
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000053
　上記表に示す通り、実施例はいずれも耐水密着性が良好で、凝集サイズの小さい硬化膜を製造することができた。
　尚、実施例１において、開始剤２の代わりに特表２０１４－５２１７７２記載の実施例１７の開始剤を使用しても、実施例１と同様な効果が得られた。 As shown in the above table, all of the examples had good water-resistant adhesion and were able to produce a cured film having a small aggregation size.
In Example 1, even when the initiator of Example 17 described in JP-A-2014-521772 was used instead of the initiator 2, the same effect as that of Example 1 was obtained.
１１０：固体撮像素子、１１１：近赤外線カットフィルタ、１１２：カラーフィルタ、１１４：赤外線透過フィルタ、１１５：マイクロレンズ、１１６：平坦化層
  110: solid-state imaging device, 111: near infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims (16)

  1. 　近赤外線吸収色素と、環状エーテル基を有する化合物と、ラジカル重合性化合物と、熱ラジカル重合開始剤とを含む硬化性組成物。 A curable composition comprising a near infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
  2. 　前記環状エーテル基は、エポキシ基である、請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the cyclic ether group is an epoxy group.
  3. 　前記環状エーテル基を有する化合物は、芳香族環を含む化合物である、請求項１または２に記載の硬化性組成物。 The curable composition according to claim 1, wherein the compound having a cyclic ether group is a compound containing an aromatic ring.
  4. 　前記環状エーテル基を有する化合物の１００質量部に対して、前記ラジカル重合性化合物を１～１００質量部含む、請求項１～３のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, comprising 1 to 100 parts by mass of the radically polymerizable compound relative to 100 parts by mass of the compound having a cyclic ether group.
  5. 　前記ラジカル重合性化合物の１００質量部に対して、前記熱ラジカル重合開始剤を０．０５～２００質量部含む、請求項１～４のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the heat radical polymerization initiator is contained in an amount of 0.05 to 200 parts by mass with respect to 100 parts by mass of the radically polymerizable compound.
  6. 　前記熱ラジカル重合開始剤は、ピナコール化合物およびα－ヒドロキシアセトフェノン化合物から選ばれる少なくとも１種である、請求項１～５のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, wherein the thermal radical polymerization initiator is at least one selected from a pinacol compound and an α-hydroxyacetophenone compound.
  7. 　前記近赤外線吸収色素は、単環または縮合環の芳香族環を含むπ共役平面を有する化合物である、請求項１～６のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, wherein the near-infrared absorbing dye is a compound having a π conjugated plane including an aromatic ring of a single ring or a condensed ring.
  8. 　前記近赤外線吸収色素は、ピロロピロール化合物、スクアリリウム化合物およびシアニン化合物から選ばれる少なくとも１種である、請求項１～６のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, wherein the near infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, squarylium compounds and cyanine compounds.
  9. 　請求項１～８のいずれか１項に記載の硬化性組成物から得られる硬化膜。 A cured film obtained from the curable composition according to any one of claims 1 to 8.
  10. 　支持体上に請求項１～８のいずれか１項に記載の硬化性組成物を適用して硬化性組成物層を形成する工程と、
    　前記硬化性組成物層を加熱硬化する工程と、を含む硬化膜の製造方法。     Applying the curable composition according to any one of claims 1 to 8 on a support to form a curable composition layer;
    And heat curing the curable composition layer.
  11. 　前記支持体が銅を含有するガラス基材である、請求項１０に記載の硬化膜の製造方法。 The manufacturing method of the cured film of Claim 10 which is a glass base material in which the said support body contains copper.
  12. 　請求項９に記載の硬化膜を有する近赤外線カットフィルタ。 The near-infrared cut off filter which has a cured film of Claim 9.
  13. 　銅を含有するガラス基材の表面に前記硬化膜を有する、請求項１２に記載の近赤外線カットフィルタ。 The near-infrared cut off filter according to claim 12, wherein the cured film is provided on the surface of a copper-containing glass substrate.
  14. 　請求項９に記載の硬化膜を有する固体撮像素子。 The solid-state image sensor which has a cured film of Claim 9.
  15. 　請求項９に記載の硬化膜を有する画像表示装置。 The image display apparatus which has a cured film of Claim 9.
  16. 　請求項９に記載の硬化膜を有する赤外線センサ。
    　　　　　　　　　　　　　　　　　      An infrared sensor having the cured film according to claim 9.
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