Near infrared absorbing composition, film, infrared cut filter, solid-state imaging element, infrared absorber and compound

Abstract

The present invention provides a near-infrared absorbing composition, a film, an infrared cut filter, a solid-state imaging element, an infrared absorber and a compound capable of producing a film having excellent infrared shielding properties and visible transparency. The near-infrared absorbing composition comprises a squarylium salt compound represented by the following formula (1) and having a maximum absorption wavelength of 700 nm or more and a resin. 1 and Ar 2 Each independently represents a divalent conjugated group having a heteroaromatic ring containing a chalcogen atom, R 1 ~R 4 Each independently represents a hydrogen atom or a substituent. The film and the infrared cut filter are composed of a near-infrared absorbing composition. The solid-state imaging element has an infrared cut filter.

Description

[0001] This application is a divisional application of the application No. 201680067876.5 filed by the applicant, and the invention title is “Near-infrared absorbing composition, film, infrared cut filter, solid-state imaging element, infrared absorber and compound”. The filing date of the parent case is November 02, 2016, and the earliest priority date is December 17, 2015. Technical Field

[0002] The present invention relates to a near-infrared absorbing composition, a film, an infrared cut filter, a solid-state imaging element, an infrared absorber and a compound. Background Art

[0003] CCD (charge coupled device) or CMOS (complementary metal oxide semiconductor) as a solid-state imaging element for color images is used in video cameras, digital cameras, mobile phones with camera functions, etc. In these solid-state imaging elements, in order to use silicon photodiodes that sense infrared light for the light receiving part, luminous efficiency correction is required, and infrared cut filters are often used in combination. As near-infrared absorbing compounds, squarylium salt compounds are known.

[0004] Patent Document 1 describes that the following compounds and the like are used as toners for electrophotography.

[0005] [Chemical formula 1]

[0006]

[0007] Furthermore, Patent Document 2 describes the following compounds.

[0008] [Chemical formula 2]

[0009]

[0010] Furthermore, Non-Patent Document 1 is a paper on the two-photon absorption of squarylium ylide compounds, and describes the two-photon absorption of the following compounds.

[0011] [Chemical formula 3]

[0012]

[0013] Furthermore, Non-Patent Document 2 describes the following compound.

[0014] [Chemical formula 4]

[0015]

[0016] Previous technical literature

[0017] Patent Literature

[0018] [Patent Document 1]: Japanese Patent Application Publication No. 2009-15114

[0019] [Patent Document 2]: German Patent Application Publication No. 4122563

[0020] Non-patent literature

[0021] [Non-patent document 1]: Chem. Eur. J., 2008, 14, 11082-11091

[0022] [Non-patent document 2]: H. Meier et al., Helv. Chem. Acta 2004, 87, 1109-1118. Summary of the invention

[0023] Technical issues to be solved by the invention

[0024] Infrared cut filters are required to have excellent infrared shielding properties and visible transparency. In recent years, there has been a demand for further improvement of these properties.

[0025] Patent Document 1 is an invention about a toner for electrophotography, and does not describe any infrared cut filter. Furthermore, the inventors of the present invention studied the compound described in Patent Document 1 and found that it is difficult to achieve both infrared shielding properties and visible transparency.

[0026] Furthermore, although Patent Document 2, Non-Patent Document 1 and Non-Patent Document 2 describe specific squarylium salt compounds, they do not describe the infrared shielding properties and visible transparency of the compounds. Furthermore, there is no description or suggestion of using the compounds in infrared cut filters.

[0027] Therefore, an object of the present invention is to provide a near-infrared absorbing composition, a film, an infrared cut filter, a solid-state imaging element, an infrared absorber, and a compound capable of producing a film having excellent infrared shielding properties and visible transparency.

[0028] Means for solving technical problems

[0029] As a result of various studies, the present inventors have found that the above-mentioned object can be achieved by using a near-infrared absorbing composition containing a squarylium salt compound represented by formula (1) and having a maximum absorption wavelength in the range of 700 nm or more and a resin, which is described later, and have completed the present invention. The present invention provides the following.

[0030] <1> A near infrared absorbing composition comprising a squarylium salt compound represented by the following formula (1) and having a maximum absorption wavelength of 700 nm or more and a resin,

[0031] [Chemical formula 5]

[0032]

[0033] In the formula, Ar 1 and Ar 2 Each independently represents a divalent conjugated group having a heteroaromatic ring containing a chalcogen atom, R 1 ~R 4 Each independently represents a hydrogen atom or a substituent, R 1 Can be used with R 2 or Ar 1 Bond to form a ring, R 3 Can be used with R 4 or Ar 2 Bond to form a ring,

[0034] Among them, Ar 1 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom, R 1 and R 2 Each independently represents an aryl or heteroaryl group, Ar 2 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom, R 3 and R 4 Each independently represents an aryl group or a heteroaryl group.

[0035] <2> according to <1> The near-infrared absorbing composition, wherein the squarylium salt compound comprises Ar of formula (1): 1 and Ar 2 The plane has a π-conjugated plane with 16 to 54 atoms.

[0036] <3> according to <1> or <2> In the near-infrared absorbing composition, the chalcogen atom is a sulfur atom.

[0037] <4> according to <1> or <2> The near-infrared absorbing composition, wherein Ar 1 and Ar 2 Each independently represents a thiophene ring, a thiazole ring, a condensed ring containing at least one of these rings, or a divalent conjugated group containing these rings.

[0038] <5> according to <1> ~ <4> The near-infrared absorbing composition according to any one of the preceding claims, wherein Ar 1 and Ar 2 Each independently contains a thiophene ring or a thiazole ring,

[0039] R 1 ~R 4 Each independently represents an aryl group or a heteroaryl group.

[0040] <6> according to <5> The near-infrared absorbing composition, wherein R 1 ~R 4 At least one of them represents an aryl group or a heteroaryl group having 8 or more atoms constituting the ring.

[0041] <7> according to <5> The near-infrared absorbing composition, wherein R 1 ~R 4 At least one of represents a naphthyl group.

[0042] <8> according to <1> ~ <4> The near-infrared absorbing composition according to any one of the preceding claims, wherein Ar 1 and Ar 2 Each independently represents a divalent conjugated group having a π-conjugated plane with 8 or more atoms,

[0043] R 1 ~R 4 Each independently represents an alkyl group, an aryl group or a heteroaryl group.

[0044] <9> according to <8> The near-infrared absorbing composition, wherein Ar 1 and Ar 2 Each independently represents a divalent conjugated group including at least one selected from a condensed ring, a thiophene ring or a thiazole ring, and the condensed ring includes at least one selected from a thiophene ring and a thiazole ring.

[0045] <10> according to <8> The near-infrared absorbing composition, wherein Ar 1 and Ar 2 Each independently represents a condensed ring including at least one selected from a thiophene ring and a thiazole ring.

[0046] <11> according to <1> ~ <10> Any of the near-infrared absorbing compositions described in , wherein Ar 1 ,Ar 2 , R 1 , R 2 , R 3 and R 4 At least one of them has a group represented by the following formula (W),

[0047] -S 1 -L 1 -T 1 ……(W)

[0048] In formula (W), S 1 represents a single bond, an arylene group or a heteroarylene group, L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONRL1 -、-NR L1 CO-, -SO2-, -OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group,

[0049] T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group,

[0050] S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group, 1 and T 1 The total number of carbon atoms contained is 5 or more,

[0051] S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

[0052] <12> according to <1> ~ <4> The near infrared absorbing composition according to any one of the preceding claims, wherein the squarylium salt compound is a compound represented by the following formula (1a):

[0053] [Chemical formula 6]

[0054]

[0055] In the formula, Ar 11 and Ar 12 Each independently represents a thiophene ring, a thiazole ring, or a condensed ring containing at least one of these rings,

[0056] R 11 ~R 14 each independently represents an alkyl group, an aryl group or a heteroaryl group,

[0057] R 11 Can be used with R 12 or Ar 11 Bond to form a ring,

[0058] R 13 Can be used with R 14 or Ar 12 Bond to form a ring,

[0059] Ar 11 When it is a thiophene ring or a thiazole ring, R 11 and R12 At least one of represents an aryl or heteroaryl group having 8 or more atoms,

[0060] Ar 12 When it is a thiophene ring or a thiazole ring, R 13 and R 14 At least one of them represents an aryl group or a heteroaryl group having 8 or more atoms.

[0061] <13> A membrane comprising <1> to <12> The near-infrared absorbing composition described in any one of the above is formed.

[0062] <14> An infrared cut-off filter comprising <1> to <12> The near-infrared absorbing composition described in any one of the above is formed.

[0063] <15> A solid-state imaging element having <14> Infrared cut filter as described in .

[0064] <16> An infrared absorbent represented by the following formula (1a):

[0065] [Chemical formula 7]

[0066]

[0067] In the formula, Ar 11 and Ar 12 Each independently represents a thiophene ring, a thiazole ring, or a condensed ring containing at least one of these rings,

[0068] R 11 ~R 14 each independently represents an alkyl group, an aryl group or a heteroaryl group,

[0069] R 11 Can be used with R 12 or Ar 11 Bond to form a ring,

[0070] R 13 Can be used with R 14 or Ar 12 Bond to form a ring,

[0071] Ar 11 When it is a thiophene ring or a thiazole ring, R 11 and R 12 At least one of represents an aryl or heteroaryl group having 8 or more atoms,

[0072] Ar 12 When it is a thiophene ring or a thiazole ring, R 13 and R 14 At least one of them represents an aryl group or a heteroaryl group having 8 or more atoms.

[0073] <17> A compound represented by the following formula (1a),

[0074] [Chemical formula 8]

[0075]

[0076] In the formula, Ar 11 and Ar 12 Each independently represents a thiophene ring, a thiazole ring, or a condensed ring containing at least one of these rings,

[0077] R 11 ~R 14 each independently represents an alkyl group, an aryl group or a heteroaryl group,

[0078] R 11 Can be used with R 12 or Ar 11 Bond to form a ring,

[0079] R 13 Can be used with R 14 or Ar 12 Bond to form a ring,

[0080] Ar 11 When it is a thiophene ring or a thiazole ring, R 11 and R 12 At least one of represents an aryl or heteroaryl group having 8 or more atoms,

[0081] Ar 12 When it is a thiophene ring or a thiazole ring, R 13 and R 14 At least one of them represents an aryl group or a heteroaryl group having 8 or more atoms.

[0082] <18> according to <17> The compound, wherein R 11 ~R 14 At least one of represents a naphthyl group.

[0083] <19> according to <17> or <18> The compound, wherein, is selected from Ar 11 ,Ar 12 , R 11 , R 12 , R 13 and R 14 At least one of them has a group represented by the following formula (W),

[0084] -S 1 -L 1 -T 1 ……(W)

[0085] In formula (W), S1 represents a single bond, an arylene group or a heteroarylene group, L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO2-, -OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group,

[0086] T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group,

[0087] S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group, 1 and T 1 The total number of carbon atoms contained is 5 or more,

[0088] S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

[0089] Effects of the Invention

[0090] According to the present invention, a near-infrared absorbing composition capable of producing a film having excellent infrared shielding properties and visible transparency can be provided. In addition, a film having excellent infrared shielding properties and visible transparency, an infrared cut filter, a solid-state imaging element, an infrared absorber, and a compound can be provided. DETAILED DESCRIPTION

[0091] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In addition, the solid content refers to the solid content at 25°C.

[0092] In the marking of groups (atomic groups) in this specification, the markings that do not describe substitution and unsubstituted include both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0093] The term "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. In addition, in the present invention, light refers to activating light or radiation. Unless otherwise specified, "exposure" in this specification refers not only to exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, X-rays, EUV, etc., but also to drawing using particle beams such as electron beams and ion beams.

[0094] In this specification, near infrared rays refer to light (electromagnetic waves) having a wavelength range of 700 to 2500 nm.

[0095] In the present specification, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)allyl” means both or either allyl and methallyl, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0096] In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0097] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.

[0098] In this specification, "weight average molecular weight" and "number average molecular weight" are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC).

[0099] <Near infrared absorbing composition>

[0100] The near infrared absorbing composition of the present invention (hereinafter also referred to as the composition of the present invention) comprises a squarylium ylide compound represented by the following formula (1) and having a maximum absorption wavelength of 700 nm or longer (hereinafter also referred to as squarylium ylide compound (1)) and a resin.

[0101] [Chemical formula 9]

[0102]

[0103] In the squarylium salt compound (1), in Ar 1 and Ar 2 Since a divalent conjugated group having a heteroaromatic ring including a chalcogen atom is introduced at the position of , it is considered that the contribution of the quinone type of the compound is increased and the maximum absorption wavelength is further shifted to the longer wavelength side.

[0104] Moreover, by 1 or Ar 2 The effective conjugation length is lengthened by using a group having a larger π conjugated plane such as a divalent conjugated group having a heteroaromatic ring of a condensed ring containing a chalcogen atom (e.g., a condensed ring containing a thiophene ring or a thiazole ring). As a result, the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap becomes smaller, so that the maximum absorption wavelength of the compound can be further shifted to the long wavelength side.

[0105] Moreover, Ar 1 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom (for example, a thiophene ring or a thiazole ring), by replacing R 1 and R 2 If it is set as an aryl or heteroaryl group, the effective conjugation length becomes longer, Ar 2 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom (for example, a thiophene ring or a thiazole ring), by replacing R 3 and R 4 By using an aryl group or a heteroaryl group, the effective conjugation length is increased, thereby reducing the HOMO-LUMO gap, and thus the maximum absorption wavelength of the compound can be easily adjusted to 700 nm or more.

[0106] Here, as a method for adjusting the maximum absorption wavelength of the squarylium salt compound (1) to 700 nm or more, there can be mentioned a method of adding a squarylium salt compound (1) containing Ar 1 and Ar 2 The plane is the approach to the larger π conjugated plane (lengthened with -NR 1 R 2 and-NR 3 R 4 The conjugation method of the clamped part), R 1 ~R 4 As a conjugated group method. 1 and Ar 2 When the plane is used as a larger π-conjugated plane, the spatial expansion of HOMO and LUMO can be more effectively induced, so the effective conjugation length can be easily lengthened, and the maximum absorption wavelength of the compound can be easily adjusted to more than 700 nm.

[0107] Furthermore, through research conducted by the present inventors, it was found that compounds represented by the following formula (1) having a maximum absorption wavelength of 700 nm or more have excellent visible transparency and infrared shielding properties. Furthermore, it was found that by blending a squarylium salt compound (1) with a composition containing a resin, a film having excellent infrared shielding properties and visible transparency can be produced.

[0108] Furthermore, in the squarylium salt compound (1), Ar1 and Ar 2 The composition of the present invention is a divalent conjugated group having a heteroaromatic ring of a condensed ring containing a chalcogen atom, thereby improving heat resistance and light resistance, and is less likely to be colored by heating or light irradiation. Therefore, according to the composition of the present invention, a film having excellent visible transparency even after heating or light irradiation can be produced.

[0109] Hereinafter, each component of the composition of the present invention will be described.

[0110] <<Squarylium salt compound represented by formula (1)>>

[0111] The composition of the present invention comprises a squarylium salt compound (squarylium salt compound (1)) represented by the following formula (1) and having a maximum absorption wavelength of 700 nm or more. In the present invention, the maximum absorption wavelength of the squarylium salt compound (1) is preferably 710 nm or more, more preferably 720 nm or more. The upper limit is, for example, preferably 1200 nm or less, more preferably 1000 nm or less. By having a maximum absorption wavelength within the above range, a film having excellent infrared shielding properties and visible transparency can be manufactured.

[0112] The value of the maximum absorption wavelength of the squarylium salt compound (1) is a value measured using a chloroform solution of the squarylium salt compound adjusted so that the absorbance at the maximum absorption wavelength falls within the range of 0.7 to 1.2.

[0113] The content of the squarylium salt compound (1) is preferably set to 0.1 to 70% by mass in the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less. By setting it within this range, good infrared absorption energy can be imparted. When the composition includes two or more squarylium salt compounds (1), the total amount is preferably within the above range.

[0114] [Chemical formula 10]

[0115]

[0116] In the formula, Ar 1 and Ar 2 Each independently represents a divalent conjugated group having a heteroaromatic ring containing a chalcogen atom, R 1 ~R 4 Each independently represents a hydrogen atom or a substituent, R 1 Can be used with R 2 or Ar 1 Bond to form a ring, R 3 Can be used with R 4 or Ar 2 Bond to form a ring,

[0117] Among them, Ar 1 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom, R 1 and R 2 Each independently represents an aryl or heteroaryl group, Ar 2 In the case of a monocyclic heteroaromatic ring containing a chalcogen atom, R 3 and R 4 Each independently represents an aryl group or a heteroaryl group.

[0118] Ar 1 and Ar 2 Each independently represents a divalent conjugated group having a heteroaromatic ring containing a chalcogen atom. Examples of the chalcogen atom include a sulfur atom, an oxygen atom, a selenium atom, and a tellurium atom, preferably a sulfur atom. In addition, in the present invention, a heteroaromatic ring refers to an aromatic ring composed of two or more atoms.

[0119] The heteroaromatic ring group containing a chalcogen atom may have a substituent or may be unsubstituted. As the substituent, a group described by the substituent group T group and a group represented by formula (W) can be cited. From the viewpoint of spectroscopy and solubility, the substituent is preferably a group represented by formula (W). In addition, in the present invention, the divalent conjugated group having a heteroaromatic ring containing a chalcogen atom may be composed only of a heteroaromatic ring containing a chalcogen atom, or may be a divalent conjugated group composed of a heteroaromatic ring containing a chalcogen atom and a connecting group. The divalent conjugated group is preferably composed only of a heteroaromatic ring containing a chalcogen atom.

[0120] Examples of heteroaromatic rings containing chalcogen atoms include condensed rings containing a ring represented by (Ht) below and a ring represented by (Ht) below. Examples of condensed rings include condensed rings in which two or more rings represented by (Ht) below are condensed, or condensed rings in which a ring represented by (Ht) below is condensed with a heteroaromatic ring that does not contain an aromatic hydrocarbon ring and / or a chalcogen atom. The heteroaromatic ring containing a chalcogen atom preferably contains a condensed ring containing at least one selected from a thiophene ring and a thiazole ring. The number of condensed condensed rings is preferably 2 to 8, more preferably 2 to 5, and further preferably 2 to 3.

[0121] [Chemical formula 11]

[0122]

[0123] Where, X 1 and X 2 Each independently represents a nitrogen atom, CR x . R x represents a hydrogen atom or a substituent. The substituent may be exemplified by the following R 1 ~R 4 The substituent group T and the group represented by the formula (W) are described. 1represents a chalcogen atom. Examples of the chalcogen atom include a sulfur atom, an oxygen atom, a selenium atom, and a tellurium atom, and a sulfur atom is preferred. * represents a connecting bond.

[0124] Specific examples of the heteroaromatic ring containing a chalcogen atom include a thiophene ring and a thiazole ring as a monocyclic ring, and the following rings as condensed rings.

[0125] [Chemical formula 12]

[0126]

[0127] In the formula K, Z represents -CR2-, -CR=CR-, -SIR2-, -CO-, -S-, -SO-, -SO2-. * represents a linking bond. R represents a hydrogen atom or a substituent. The substituent may be any of the following R 1 ~R 4 The substituent group T and the group represented by the formula (W) are explained.

[0128] Examples of the divalent conjugated group having a heteroaromatic ring containing a chalcogen atom include the following (1) to (5), and embodiment (1) is preferred. Among embodiment (1), an embodiment in which the heteroaromatic ring containing a chalcogen atom is a condensed ring is more preferred.

[0129] (1) A group consisting only of a heteroaromatic ring having a chalcogen atom (a divalent conjugated group consisting of a heteroaromatic ring containing a chalcogen atom).

[0130] (2) A group in which two or more heteroaromatic rings containing a chalcogen atom are bonded via a single bond.

[0131] (3) A group comprising a combination of one or more heteroaromatic rings containing a chalcogen atom and a methine chain containing 1 to 4 methine groups.

[0132] (4) A group in which one or more heteroaromatic rings containing a chalcogen atom and one or more heteroaromatic rings not containing a chalcogen atom are bonded via a single bond or a methine chain containing 1 to 4 methine groups.

[0133] (5) A group in which one or more heteroaromatic rings containing a chalcogen atom and one or more aromatic hydrocarbon rings are bonded via a single bond or a methine chain containing 1 to 4 methine groups.

[0134] Ar 1 and Ar 2 Each of them is independently a thiophene ring, a thiazole ring, or a condensed ring containing at least one of these rings, or a divalent conjugated group containing these rings, more preferably a condensed ring containing at least one selected from a thiophene ring, a thiazole ring, or a thiophene ring and a thiazole ring, and further preferably a condensed ring containing at least one selected from a thiophene ring and a thiazole ring.

[0135] Moreover, Ar1 and Ar 2 It is also preferred that each independently be a divalent conjugated group having a π-conjugated plane with 8 or more atoms (preferably 8 to 14 atoms, more preferably 8 to 12 atoms). According to this embodiment, a film having excellent visible transparency and infrared shielding properties can be easily produced.

[0136] The divalent conjugated group having a π conjugated plane with more than 8 atoms is preferably a divalent conjugated group comprising the following rings: a condensed ring comprising at least one selected from a thiophene ring and a thiazole ring or at least one selected from a thiophene ring, a thiazole ring and a condensed ring comprising these rings, more preferably a condensed ring comprising at least one selected from a thiophene ring and a thiazole ring. In addition, the π conjugated plane in the present invention is composed of atoms other than hydrogen atoms. For example, in the case of the conjugated group (A), the number of atoms in the π conjugated plane is 10, in the case of the conjugated group (B), the number of atoms in the π conjugated plane is 12, and in the case of the conjugated group (C), the number of atoms in the π conjugated plane is 8.

[0137] [Chemical formula 13]

[0138]

[0139] In formula (1), -NR 1 R 2 and-NR 3 R 4 The sandwiched portion preferably has a π-conjugated plane with 16 to 54 atoms (preferably 16 to 44 atoms, more preferably 16 to 34 atoms). According to this method, the visible transparency and infrared shielding properties can be easily further improved. In addition, the π-conjugated plane in the present invention is composed of atoms other than hydrogen atoms. For example, in the case of the following compound, -NR 1 R 2 and-NR 3 R 4 The sandwiched part has a π-conjugated plane with an atomic number of 22. In addition, Ar 1 and / or Ar 2 When there is a substituent, it indicates the number of atoms of the portion excluding the substituent. Specifically, it indicates the number of atoms of the π-conjugated plane formed by the structure in which the substituent is substituted with a hydrogen atom.

[0140] [Chemical formula 14]

[0141]

[0142] In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom or a substituent. 1 When it is a thiophene ring or a thiazole ring, R1 and R 2 Each independently represents an aryl or heteroaryl group, Ar 2 When it is a thiophene ring or a thiazole ring, R 3 and R 4 Each independently represents an aryl group or a heteroaryl group.

[0143] As R 1 ~R 4 The substituent represented by includes the groups explained in the substituent group T group and the group represented by the formula (W) described later, and is preferably an alkyl group, an aryl group or a heteroaryl group, and more preferably an aryl group or a heteroaryl group.

[0144] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0145] The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group is preferably a naphthyl group.

[0146] The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The number of atoms constituting the ring of the heteroaryl group is preferably 5 or more, more preferably 6 or more, and further preferably 8 or more. The upper limit can be, for example, 30 or less, preferably 18 or less, and more preferably 12 or less.

[0147] The alkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. As the substituent, the following substituent group T can be mentioned. In addition, as a substituent, the group represented by the formula (W) described below may be further included.

[0148] (Substituent T group)

[0149] Halogen atoms, cyano, nitro, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, -OR Z 1 、-COR Z 1 、-COOR Z 1 、-OCOR Z 1 、-NR Z 1 R Z 2 、-NHCOR Z 1 、-CONR Z 1 R Z2 、-NHCONR Z 1 R Z 2 、-NHCOOR Z 1 、-SR Z 1 、-S02R Z 1 、-SO2OR Z 1 、-NHSO2R Z 1 or -SO2NR Z 1 R Z 2 . R Z 1 and R Z 2 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group, and R Z 1 With R Z 2 Can bond to form a ring. Z 1 R Z 1 When it is hydrogen (i.e., carboxyl group), the hydrogen atom may be dissociated (i.e., carbonate group) or may be in the state of salt. Z 1 R Z 1 When it is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in a salt state.

[0150] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0151] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0152] The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0153] The number of carbon atoms in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0154] The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms.

[0155] The alkyl part of the aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the above-mentioned aryl group. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.

[0156] The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12.

[0157] Alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl may have a substituent or may be unsubstituted. As a substituent, the above-mentioned substituent group T can be mentioned. For example, an alkyl, aryl, heteroaryl etc. can be mentioned. In addition, as a substituent, a group represented by formula (W) described below can be mentioned.

[0158] In formula (1), R 1 Can be used with R 2 or Ar 1 Bond to form a ring, R 3 Can be used with R 4 or Ar 2 bonds to form a ring. 1 With R 2 or Ar 1 The ring formed by bonding and R 3 With R 4 or Ar 2 The ring formed by bonding includes an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, a heterocyclic ring, etc. The ring may be a monocyclic ring or a polycyclic ring. As a connecting group when forming the above-mentioned ring, it can be connected through a divalent connecting group selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and a combination thereof.

[0159] As R 1 (R 3 ) and R 2 (R 4 ) or Ar 1 (Ar 2 ) are bonded to form a ring, for example, the following structure and the following structural formula, wherein X represents a hydrogen atom or a substituent.

[0160] [Chemical formula 15]

[0161]

[0162] As a preferred embodiment of formula (1), the following can be mentioned: <1> and <2> , preferably <2> .

[0163] <1> In formula (1), Ar 1 and Ar 2 Each independently represents a thiophene ring or a thiazole ring, R 1 ~R 4 Each independently represents an aryl group or a heteroaryl group.

[0164] <2> In formula (1), Ar 1 and Ar 2 Each independently represents a divalent conjugated group having a π-conjugated plane with 8 or more atoms, R 1 ~R 4 Each independently represents an alkyl group, an aryl group or a heteroaryl group.

[0165] Above <1> In the method, R 1 ~R 4 At least one of the above is preferably an aryl group having 8 or more atoms constituting the ring or a heteroaryl group having 8 or more atoms constituting the ring. According to this embodiment, visible transparency and infrared shielding properties can be further improved. Moreover, the aryl group and the heteroaryl group are preferably condensed rings. As specific examples, naphthyl and the groups shown below can be cited, and naphthyl is preferred. In the following structural formula, * is a bond to a nitrogen atom.

[0166] [Chemical formula 16]

[0167]

[0168] Above <2> In the method, Ar 1 and Ar 2 Preferably, each independently represents a divalent conjugated group containing the following rings: a condensed ring containing at least one selected from a thiophene ring and a thiazole ring, or at least one selected from a thiophene ring, a thiazole ring, and a condensed ring containing these rings, and more preferably represents a condensed ring containing at least one selected from a thiophene ring and a thiazole ring. According to this embodiment, visible transparency and infrared shielding can be further improved.

[0169] In the squarylium salt compound (1), selected from Ar 1 ,Ar 2 , R 1 , R 2 , R 3 and R 4 It is also preferred that at least one of the groups has a group represented by the following formula (W).

[0170] According to this embodiment, the solubility of the compound in solvents or resins can be improved, and aggregation or precipitation of the compound in the composition can be suppressed. Thus, when the composition of the present invention is used to manufacture a film, defects derived from insolubles can be suppressed, and a uniform film with good film quality can be manufactured.

[0171] In addition, Ar 1 (Ar 2 ) has a substituent, Ar 1 (Ar 2 ) It is preferred that there is no aryl or heteroaryl group at the ortho position relative to the square acid site. For example, as in the following compounds, when there is an aryl group at the ortho position, there is a tendency for the bond to be distorted and shortened or the firmness to be reduced due to steric hindrance. In addition, the side absorption increases due to the transition from the ortho position aryl group, so that the transparency is sometimes reduced.

[0172] [Chemical formula 17]

[0173]

[0174] (Group represented by formula (W))

[0175] This is carried out for the group represented by formula (W).

[0176] -S 1 -L 1 -T 1 ……(W)

[0177] In formula (W), S 1 represents a single bond, an arylene group or a heteroarylene group,

[0178] L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO2-, -OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group,

[0179] T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group,

[0180] S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group,1 and T 1 The total number of carbon atoms contained is 5 or more,

[0181] S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

[0182] In formula (W), S 1 represents an arylene group or a heteroarylene group, and is preferably a single bond.

[0183] The arylene group may be monocyclic or polycyclic, preferably monocyclic. The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.

[0184] The heteroarylene group may be a monocyclic group or a polycyclic group. A monocyclic group is preferred. The number of heteroatoms constituting the ring of the heteroarylene group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroarylene group are preferably nitrogen atoms, oxygen atoms, sulfur atoms or selenium atoms. The number of carbon atoms constituting the ring of the heteroarylene group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12.

[0185] In formula (W), L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO2-, -OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 L represents an alkylene group. 1 Preferred are alkylene, alkenylene, alkynylene, -O-, -S-, -NR L1 -, -COO-, -OCO-, -CONR L1 -、-SO2-、-OR L2 - or a combination of these, and from the viewpoint of flexibility and solvent solubility, alkylene, alkenylene, -O-, -OR L2 - or a group formed by combining these, more preferably an alkylene group, an alkenylene group, -O- or -OR L2 -, particularly preferably alkylene, -O- or -OR L2 -.

[0186] L 1The number of carbon atoms of the alkylene group represented is preferably 1 to 40. The lower limit is more preferably 3 or more, further preferably 5 or more, further preferably 10 or more, and particularly preferably 13 or more. The upper limit is more preferably 35 or less, and further preferably 30 or less. The alkylene group may be any of a straight chain, a branched group, or a cyclic group, but a straight chain or a branched group is preferred, and a branched group is particularly preferred. The number of branches is, for example, preferably 2 to 10, and more preferably 2 to 8. When the number of branches is within the above range, solvent solubility is good.

[0187] L 1 The number of carbon atoms of the alkenylene group and alkynylene group represented is preferably 2 to 40. The lower limit is, for example, more preferably 3 or more, further preferably 5 or more, further preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and further preferably 30 or less. The alkenylene group and alkynylene group may be either straight chain or branched, but are preferably straight chain or branched, and particularly preferably branched. The number of branches is preferably 2 to 10, and more preferably 2 to 8. When the number of branches is within the above range, solvent solubility is good.

[0188] R L1 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 4, and particularly preferably 1 to 2. The alkyl group may be either linear or branched.

[0189] R L2 R represents an alkylene group. L2 The meaning of the alkylene group represented by L 1 The alkylene group described above is the same and the preferred range is also the same.

[0190] In formula (W), T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group.

[0191] The number of carbon atoms in the alkyl group, the alkyl group of the trialkylsilyl group, and the alkyl group of the trialkoxysilyl group is preferably 1 to 40. The lower limit is more preferably 3 or more, further preferably 5 or more, further preferably 10 or more, and particularly preferably 13 or more. The upper limit is more preferably 35 or less, further preferably 30 or less. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched.

[0192] The meanings of aryl and heteroaryl are the same as those of 1 and R 2 The aryl group and heteroaryl group are the same as those described above, and the preferred ranges are also the same.

[0193] In formula (W), S 1 is a single bond, l 1 is an alkylene group, T 1 In the case of an alkyl group, L1 With T 1 The total number of carbon atoms contained in is preferably 5 or more, more preferably 6 or more, and further preferably 8 or more from the viewpoint of solvent solubility. The upper limit is preferably 40 or less, and more preferably 35 or less. 1 When L represents an arylene group or a heteroarylene group, 1 With T 1 The total number of carbon atoms contained in is preferably 5 or more, more preferably 6 or more, and further preferably 8 or more from the viewpoint of solvent solubility. The upper limit is, for example, preferably 40 or less, and more preferably 35 or less.

[0194] -L 1 -T 1 When the number of carbon atoms in the moiety is 5 or more, the solubility is good, the generation of defects due to insoluble matter etc. can be suppressed, and a uniform film with good film quality can be produced. 1 -T 1 The number of carbon atoms in the part is set to 5 or more, which can suppress crystallinity. If the crystallinity of the compound is high and the film is heated, the crystallization of the compound progresses, and sometimes the absorption characteristics of the film change, but since the crystallinity of the compound can be suppressed, the crystallization of the compound during heating can be suppressed, and the change of the absorption characteristics of the heated film can be suppressed.

[0195] In the present invention, as a preferred embodiment of formula (W), S 1 is a single bond, and L 1 Alkylene, alkenylene, alkynylene, -O-, -S-, -NR L1 、-COO-、-OCO-、-CONR L1 -、-SO2-、-OR L2 - or a group consisting of these, and T 1 is a combination of alkyl or trialkylsilyl groups. 1 More preferably, alkylene, alkenylene, -O-, -OR L2 - or a group formed by combining these, more preferably an alkylene group, an alkenylene group, -O- or -OR L2 , particularly preferably alkylene, -O- or -OR L2 -.T 1 An alkyl group is more preferred.

[0196] In formula (W), -L 1 -T 1 The moiety also preferably contains a branched alkyl structure. 1 -T 1 Part of them is a branched alkyl group or a branched alkoxy group. 1 -T 1The number of branches of the moiety is preferably 2 to 10, more preferably 2 to 8. 1 -T 1 The number of carbon atoms in the moiety is preferably 5 or more, more preferably 9 or more, and further preferably 10 or more. The upper limit is, for example, preferably 40 or less, and more preferably 35 or less.

[0197] In formula (W), -L 1 -T 1 The part also preferably contains an asymmetric carbon. According to this embodiment, the squarylium salt compound (1) can contain a plurality of optical isomers, and as a result, the solvent solubility of the compound (1) can be further improved. The number of asymmetric carbons is preferably one or more. The upper limit of the asymmetric carbon is not particularly limited, for example, preferably 4 or less.

[0198] In the formula (1), the cation exists in a delocalized form as shown below.

[0199] [Chemical formula 18]

[0200]

[0201] In the present invention, the squarylium salt compound (1) is preferably a compound represented by the following formula (1a). The compound represented by formula (1a) is also a compound of the present invention.

[0202] [Chemical formula 19]

[0203]

[0204] In the formula, Ar 11 and Ar 12 Each independently represents a thiophene ring, a thiazole ring, or a condensed ring containing at least one of these rings,

[0205] R 11 ~R 14 each independently represents an alkyl group, an aryl group or a heteroaryl group,

[0206] R 11 Can be used with R 12 or Ar 11 Bond to form a ring,

[0207] R 13 Can be used with R 14 or Ar 12 Bond to form a ring,

[0208] Ar 11 When it is a thiophene ring or a thiazole ring, R 11 and R 12 At least one of represents an aryl or heteroaryl group having 8 or more atoms,

[0209] Ar12 When it is a thiophene ring or a thiazole ring, R 13 and R 14 At least one of them represents an aryl group or a heteroaryl group having 8 or more atoms.

[0210] As Ar 11 and Ar 12 The condensed ring represented by the formula (a) includes at least one selected from a thiophene ring and a thiazole ring, and the condensed ring may be Ar 1 and Ar 2 The preferred range is the same as that of the condensed ring described above. 11 and Ar 12 The ring represented may have a substituent or may be unsubstituted. Examples of the substituent include the substituent group T and the group represented by the above formula (W). The group represented by the formula (W) is preferred.

[0211] R 11 ~R 14 The alkyl, aryl and heteroaryl represented by R 1 ~R 4 The alkyl, aryl and heteroaryl groups described above have the same meanings and the same preferred ranges. 11 ~R 14 The alkyl group, aryl group and heteroaryl group represented by the formula (W) may have a substituent or may be unsubstituted. As the substituent, there can be mentioned the substituent group T group and the group represented by the formula (W) above. The group represented by the formula (W) is preferred.

[0212] By R 11 With R 12 or Ar 11 The ring formed by bonding and R 13 With R 14 or Ar 12 The ring formed by bonding can be exemplified by the formula (1), wherein R 1 With R 2 or Ar 1 The preferred range is also the same for the ring formed by bonding.

[0213] In formula (1a), preferably selected from Ar 11 ,Ar 12 , R 11 , R 12 , R 13 and R 14 At least one of them has the above-mentioned group represented by formula (W).

[0214] Specific examples of the squarylium salt compound (1) include the compounds described below, but are not limited thereto.

[0215] [Chemical formula 20]

[0216]

[0217] [Chemical formula 21]

[0218]

[0219] [Chemical formula 22]

[0220]

[0221] [Chemical formula 23]

[0222]

[0223] (Synthesis method of squarylium salt compound (1))

[0224] The squarylium salt compound (1) can be synthesized by a conventionally known method, for example, by the method described in Chem. Eur. J., 2008, 14, 11082-11091 or by the method described in paragraphs 0057 to 0062 of JP-A-2009-15114.

[0225] Furthermore, the following intermediate (A) can be synthesized by a cross coupling method, and the obtained intermediate A can be reacted with the following compound (B). This synthesis method is preferred because it can obtain the target compound in good yield.

[0226] [Chemical formula 24]

[0227]

[0228] In the above formula, Ar represents a divalent conjugated group having a heteroaromatic ring containing a chalcogen atom. R represents a hydrogen atom or a substituent independently of each other. X represents a halogen atom such as chlorine, bromine, iodine, and a leaving group such as trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy. Y represents OH, Cl or OR' independently of each other, and R' represents an aryl group.

[0229] In the synthesis of the intermediate (A), it is preferred to use a transition metal catalyst and synthesize the intermediate (A) by a cross coupling method. Examples of the transition metal catalyst include palladium catalysts, copper catalysts, and nickel catalysts.

[0230] <<Other near-infrared absorbing compounds>>

[0231] The composition of the present invention may further contain a near infrared absorbing compound other than the above-mentioned squarylium salt compound (1) (hereinafter, also referred to as other near infrared absorbing compounds). The other near infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm, more preferably a compound having a maximum absorption wavelength in the range of 700 to 1000 nm.

[0232] As other near-infrared absorbing compounds, for example, phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complexes, naphthoquinone compounds, iminium compounds, azo compounds, etc. As pyrrolopyrrole compounds, for example, compounds described in paragraphs 0016 to 0058 of Japanese Patent Publication No. 2009-263614, etc. can be mentioned. In addition, squarylium salt compounds other than the above-mentioned squarylium salt compound (1) can also be used. Phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, cyanine compounds, squarylium salt compounds and keto acid compounds can use compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Publication No. 2010-111750, and the contents are incorporated into this specification. For cyanine compounds, for example, reference can be made to "Functional Pigments, Okawara Nobuyuki, Matsuoka Ken, Kitao Teijiro, Hirashima Tsuneaki, Kodansha Scientific", and the contents are incorporated into this specification.

[0233] When the composition of the present invention contains other near-infrared absorbing compounds, the content of the other near-infrared absorbing compounds is preferably set to 0.1 to 70% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less. When the composition of the present invention contains two or more other near-infrared absorbing compounds, the total amount is preferably within the above range.

[0234] Furthermore, the composition of the present invention may also be configured to contain no other near-infrared absorbing compounds. The fact that the composition of the present invention substantially contains no other near-infrared absorbing compounds means that the content of the other near-infrared absorbing compounds is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and further preferably not contained in the total solid content of the composition of the present invention.

[0235] <<Color coloring agent>>

[0236] The composition of the present invention may contain a chromatic colorant. In the present invention, the chromatic colorant refers to a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant having a maximum absorption wavelength in the range of 400 to 650 nm.

[0237] In the present invention, the coloring agent may be a pigment or a dye, and a pigment is preferred.

[0238] The pigment is preferably an organic pigment, and the following organic pigments may be mentioned. However, the present invention is not limited thereto.

[0239] Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 18, 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, etc. (the above are yellow pigments),

[0240] CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments),

[0241] CI 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, 145 6, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (the above are red pigments),

[0242] CI Pigment Green 7, 10, 36, 37, 58, 59, etc. (the above are green pigments),

[0243] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments),

[0244] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments),

[0245] These organic pigments may be used alone or in combination of two or more.

[0246] As dye, there is no particular restriction, known dye can be used. As chemical structure, dyes such as pyrazole azo system, aniline azo system, triphenylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azoimine system, xanthene (xanthene) system, phthalocyanine system, benzopyran system, indigo system, methylene pyrrole system. And, the polymer of these dyes can also be used. And, the dye of recording in Japanese Patent Laid-Open No. 2015-028144 Gazette, Japanese Patent Laid-Open No. 2015-34966 Gazette can be used.

[0247] Furthermore, as the dye, an acid dye and / or a derivative thereof may be appropriately used.

[0248] In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be effectively used.

[0249] Specific examples of the acid dye are given below, but the present invention is not limited to these. For example, the following dyes and derivatives of these dyes can be given.

[0250] Acid Alizarin Violet N,

[0251] Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,

[0252] Acid chrome violet K,

[0253] Acid fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50,

[0254] Acid Orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95,

[0255] Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

[0256] Acid violet 6B, 7, 9, 17, 19,

[0257] Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243,

[0258] Food Yellow 3

[0259] Azo, xanthene, and phthalocyanine acid dyes other than those mentioned above are also preferred. Acid dyes such as CI Solvent Blue 44 and 38, CI Solvent Orange 45, Rhodamine B, and Rhodamine 110, and derivatives of these dyes can also be preferably used.

[0260] Among them, as the dye, it is preferred to select a colorant from triarylmethane series, anthraquinone series, azomethine series, benzylidene series, oxocyanine series, cyanine series, phenothiazine series, pyrrolopyrazole azoimine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrazole azo series, aniline azo series, pyrazolo azo series, pyridone azo series, anthrapyridone series, and methylene pyrrole series.

[0261] Furthermore, a pigment and a dye may be used in combination.

[0262] When the composition of the present invention contains a color colorant, the content of the color colorant is preferably set to 0.1 to 70% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less.

[0263] The content of the color colorant is preferably 10 to 1000 parts by mass, more preferably 50 to 800 parts by mass, based on 100 parts by mass of the squarylium salt compound (1).

[0264] Furthermore, the total amount of the color colorant, the squarylium salt compound (1), and the above-mentioned other near-infrared absorbing compound is preferably set to 1 to 80% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

[0265] When the composition of the present invention contains two or more color colorants, the total amount thereof is preferably within the above range.

[0266] <<Color material that transmits at least a portion of light in the infrared region and blocks light in the visible region (color material that blocks visible light)>>

[0267] The composition of the present invention may also contain a colorant that blocks visible light. In the colorant that blocks visible light, the content of the pigment is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more relative to the total mass of the colorant that blocks visible light. The colorant that blocks visible light preferably presents black, gray, or a color close to them by combining a plurality of colorants. Moreover, the colorant that blocks visible light preferably absorbs light in the wavelength region from violet to red. Moreover, the colorant that blocks visible light preferably blocks light in the wavelength region of 450 to 650 nm.

[0268] In the present invention, the color material that blocks visible light preferably satisfies at least one of the following elements (1) and (2), and more preferably satisfies the element (1).

[0269] (1) Contains two or more colorants

[0270] (2) Method containing an organic black colorant

[0271] In addition, in the present invention, the organic black colorant as a color material for shielding visible light refers to a material that absorbs light in the visible region but transmits at least a portion of light in the infrared region. Therefore, in the present invention, the organic black colorant as a color material for shielding visible light does not include a black colorant that absorbs both light in the infrared region and light in the visible region, that is, it does not include carbon black or titanium black.

[0272] As the color coloring agent, the above-mentioned color coloring agents can be mentioned. As the organic black coloring agent, for example, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. can be mentioned, preferably bisbenzofuranone compounds, perylene compounds. As the bisbenzofuranone compound, the compounds described in Japanese Patent Table 2010-534726 Gazette, Japanese Patent Table 2012-515233 Gazette, Japanese Patent Table 2012-515234 Gazette, etc. can be mentioned, for example, it can be obtained as BASF company "Irgaphor Black". As the perylene compound, CI Pigment Black 31, 32, etc. can be mentioned. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664. For example, it is available as "CHROMOFINE BLACKA1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0273] In the present invention, in the color material that blocks visible light, for example, A / B, which is the ratio of the minimum absorbance value A in the wavelength range of 450 to 650 nm to the minimum absorbance value B in the wavelength range of 900 to 1300 nm, is preferably 4.5 or more.

[0274] The above characteristics may be satisfied by a single raw material or by combining a plurality of raw materials. For example, in the case of the above embodiment (1), it is preferable to combine a plurality of coloring agents to satisfy the above spectral characteristics.

[0275] When two or more chromatic colorants are included as the color material for shielding visible light, the chromatic colorants are preferably selected from red colorants, green colorants, blue colorants, yellow colorants, violet colorants, and orange colorants.

[0276] When two or more chromatic colorants are combined to form a color material that blocks visible light, examples of the combination of chromatic colorants include the following.

[0277] (1) Containing yellow colorant, blue colorant, purple colorant and red colorant

[0278] (2) Containing yellow colorant, blue colorant and red colorant

[0279] (3) Containing yellow colorant, purple colorant and red colorant

[0280] (4) Containing yellow colorant and purple colorant

[0281] (5) Containing green colorant, blue colorant, purple colorant and red colorant

[0282] (6) Containing purple colorant and orange colorant

[0283] (7) Containing green colorant, purple colorant and red colorant

[0284] (8) Containing green colorant and red colorant

[0285] Specific examples of the above-mentioned embodiment (1) include an embodiment containing CI Pigment Yellow 139 or CI Pigment Yellow 185 as a yellow pigment, CI Pigment Blue 15:6 as a blue pigment, CI Pigment Violet 23 as a violet pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0286] Specific examples of the embodiment (2) include an embodiment containing CI Pigment Yellow 139 or CI Pigment Yellow 185 as a yellow pigment, CI Pigment Blue 15:6 as a blue pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0287] Specific examples of the above-mentioned embodiment (3) include an embodiment containing CI Pigment Yellow 139 or CI Pigment Yellow 185 as a yellow pigment, CI Pigment Violet 23 as a violet pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0288] As a specific example of the above-mentioned embodiment (4), there is mentioned an embodiment containing CI Pigment Yellow 139 or CI Pigment Yellow 185 as a yellow pigment and CI Pigment Violet 23 as a violet pigment.

[0289] Specific examples of the above-mentioned embodiment (5) include an embodiment containing CI Pigment Green 7 or CI Pigment Green 36 as a green pigment, CI Pigment Blue 15:6 as a blue pigment, CI Pigment Violet 23 as a violet pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0290] As a specific example of the above-mentioned embodiment (6), there is mentioned an embodiment containing CI Pigment Violet 23 as a violet pigment and CI Pigment Orange 71 as an orange pigment.

[0291] Specific examples of the above (7) include a form containing CI Pigment Green 7 or CI Pigment Green 36 as a green pigment, CI Pigment Violet 23 as a violet pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0292] As a specific example of the above (8), there is mentioned an embodiment containing CI Pigment Green 7 or CI Pigment Green 36 as a green pigment, and CI Pigment Red 254 or CI Pigment Red 224 as a red pigment.

[0293] Examples of the ratio (mass ratio) of each coloring agent include the following.

[0294] [Table 1]

[0295] No. Yellow colorant Green colorant Blue colorant Purple colorant Red colorant Orange colorant 1 0.1～0.4 0.1～0.6 0.01～0.3 0.1～0.6 2 0.1～0.4 0.1～0.6 0.2～0.7 3 0.1～0.6 0.1～0.6 0.1～0.6 4 0.2～0.8 0.2～0.8 5 0.1～0.4 0.1～0.4 0.1～0.4 0.1～0.4 6 0.2～0.6 0.4～0.8 7 0.1～0.5 0.2～0.7 0.1～0.4 8 0.5～0.8 0.2～0.5

[0296] When the composition of the present invention contains a color material that blocks visible light, the content of the color material that blocks visible light is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less relative to the total solid content of the composition. The lower limit can be, for example, 0.01% by mass or more, or 0.5% by mass or more.

[0297] Moreover, the composition of the present invention can be set to a mode that does not substantially contain a color material that blocks visible light. The situation that does not substantially contain a color material that blocks visible light means that the content of the color material that blocks visible light is preferably less than 0.005% by mass of the total solid content of the composition of the present invention, more preferably less than 0.001% by mass, and further preferably does not contain a color material that blocks visible light.

[0298] <<Pigment Derivatives>>

[0299] The composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a portion of the pigment is substituted by an acidic group or a basic group. From the viewpoint of dispersibility and dispersion stability, it is preferred that the pigment derivative contain a pigment derivative having an acidic group or a basic group.

[0300] <<Resin>>

[0301] The composition of the present invention contains a resin. The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

[0302] In the case of epoxy resin, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more, more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 100 or more, more preferably 200 or more.

[0303] Examples of the resin include (meth) acrylic resins, epoxy resins, ene thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, etc. These resins may be used alone or in combination of two or more.

[0304] Among them, from the viewpoint of the solubility of the resin in the squarylium salt compound (1) and the visual transparency, (meth)acrylic resins, polyester resins and epoxy resins are preferred, and (meth)acrylic resins are more preferred.

[0305] Examples of the (meth)acrylic resin include polymers containing structural units derived from (meth)acrylic acid and / or esters thereof, and specifically, polymers obtained by polymerizing at least one selected from (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile.

[0306] Examples of the polyester resin include polymers obtained by the reaction of a polyol (e.g., ethylene glycol, propylene glycol, glycerol, trimethylolpropane) with a polyacid (e.g., aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atoms of these aromatic nuclei are substituted with methyl, ethyl, phenyl, etc., aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid), and polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (e.g., polycaprolactone).

[0307] Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and aliphatic epoxy resin.

[0308] Examples of the bisphenol A epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, and JER1010 (all manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC CORPORATION).

[0309] Examples of the bisphenol F epoxy resin include JER806, JER807, JER4004, JER4005, JER4007, and JER4010 (all manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON830 and EPICLON835 (all manufactured by DICCORPORATION), and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.).

[0310] Examples of the phenol novolac epoxy resin include JER 152, JER 154, JER 157S70, and JER 157S65 (all manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC CORPORATION).

[0311] Examples of the cresol novolac epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DICCORPORATION), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0312] Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (all manufactured by ADEKA CORPORATION), CELOXIDE 2021P, CELOXIDE 2081, CELOXIDE 2083, CELOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (all manufactured by Daicel Corporation), DENACOL EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Corporation), and the like.

[0313] In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (all manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION), JER1031S (manufactured by Mitsubishi Chemical Co., Ltd.), RIPOXY SPCF-9X (manufactured by SHOWA DENKO KK), etc. can be mentioned.

[0314] Furthermore, the resin may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The acid groups may be one or more.

[0315] As the resin having an acid group, polymers having a carboxyl group in the side chain are preferred, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolac resins, and acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding anhydride to a polymer having a hydroxyl group. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are preferred. As other monomers copolymerizable with (meth)acrylic acid, alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, etc. can be cited. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include 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, and cyclohexyl (meth)acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, polystyrene macromonomers, and polymethyl methacrylate macromonomers. Examples of the N-substituted maleimide monomer described in Japanese Patent Application Laid-Open No. 10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, other monomers copolymerizable with these (meth)acrylic acids may be used alone or in combination of two or more.

[0316] The resin having an acid group can preferably include a multi-component copolymer including benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylic acid / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylic acid copolymer, and benzyl (meth) acrylic acid / (meth) acrylic acid / other monomers. In addition, a copolymer of 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in Japanese Patent Laid-Open No. 7-140654, 2-hydroxy-3-phenoxypropyl ester / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl acrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, and 2-hydroxyethyl acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

[0317] The resin having an acid group also preferably includes a polymer obtained by polymerizing monomer components including a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

[0318] [Chemical formula 25]

[0319]

[0320] In the general formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[0321] [Chemical formula 26]

[0322]

[0323] In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the general formula (ED2) can be found in Japanese Unexamined Patent Application Publication No. 2010-168539.

[0324] In the general formula (ED1), as R 1 and R 2The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited, and examples thereof include straight-chain or branched alkyl groups such as methyl, ethyl, isopropyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl, etc. Among them, substituents of primary or secondary carbon which are not easily removed by acid and heat such as methyl, ethyl, cyclohexyl, and benzyl are particularly preferred from the viewpoint of heat resistance.

[0325] As a specific example of the ether dimer, for example, reference can be made to paragraph 0317 of Japanese Patent Application Publication No. 2013-29760, and the content is incorporated into this specification. The ether dimer may be only one type or two or more types. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

[0326] The resin having an acid group may contain a structural unit derived from a compound represented by the following formula (X).

[0327] [Chemical formula 27]

[0328]

[0329] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

[0330] In the above formula (X), the carbon number of the alkylene group of R2 is preferably 2 to 3. The carbon number of the alkyl group of R3 is 1 to 20, more preferably 1 to 10, and the alkyl group of R3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R3 include benzyl and 2-phenyl(iso)propyl.

[0331] As the resin having an acid group, reference may be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (the corresponding U.S. Patent Application Publication No. 2012 / 0235099). <0685> ~ <0700> The descriptions in paragraphs 0076 to 0099 of Japanese Patent Application Laid-Open No. 2012-198408 are incorporated into this specification.

[0332] The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less.

[0333] The resin may have a crosslinkable group. In the present invention, a crosslinkable group refers to a group that reacts by the action of heat, light or free radicals to form a chemical bond. Specifically, a group having an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group, an alkoxysilyl group, a chlorosilyl group, etc. may be mentioned. As a resin having a crosslinkable group, for example, a resin containing a structural unit having a crosslinkable group or the above-mentioned epoxy resin may be mentioned. As a structural unit having a crosslinkable group, the following formula (A2-1) to formula (A2-4) may be mentioned.

[0334] [Chemical formula 28]

[0335]

[0336] R 1 represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. 1 A hydrogen atom or a methyl group is preferred.

[0337] L 51 represents 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-, -SO2-, -NR 10 -(R 10 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom) or a group containing a combination thereof, preferably a group containing a combination of at least one of an alkylene group, an arylene group, and an alkylene group and -O-. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 10. The alkylene group may have a substituent, preferably unsubstituted. The alkylene group may be any of a straight chain, a branched group, and a cyclic group. Moreover, the cyclic alkylene group may be any of a monocyclic group and a polycyclic group. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10.

[0338] P 1Represents a crosslinking group. As a crosslinking group, a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, an alkoxysilyl group, a chlorosilyl group, etc. can be cited. A group having an ethylenically unsaturated bond, a cyclic ether group, an alkoxysilyl group, and a chlorosilyl group are preferred. As a group having an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, etc. can be cited. As a cyclic ether group, an epoxy group (oxiranyl), an oxetane group, etc. can be cited. As an alkoxysilyl group, a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group can be cited. The group having an ethylenically unsaturated bond is preferably a (meth)acryloyl group and a (meth)acryloyloxy group. The cyclic ether group is preferably an epoxy group. The alkoxysilyl group is preferably a dialkoxysilyl group and a trialkoxysilyl group. Moreover, the number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. Examples of the chlorosilyl group include a monochlorosilyl group, a dichlorosilyl group, and a trichlorosilyl group, among which a dichlorosilyl group and a trichlorosilyl group are preferred, and a trichlorosilyl group is more preferred.

[0339] Examples of the crosslinkable group-containing resin include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing urethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), VISCOTE R-264, KS resist 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (both manufactured by Daicel Corporation Co., Ltd.), Ebecry 13800 (manufactured by Daicel UCB Co., Ltd.), Akurikua-RD-F8 (manufactured by NIPPON SHOKUBAICO., LTD.), etc. In addition, the above-mentioned epoxy resins and the like can be cited.

[0340] The resin also preferably has a structural unit represented by the following formula (A3-1) to formula (A3-7).

[0341] [Chemical formula 29]

[0342]

[0343] In the formula, R 5 represents a hydrogen atom or an alkyl group, L 4 ~L 7 Each independently represents a single bond or a divalent linking group, R 10 ~R13 R each independently represents an alkyl group or an aryl group. 14 and R 15 Each independently represents a hydrogen atom or a substituent.

[0344] R 5 R of formula (A2-1) to formula (A2-4) 1 The meanings are the same, and the preferred ranges are also the same.

[0345] L 4 ~L 7 and L of formula (A2-1) to formula (A2-4) 1 The meanings are the same, and the preferred ranges are also the same.

[0346] R 10 The alkyl group represented may be linear, branched or cyclic, preferably cyclic. The alkyl group may have the above-mentioned substituents or may be unsubstituted. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. 10 The number of carbon atoms in the aryl group represented by is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. 10 A cyclic alkyl group or an aryl group is preferred.

[0347] R 11 , R 12 The alkyl group represented may be linear, branched or cyclic, preferably linear or branched. The alkyl group may have the above-mentioned substituents or may be unsubstituted. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 4. R 11 , R 12 The number of carbon atoms in the aryl group represented by is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. 11 , R 12 A linear or branched alkyl group is preferred.

[0348] R 13 The alkyl group represented may be linear, branched or cyclic, preferably linear or branched. The alkyl group may have the above-mentioned substituents or may be unsubstituted. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 4. 13 The number of carbon atoms in the aryl group represented by is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. 13 A linear or branched alkyl group or an aryl group is preferred.

[0349] R 14 and R 15 The substituent represented by may include the groups explained with reference to the substituent group T. Among them, R 14 and R15 At least one of them represents cyano or -COOR a Ra represents a hydrogen atom or a substituent. The substituent that Ra may have includes the groups described in the substituent group T. For example, an alkyl group and an aryl group are preferred.

[0350] The content of the resin is preferably 1 to 80% by mass relative to the total solid content of the composition, with a lower limit of preferably 5% by mass or more, more preferably 7% by mass or more, and an upper limit of preferably 50% by mass or less, more preferably 30% by mass or less.

[0351] <<Compound having a cross-linking group (cross-linking compound)>>

[0352] The composition of the present invention may contain a compound having a crosslinking group (crosslinking compound). The composition contains a crosslinking compound, thereby forming a film with excellent heat resistance and solvent resistance. As a crosslinking compound, a known compound that can be crosslinked by free radicals, acid, and heat can be used. For example, a compound having a group containing an ethylenically unsaturated bond, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxysilyl group, a chlorosilyl group, etc. can be cited. Regarding the details of the group having an ethylenically unsaturated bond, the cyclic ether group, the alkoxysilyl group, and the chlorosilyl group, the groups described in the above-mentioned resin can be cited.

[0353] The cross-linking compound may be any form of a monomer or a polymer, preferably a monomer. The molecular weight of the monomer type cross-linking compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. Moreover, the cross-linking compound is also preferably a compound that does not substantially have a molecular weight distribution. Here, substantially having no molecular weight distribution means that the dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the compound is preferably 1.0 to 1.5, more preferably 1.0 to 1.3.

[0354] [Compound containing a group having an ethylenically unsaturated bond]

[0355] In the present invention, a compound containing a group having an ethylenically unsaturated bond can be used as a crosslinking compound. The compound containing a group having an ethylenically unsaturated bond is preferably a monomer. The molecular weight of the compound containing a group having an ethylenically unsaturated bond is preferably 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. The compound containing a group having an ethylenically unsaturated bond is preferably a 3-15-functional (meth)acrylate compound, and more preferably a 3-6-functional (meth)acrylate compound.

[0356] As examples of the above compounds, reference can be made to paragraphs 0033 to 0034 of JP-A-2013-253224, the contents of which are incorporated herein. Preferred examples of the compound include vinyloxy-modified pentaerythritol tetraacrylate (commercially available as NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which such (meth)acryloyl groups are interposed with ethylene glycol and propylene glycol residues. Moreover, their oligomer types can also be used. Moreover, the description of polymerizable compounds in paragraphs 0034 to 0038 of Japanese Patent Publication No. 2013-253224 can be referred to, and the contents are incorporated into this specification. Moreover, paragraph 0477 of Japanese Patent Publication No. 2012-208494 (the corresponding U.S. Patent Application Publication No. 2012 / 0235099) can be cited. <0585> The polymerizable monomers described in paragraph ) are incorporated into this specification.

[0357] Furthermore, diglycerol E0 (ethylene oxide) modified (meth) acrylate (commercially available as M-460; manufactured by Toagosei Co., Ltd.) is preferred. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred. Their oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited.

[0358] The compound containing a group having an ethylenically unsaturated bond may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the above-mentioned compound having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids can be cited. It is preferred that the unreacted hydroxyl groups of aliphatic polyhydroxy compounds react with non-aromatic carboxylic anhydrides to form a compound having an acid group, and it is particularly preferred that in the ester, the aliphatic polyhydroxy compound is a compound of pentaerythritol and / or dipentaerythritol. As commercial products, for example, as polybasic acid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD., M-305, M-510, M-520 of the ARONIX series can be cited. The acid value of the compound having an acid group is preferably 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

[0359] As a compound including a group with an ethylenically unsaturated bond, a compound with a caprolactone structure is also a preferred embodiment. As a compound with a caprolactone structure, there is no particular limitation within the scope of having a caprolactone structure in the molecule, for example, it is possible to cite an ε-caprolactone modified multifunctional (meth) acrylate obtained by esterifying a polyol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. As a compound with a caprolactone structure, reference can be made to the compounds described in paragraphs 0042 to 0045 of Japanese Patent Publication No. 2013-253224, and the content is incorporated into this specification. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as the KAYARAD DPCA series from Nippon Kayaku Co., Ltd., SR-494, which is a tetrafunctional acrylate having four vinyloxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyloxy chains, manufactured by Sartomer Company, Inc.

[0360] As the compound containing a group having an ethylenically unsaturated bond, urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also preferred. In addition, addition polymerizable compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 1-105238 can be used.

[0361] Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

[0362] [Compounds having a cyclic ether group]

[0363] In the present invention, as a crosslinking compound, a compound having a cyclic ether group can be used. As a cyclic ether group, an epoxy group, an oxetane group, etc. can be cited, preferably an epoxy group. As a compound having a cyclic ether group, a monofunctional or multifunctional glycidyl ether compound, a multifunctional aliphatic glycidyl ether compound, etc. can be cited. In addition, a compound having a glycidyl group or a compound having an alicyclic epoxy group as an epoxy group can be used, such as glycidyl (meth) acrylate or allyl glycidyl ether. As such a compound, for example, the records of paragraph 0045 of Japanese Patent Publication No. 2009-265518 can be referred to, and the content is incorporated into this specification. In addition, the epoxy resin described in the above-mentioned resin can also be cited. As a commercially available product of a compound having a cyclic ether group, for example, the records of paragraph 0191 of Japanese Patent Publication No. 2012-155288 can be referred to, and the content is incorporated into this specification.

[0364] [Compounds having an alkoxysilyl group]

[0365] In the present invention, as a crosslinking compound, a compound having an alkoxysilyl group can also be used. The number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. The alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group. Alkoxysilane preferably has two or more in one molecule, and more preferably has 2 to 3. Specific examples of the compound having an alkoxysilyl group include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyl ... silane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyl ether propylmethyldimethoxysilane, 3-glycidyl ether propyltrimethoxysilane, 3-glycidyl ether propylmethyldiethoxysilane, 3-glycidyl ether propyltriethoxysilane, p-phenylenediyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methyl Acryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1 , 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, the hydrochloride of N-(vinyl benzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilyl propyl) isocyanurate, 3-ureapropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, 3-mercaptopropyl trimethoxy silane, bis(triethoxysilyl propyl) tetrasulfide, 3-isocyanate propyl triethoxy silane etc. And, alkoxy oligomers can also be used in addition to the above. And, the following compounds can also be used.

[0366] [Chemical formula 30]

[0367]

[0368] Examples of commercially available products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 , KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-90 3. KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE- 846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-181 0. X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, 0. KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308,

[0369] [Compounds having a chlorosilyl group]

[0370] In the present invention, a compound having a chlorosilyl group can be used as a crosslinking compound. The chlorosilyl group is a dichlorosilyl group or a trichlorosilyl group. It is preferred that there are two or more chlorosilyl groups in one molecule, and it is further preferred that there are 2 to 3 chlorosilyl groups. Examples of the compound having a chlorosilyl group include methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dichloro(methyl)phenylsilane, dimethyldichlorosilane, and diethyldichlorosilane.

[0371] The content of the crosslinkable compound is preferably 1 to 90% by mass relative to the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 75% by mass or less.

[0372] The crosslinking compound may be used alone or in combination of two or more. When used in combination of two or more, the total amount is preferably within the above range.

[0373] <<Photopolymerization Initiator>>

[0374] The composition of the present invention may contain a photopolymerization initiator. In particular, when the composition contains a resin or a crosslinking compound having the following group, or a free radical polymerizable component, it is preferred to contain a photopolymerization initiator, wherein the group has an ethylenically unsaturated bond. There is no particular limitation on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, a polymerization initiator that is photosensitized to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator. Moreover, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300nm to 800nm ​​(more preferably 330nm to 500nm).

[0375] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds (thio compounds), ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compounds described in British Patent No. 1388492, the compounds described in Japanese Unexamined Patent Publication No. 53-133428, the compounds described in German Patent No. 3337024, the compounds described in J. Org. Chem., 29, 1527 (1964) based on FC Schaefer et al., the compounds described in Japanese Unexamined Patent Publication No. 62-58241, the compounds described in Japanese Unexamined Patent Publication No. 5-281728, the compounds described in Japanese Unexamined Patent Publication No. 5-34920, the compounds described in U.S. Patent No. 4212976, and the like.

[0376] Furthermore, from the viewpoint of exposure sensitivity, it is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0377] As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and the acylphosphine-based initiators described in Japanese Patent Publication No. 4225898 can also be used. As hydroxyacetophenone-based initiators, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (product names: all made by BASF) can be used. As aminoacetophenone-based initiators, commercially available IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (product names: all made by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as 365 nm or 405 nm can be used.

[0378] As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (product names: both manufactured by BASF Corporation) can be used.

[0379] As the photopolymerization initiator, more preferably an oxime compound is used. Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166.

[0380] Examples of the oxime compounds that can be preferably used include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In addition, compounds described in JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese Patent Application Publication No. 2000-66385, Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2006-342166, etc. can also be mentioned. Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. Furthermore, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.) and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used.

[0381] As oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the N position of carbazole, compounds described in U.S. Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone site, compounds described in JP-A-2010-15025 and U.S. Pat. No. 2009-292039 in which a nitro group is introduced into the pigment site, and compounds described in International Publication No. 2006-11-16326 The ketoxime compounds described in U.S. Patent No. 2009-131189, the compounds described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, the compounds described in Japanese Patent Publication No. 2009-221114 having maximum absorption at 405 nm and good sensitivity to a g-ray light source, the compounds described in paragraphs 0076 to 0079 of Japanese Patent Publication No. 2014-137466, etc.

[0382] For example, it is preferable to refer to paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 and incorporate the contents into the present specification.

[0383] Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1): In addition, the oxime may be an oxime compound in which the NO bond of the oxime is an (E)-form, an oxime compound in which the NO bond of the oxime is an (Z)-form, or a mixture of the (E)-form and the (Z)-form.

[0384] [Chemical formula 31]

[0385]

[0386] In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

[0387] In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

[0388] Examples of the monovalent non-metallic atomic group include alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl, arylthiocarbonyl, etc. Furthermore, these groups may have one or more substituents. Furthermore, the substituents may be further substituted by other substituents.

[0389] Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

[0390] In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

[0391] In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituents include the substituents listed above.

[0392] In the present invention, an oxime compound having a fluorene ring may be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Unexamined Patent Publication No. 2014-137466. This content is incorporated into this specification.

[0393] As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Unexamined Patent Publication No. 2013-164471. This content is incorporated into this specification.

[0394] As the photopolymerization initiator, an oxime compound having a nitro group can be used. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and paragraphs 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0395] Specific examples of the oxime compound preferably used are shown below, but the present invention is not limited thereto.

[0396] [Chemical formula 32]

[0397]

[0398] [Chemical formula 33]

[0399]

[0400] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

[0401] From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method, specifically, for example, preferably using an ultraviolet visible spectrophotometer (Varian Cary-5 spectrophotometer) and measuring at a concentration of 0.01 g / L using an ethyl acetate solvent.

[0402] The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass relative to the total solid content of the composition. Within this range, better sensitivity and pattern formation can be obtained. The composition may contain only one photopolymerization initiator or may contain two or more. When containing two or more, the total amount is preferably within the above range.

[0403] <<Acid Generator>>

[0404] The composition of the present invention may contain an acid generator. In particular, when the composition contains a cationic polymerizable component such as a resin or a cross-linking compound having a cyclic ether group, it is preferred to contain an acid generator. The acid generator is preferably a compound that generates acid by light irradiation (photoacid generator). As the acid generator, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, etc., which decompose and generate acid by light irradiation, sulfonate compounds such as imide sulfonates, oxime sulfonates, diazonium disulfones, disulfones, and o-nitrobenzyl sulfonates can be cited. As the type, specific compound, and preferred example of the acid generator, the compounds described in paragraphs

[0066] to

[0122] of Japanese Patent Publication No. 2008-13646 can be cited, and the compound can be applied to the present invention.

[0405] Preferred compounds as the acid generator include compounds represented by the following formula (b1), formula (b2), and formula (b3).

[0406] [Chemical formula 34]

[0407]

[0408] In formula (b1), R 201 , R 202 and R 203 Each independently represents an organic group. - represents a non-nucleophilic anion, and preferably includes a sulfonic acid anion, a carboxylic acid anion, a bis(alkylsulfonyl)amide anion, a tri(alkylsulfonyl)methide anion, BF4 - PF6 - 、SbF6 - Or the following groups, preferably BF4 - PF6 - 、SbF6 - .

[0409] Examples of commercially available acid generators include WPAG-469 (manufactured by Wako Pure Chemical Co., Ltd.) and CPI-100P (manufactured by San-Apro Ltd.).

[0410] The content of the acid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass relative to the total solid content of the composition. The composition of the present invention may contain only one acid generator or two or more. When containing two or more, the total amount thereof is preferably within the above range.

[0411] <<Crosslinking Aid>>

[0412] The composition of the present invention is preferably provided with a crosslinking aid for the purpose of promoting the crosslinking reaction of a crosslinking component (resin or crosslinking compound having a crosslinking group). As a crosslinking aid, it is preferred to include at least one selected from a polyvalent thiol, an alcohol, an amine and a carboxylic acid. The content of the crosslinking aid is preferably 1 to 1000 parts by mass, more preferably 1 to 500 parts by mass, and further preferably 1 to 200 parts by mass relative to 100 parts by mass of the crosslinking compound. The composition may include only one crosslinking aid or may include two or more. When including two or more, the total amount is preferably within the above range.

[0413] (Multifunctional thiol)

[0414] Examples of the polyfunctional thiol include compounds having two or more thiol groups in the molecule. The polyfunctional thiol is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).

[0415] General formula (T1)

[0416] [Chemical formula 35]

[0417]

[0418] (In formula (T1), n ​​represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

[0419] In the above general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and it is particularly preferred that n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and compounds represented by formula (T2) are particularly preferred. One or more polyfunctional thiol compounds may be used in combination.

[0420] [Chemical formula 36]

[0421]

[0422] (amine)

[0423] As the amine of the cross-linking auxiliary agent, a polyvalent amine is preferred, and a diamine is more preferred. Examples thereof include hexamethylenediamine, triethylenetetramine, polyethyleneimine, and the like.

[0424] (alcohol)

[0425] The alcohol used as the crosslinking aid is preferably a polyol, more preferably a diol. For example, polyether diol compounds, polyester diol compounds, polycarbonate diol compounds, etc. can be cited. Specific examples of alcohols can be found in paragraphs 0128 to 0163 and 0172 of Japanese Patent Application Publication No. 2013-253224, and the contents are incorporated into this specification.

[0426] (carboxylic acid)

[0427] Examples of the carboxylic acid as the cross-linking aid include 3,3',4,4'-biphenyltetracarboxylic acid (anhydrous), maleic acid, phthalic acid, trimellitic acid, and the like.

[0428] <<Crosslinking Catalyst>>

[0429] The composition of the present invention can further contain a crosslinking catalyst. In particular, when a compound having an alkoxysilyl group or a chlorosilyl group is contained as a crosslinking compound, the sol-gel reaction is promoted by containing a crosslinking catalyst, thereby obtaining a solid cured film. As a crosslinking catalyst, an acid catalyst, a base catalyst, etc. can be cited. As an acid catalyst, carboxylic acids such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic acid or acetic acid, substituted carboxylic acids of the structural formula R represented by other atoms or substituents, sulfonic acids such as benzenesulfonic acid, phosphoric acid, etc. can be cited. In addition, Lewis acids such as aluminum chloride, aluminum acetylacetonate, zinc chloride, tin chloride, boron trifluoride diethyl ether complex, and trimethyl iodosilane can also be used. In addition, as a base catalyst, ammonia base compounds such as ammonia water, organic amines such as ethylamine or aniline, etc. can be cited. In addition, the crosslinking catalyst can also use the catalysts described in paragraphs 0070 to 0076 of Japanese Patent Publication No. 2013-201007.

[0430] The content of the crosslinking catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and further preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the crosslinking compound. The composition may contain only one crosslinking catalyst or two or more. When containing two or more, the total amount is preferably within the above range.

[0431] <<Solvents>>

[0432] The composition of the present invention may contain a solvent. Examples of the solvent include water and organic solvents. There are no particular restrictions on the solvent as long as the solubility of each component or the coating properties of the composition are satisfied. The solvent is preferably selected in consideration of the coating properties and safety of the composition.

[0433] Examples of the organic solvent include the following solvents.

[0434] Preferred examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3- Oxypropionic acid alkyl esters (e.g., 3-oxypropionic acid methyl ester, 3-oxypropionic acid ethyl ester, etc. (e.g., 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-oxypropionic acid alkyl esters (e.g., 2-oxypropionic acid methyl ester, 2-oxypropionic acid ethyl ester, 2-oxypropionic acid propyl ester, etc. (e.g., 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid propyl ester, etc.) methyl propionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and ethers such as diethylene glycol dimethyl ether and tetrahydrofuran are preferably mentioned. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like, and as aromatic hydrocarbons, for example, toluene, xylene, and the like are preferably mentioned.

[0435] The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used in combination, a mixed solution consisting of two or more selected from the group consisting of 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate is particularly preferred.

[0436] As for the solvent, it is preferred to use a solvent with a low metal content, and the metal content of the solvent is preferably 10 ppb or less, for example. A ppt-grade solvent can be used as needed, and such a high-purity solvent is provided by, for example, TOYO Gosei Co., Ltd.

[0437] As a method for removing impurities such as metals from a solvent, for example, distillation (molecular distillation or thin film distillation, etc.) or filtering using a filter can be cited. As the filter aperture in the filtering using a filter, the preferred pore size is 10nm or less, more preferably 5nm or less, and further preferably 3nm or less. As the material of the filter, preferably polytetrafluoroethylene, polyethylene, or nylon filters.

[0438] The solvent may contain isomers (compounds having the same number of atoms but different structures), and may contain only one type of isomer or a plurality of types of isomers.

[0439] The peroxide content of the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0440] The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 25 to 75% by mass, based on the total amount of the composition.

[0441] <<Polymerization Inhibitor>>

[0442] The composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the crosslinking compound during production or storage of the composition.

[0443] Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, primary cerium salts, etc.). Among them, p-methoxyphenol is preferred.

[0444] The content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the composition.

[0445] <<Surfactants>>

[0446] From the viewpoint of further improving coating properties, the composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.

[0447] The composition contains a fluorine-based surfactant, thereby further improving the liquid properties (especially fluidity) when prepared as a coating liquid, and further improving the uniformity of the coating thickness or the liquid saving. That is, when a coating liquid to which a composition containing a fluorine-based surfactant is applied is used to form a film, the surface tension between the coated surface and the coating liquid decreases, the wettability of the coated surface is improved, and the coating property of the coated surface is improved. Therefore, a uniform film with less uneven thickness can be formed more appropriately.

[0448] 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. From the perspective of uniformity of the thickness of the coating film and liquid saving, a fluorine-based surfactant having a fluorine content within this range is more effective and has good solubility in the composition.

[0449] Specific examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060 to 0064 of the corresponding WO 2014 / 17669 pamphlet), and the contents are incorporated herein. Examples of commercially available fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc.

[0450] The fluorine-based surfactant may also use a block polymer, and as a specific example, the compounds described in Japanese Patent Application Laid-Open No. 2011-89090 may be cited. The fluorine-based surfactant may also preferably use a fluorine-containing polymer compound, which contains a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups), and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[0451] [Chemical formula 37]

[0452]

[0453] The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000.

[0454] Moreover, as a fluorine-based surfactant, it can also be used for a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. As a specific example, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, RS-718K, RS-72-K made by DIC CORPORATION, etc. can be cited. In addition, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain is equivalent to a surfactant, and is a component different from the resin and crosslinking compound having a crosslinking group described above. Fluorine-based surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327.

[0455] Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited), and the like. Furthermore, NCW-101, NCW-1001, and NCW-1002 manufactured by WakoPure Chemical Industries, LTD. can also be used.

[0456] Specific examples of the cationic surfactant include phthalocyanine derivatives (product name: EFKA-745, manufactured by MORISHITA & CO., LTD.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., LTD.), (meth)acrylic (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., LTD.).

[0457] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and Sandetto BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0458] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Corporation), and the like.

[0459] The surfactant may be used alone or in combination of two or more.

[0460] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0461] <<Ultraviolet light absorber>>

[0462] The composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is preferably a conjugated diene compound, and more preferably a compound represented by the following general formula (1).

[0463] [Chemical formula 38]

[0464]

[0465] R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 With R 2 They may be the same as or different from each other, but they do not both represent hydrogen atoms.

[0466] R 3 and R 4 represents an electron withdrawing group. Here, the electron withdrawing group is a group having a Hammett substituent constant σp value (hereinafter referred to as "σp value") of 0.20 or more and 1.0 or less. Preferably, the σp value is 0.30 or more and 0.8 or less. 3 , R 4 , preferably acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, aminosulfonyl, particularly preferably acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, alkylsulfonyl, arylsulfonyl, sulfonyloxy, aminosulfonyl. For the above general formula (1), reference may be made to paragraphs 0148 to 0158 of Japanese Patent Application Publication No. 2010-049029, and the contents are incorporated into this specification.

[0467] Specific examples of the compound represented by the general formula (1) include the following compounds: In addition, compounds described in paragraphs 0160 to 0162 of JP-A-2010-049029 are also exemplified, and the contents are incorporated into the present specification.

[0468] [Chemical formula 39]

[0469]

[0470] As a commercial item of an ultraviolet absorber, UV503 (DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example.

[0471] The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition of the present invention.

[0472] <<Other ingredients>>

[0473] The near infrared absorbing composition may contain dispersants, sensitizers, curing accelerators, fillers, thermosetting accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.) as needed. By appropriately containing these ingredients, the stability of the target infrared cut filter, film properties, and other properties can be adjusted. For these ingredients, for example, reference can be made to paragraph 0183 and thereafter of Japanese Patent Application Publication No. 2012-003225 (the corresponding U.S. Patent Application Publication No. 2013 / 0034812). <0237> The descriptions in paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, etc., are incorporated into this specification. Moreover, as antioxidants, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. Phenol compounds with a molecular weight of 500 or more, phosphite compounds with a molecular weight of 500 or more, or thioether compounds with a molecular weight of 500 or more are more preferred. Two or more of these can be mixed and used. As phenol compounds, any phenol compounds known as phenol-based antioxidants can be used. As preferred phenol compounds, hindered phenol compounds can be cited. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are particularly preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and a methyl group, an ethyl group, a propionyl group, an isopropionyl group, a butyl group, an isobutyl group, a tert-pentyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, an octyl group, an isooctyl group, and a 2-ethylhexyl group are more preferred. In addition, a compound (antioxidant) having a phenol group and a phosphite group in the same molecule is also preferred. In addition, the antioxidant can also appropriately use a phosphorus antioxidant. Examples of the phosphorus-based antioxidant include at least one compound selected from the group consisting of tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinoheptan-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinoheptan-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tert-butyl-6-methylphenyl). These are easily available as commercial products, and examples thereof include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, and ADKSTAB A0-330 (ADEKA CORPORATION). The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, relative to the total solid content of the composition.The antioxidant may be used alone or in combination of two or more. When used in combination of two or more, the total amount is preferably within the above range.

[0474] <Method for preparing composition>

[0475] The composition of the present invention can be prepared by mixing the ingredients.

[0476] When preparing the composition, each component may be blended at once, or each component may be dissolved / dispersed in a solvent and then blended one by one. Moreover, the order of input and the operating conditions during blending are not particularly limited. For example, all components may be dissolved / dispersed in a solvent at the same time to prepare the composition, or each component may be appropriately prepared into two or more solutions / dispersions in advance as needed, and these may be mixed when used (when applied) to prepare the composition.

[0477] When preparing composition, for the purpose of removing impurities or reducing defects, it is preferred to utilize a filter to filter each component. As a filter, as long as it is a filter used for filtering purposes in the past, it can be used without particular restriction. For example, filters such as polyolefin resins (including high density, ultra-high molecular weight) such as polyamide resins such as polytetrafluoroethylene (PTFE), nylon (such as nylon-6, nylon-6,6), polyethylene, polypropylene (PP), etc. can be enumerated. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0478] The pore size of the filter is appropriately 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. By setting it within this range, fine impurities that hinder the preparation of a uniform and smooth composition in the subsequent process can be reliably removed. In addition, it is also preferred to use a fibrous filter material. For example, polypropylene fiber, nylon fiber, glass fiber, etc. can be cited as the filter material. Specifically, SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter elements manufactured by ROK [TECHNO CO., LTD. can be used.

[0479] When using filters, different filters can be combined. At this time, filtering using the first filter can be performed only once or twice or more.

[0480] Furthermore, the first filter of different pore diameters can also be combined within the above range. The pore diameter here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it can be selected from various filters provided by NIHON PALL LTD. (DFA4201NXEY, etc.), Advantec Toyo Kaisha, LTD., Japan Entegris Inc. (formerly Nippon Microlis Corporation) or KITZ MICROFILTFR CORPORATION.

[0481] The second filter can be formed of the same material as the above-mentioned first filter.

[0482] For example, filtration using the first filter may be performed only on the dispersion, and filtration using the second filter may be performed after mixing other components.

[0483] <Film and near infrared cut filter>

[0484] Next, the film of the present invention is described. The film of the present invention is formed by the composition of the present invention described above. The infrared shielding and visible transparency of the film of the present invention are excellent, so it can be preferably used as an infrared cut-off filter and an infrared transmission filter. Moreover, heat resistance and light resistance are also excellent. The film of the present invention may have a pattern or may be a film (flat film) without a pattern. In addition, when the film of the present invention is used as an infrared transmission filter, the infrared transmission filter may, for example, include a filter that shields visible light and transmits light with a wavelength of 900nm or more. In addition, when the film of the present invention is used as an infrared transmission filter, the infrared transmission filter is preferably formed by a composition comprising a squarylium salt compound and a color material (preferably a color material containing two or more color colorants or a color material containing at least an organic black colorant) that shields visible light, or a filter having a layer of a color material that shields visible light in addition to a layer comprising a squarylium salt compound. When the film of the present invention is used as an infrared transmission filter, the squarylium salt compound has the effect of limiting the infrared region of the transmitted light (infrared) to the long wavelength side.

[0485] Furthermore, the infrared cut filter of the present invention comprises the above-mentioned composition of the present invention.

[0486] The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The film of the present invention can be preferably used as an infrared cutoff filter of a solid-state imaging element such as a CCD (charge coupled device) or a CMOS (complementary metal oxide film semiconductor). Moreover, it can also be used in various image display devices.

[0487] The film (infrared cut filter) of the present invention can be used in combination with a color filter containing a color colorant.

[0488] Color filter can be manufactured by using a coloring composition comprising a coloring agent. As a coloring agent, the coloring agent described in the composition of the present invention can be enumerated. The coloring composition can further contain a resin, a compound with a crosslinking group, a photopolymerization initiator, a surfactant, a solvent, an inhibitor, an ultraviolet light absorber, etc. About their details, the material described in the composition of the present invention can be enumerated, and these can be used. And, the film of the present invention (infrared cut-off filter) can also be made to contain a coloring agent, thus being set as a filter having the function of an infrared cut-off filter and a color filter.

[0489] In addition, in the present invention, the infrared cut filter refers to a filter that transmits light of wavelengths in the visible light region (visible light) and blocks light of wavelengths in the infrared region (infrared light). The infrared cut filter can transmit light of all wavelengths in the visible light region, or transmit light of a specific wavelength region in the light of wavelengths in the visible light region, and block light of the specific wavelength region. Moreover, in the present invention, the color filter refers to a filter that transmits light of a specific wavelength region in the light of wavelengths in the visible light region, and blocks light of the specific wavelength region. Moreover, the infrared transmission filter refers to a filter that blocks light of wavelengths in the visible region, and transmits light of wavelengths in the infrared region (infrared light).

[0490] When the film of the present invention is used as an infrared transmission filter, it preferably has the following spectral characteristics (1): According to this aspect, a film capable of transmitting infrared rays with little interference from visible light can be obtained.

[0491] (1) The maximum value of the transmittance of light in the thickness direction of the film within the wavelength range of 400 to 830 nm is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film within the wavelength range of 1000 to 1300 nm is 80% or more. The film having such spectral characteristics can be preferably used as an infrared transmission filter that shields light in the wavelength range of 400 to 750 nm and transmits light with a wavelength of 900 nm or more.

[0492] The spectral characteristics of the film are values ​​of transmittance measured in a wavelength range of 300 to 1300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

[0493] When the film of the present invention is used as an infrared cut-off filter or an infrared transmission filter, it is also possible to use an infrared cut-off filter and an infrared transmission filter in combination. By using an infrared cut-off filter and an infrared transmission filter in combination, it is possible to preferably be used for the purpose of an infrared sensor for detecting infrared rays of a specific wavelength. When two filters are used in combination, it is possible to use the composition of the present invention to form both an infrared cut-off filter and an infrared transmission filter, or it is possible to use the composition of the present invention to form only one of them.

[0494] Furthermore, when the film of the present invention is used as an infrared cut filter, the infrared cut filter and the color filter may be adjacent or not adjacent in the thickness direction. When the infrared cut filter and the color filter are not adjacent in the thickness direction, the infrared cut filter may be formed on a substrate different from the substrate forming the color filter, or other components constituting a solid-state imaging element (e.g., a microlens, a flattening layer, etc.) may be sandwiched between the infrared cut filter and the color filter.

[0495] Moreover, the infrared cut-off filter may further have a dielectric multilayer film or an ultraviolet absorbing layer, etc., in addition to the film of the present invention. The infrared cut-off filter further has a dielectric multilayer film, thereby easily obtaining an infrared cut-off filter with a wide viewing angle and excellent infrared shielding properties. Moreover, the infrared cut-off filter of the present invention further has an ultraviolet absorbing layer, thereby obtaining an infrared cut-off filter with excellent ultraviolet shielding properties. As an ultraviolet absorbing layer, for example, the absorption layer described in paragraphs 0040 to 0070 and paragraphs 0119 to 0145 of International Publication WO2015 / 099060 can be referred to, and the content is incorporated into this specification. As a dielectric multilayer film, the dielectric multilayer film described in paragraphs 0255 to 0259 of Japanese Patent Publication No. 2014-41318 can be referred to, and the content is incorporated into this specification.

[0496] <Pattern Formation Method>

[0497] The pattern forming method includes the steps of forming a layer formed of the composition of the present invention on a support, and forming a pattern on the composition layer by photolithography or dry etching.

[0498] When manufacturing a laminated body formed by laminating the film of the present invention and the color filter, the patterning of the film of the present invention and the patterning of the color filter can be performed separately. In addition, patterning can also be performed on the laminated body of the film of the present invention and the color filter (that is, the patterning of the film of the present invention and the color filter can be performed simultaneously).

[0499] The situation of patterning of film (infrared cut-off filter) and color filter of the present invention respectively refers to the following manner.Only any one of film (infrared cut-off filter) and color filter of the present invention is patterned.Then, another filter layer is formed on the filter layer that has been patterned.Then, the filter layer that has not been patterned is patterned.

[0500] The pattern forming method may be a pattern forming method based on photolithography or a pattern forming method based on dry etching.

[0501] In the case of a pattern forming method based on photolithography, no etching step is required, so the number of steps can be reduced.

[0502] In the case of a pattern forming method based on dry etching, the composition of the present invention does not need to have a photolithography function, and therefore an effect of being able to increase the concentration of the infrared absorber and the like can be obtained.

[0503] When the patterning of the film (infrared cutoff filter) of the present invention and the patterning of the color filter are performed separately, the patterning method of each filter layer can be performed only by photolithography or only by dry etching. In addition, one filter layer can be patterned by photolithography, and another filter layer can be patterned by dry etching. When patterning is performed by dry etching and photolithography, it is preferred to perform patterning of the pattern of the first layer by dry etching, and perform patterning of the pattern of the second layer and later by photolithography.

[0504] The pattern formation based on the photolithography method preferably includes the following steps: a step of forming a composition layer on a support; a step of exposing the composition layer to a pattern; and a step of developing and removing the unexposed portion to form a pattern. A step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided as needed.

[0505] Furthermore, pattern formation based on the dry etching method preferably includes the following steps: a step of forming a composition layer on a support and curing it to form a cured product layer; a step of forming a photoresist layer on the cured product layer; a step of patterning the photoresist layer by exposing and developing it to obtain a resist pattern; and a step of dry etching the cured product layer using the resist pattern as an etching mask to form a pattern. Each step is described below.

[0506] <<Step of forming a composition layer>>

[0507] In the step of forming the composition layer, the composition is applied on a support to form the composition layer.

[0508] As the support body, for example, a solid-state imaging element substrate in which a solid-state imaging element (light receiving element) such as CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.

[0509] The pattern may be formed on the solid-state imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the solid-state imaging element non-forming surface side (back surface).

[0510] If necessary, a primer layer may be provided on the support in order to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the surface of the substrate.

[0511] Examples of a method for applying the composition to a support include various methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method.

[0512] The composition layer formed on the support may be dried (prebaked). When the pattern is formed by a low-temperature process, prebaking is not required.

[0513] When prebaking is performed, the prebaking temperature is preferably 150° C. or less, more preferably 120° C. or less, and further preferably 110° C. or less. The lower limit can be, for example, 50° C. or more, and can also be 80° C. or more. By prebaking at 150° C. or less, for example, in the case where the photoelectric conversion film of the image sensor is composed of an organic raw material, these characteristics can be more effectively maintained.

[0514] The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.

[0515] When patterning a plurality of layers at the same time, it is preferred to apply a composition for forming other layers onto the above-mentioned composition layer to form other composition layers.

[0516] (When patterning is performed by photolithography)

[0517] <<Exposure process>>

[0518] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed through a mask having a predetermined mask pattern using an exposure device such as a stepper, thereby performing pattern exposure. Thus, the exposed portion can be cured.

[0519] As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays can be preferably used (i-rays are particularly preferred). The irradiation amount (exposure amount) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / Cm 2 , most preferably 0.08~0.5j / cm 2 .

[0520] The oxygen concentration during exposure can be appropriately selected. In addition to being performed under atmospheric pressure, exposure can also be performed in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen concentration atmosphere with an oxygen concentration greater than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, and can generally be selected from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 , 15000W / m 2 、35000W / m 2 The oxygen concentration and exposure illuminance can be combined with appropriate conditions, for example, the oxygen concentration can be set to 10 volume % and the illuminance can be set to 10000 W / m 2 , oxygen concentration 35 volume % and illumination 20000W / m 2 wait.

[0521] <<Development process>>

[0522] Next, the unexposed portion is removed by development to form a pattern. The unexposed portion can be removed by development using a developer. Thus, the composition layer of the unexposed portion in the exposure step is dissolved into the developer, and only the photocured portion remains.

[0523] As the developer, an organic alkali developer which does not damage the underlying solid-state imaging element, circuit, etc. is preferably used.

[0524] The temperature of the developer is preferably, for example, 20 to 30° C. The development time is preferably 20 to 180 seconds. In order to improve the residue removal performance, the process of discarding the developer every 60 seconds and resupplying the developer may be repeated.

[0525] As the alkaline reagent used in the developer, for example, organic alkaline compounds such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene can be cited. An alkaline aqueous solution diluted with pure water in a manner such that the concentration of these alkaline reagents becomes 0.001 to 10% by mass, preferably 0.01 to 1% by mass, can be preferably used as a developer. In addition, an inorganic base can also be used as a developer. As an inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred. In addition, a surfactant can also be used as a developer. As an example of a surfactant, the surfactants described in the above-mentioned composition can be cited, preferably a nonionic surfactant. In addition, when using a developer composed of such an alkaline aqueous solution, it is usually preferred to wash (rinse) with pure water after development.

[0526] After development, it is also possible to perform a heat treatment (post-baking) after drying. Post-baking is a heat treatment after development for completely curing the film. When post-baking is performed, the post-baking temperature is preferably, for example, 100 to 240°C. From the viewpoint of film curing, 200 to 230°C is more preferred. Moreover, when an organic electroluminescent (organic EL) element is used as a light source, or when a photoelectric conversion film of an image sensor is formed with organic raw materials, the post-baking temperature is preferably 150°C or less, more preferably 120°C or less, further preferably 100°C or less, and particularly preferably 90°C or less. The lower limit can be set to, for example, 50°C or more. A heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc. can be used to post-bake the developed film in a continuous or intermittent manner to achieve the above conditions. Moreover, when a pattern is formed by a low-temperature process, post-baking may not be performed.

[0527] (In the case of forming a pattern by dry etching)

[0528] Regarding pattern formation by dry etching, the composition layer formed on the support can be cured to form a cured layer, and then, the obtained cured layer is etched using a patterned photoresist layer as a mask using an etching gas. Specifically, it is preferred to form a photoresist layer by coating a positive or negative radiation-sensitive linear composition on the cured layer and drying it. In the formation of the photoresist layer, it is preferred to further implement a pre-baking treatment. In particular, as a process for forming the photoresist layer, it is preferred to implement a heating treatment after exposure and a heating treatment after development (post-baking treatment). Regarding pattern formation by dry etching, reference can be made to the records of paragraphs 0010 to 0067 of Japanese Patent Gazette No. 2013-064993, and the contents are incorporated into this specification.

[0529] <Solid-state imaging device>

[0530] The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging device is not particularly limited as long as it has the film (infrared cut filter) of the present invention and functions as a solid-state imaging device, and examples thereof include the following structures.

[0531] The solid-state imaging element is composed of, for example, a transfer electrode including a plurality of photodiodes, polysilicon, etc., a light shielding film, a device protection film, and a film of the present invention on a support. The photodiode constitutes the light receiving area of ​​the solid-state imaging element. The light shielding film is formed on the photodiode and the transfer electrode, and is formed of tungsten or the like with only the light receiving portion of the photodiode opened. The device protection film is formed on the light shielding film, and is formed of silicon nitride or the like formed in a manner covering the entire light shielding film and the light receiving portion of the photodiode. The film of the present invention is on the device protection film.

[0532] Furthermore, the solid-state imaging element may have a focusing mechanism (eg, a microlens, etc.), which may be disposed on the device protection film and below the film (infrared cut filter) of the present invention (close to the support body), or on the film of the present invention.

[0533] <Image Display Device>

[0534] The film of the present invention can also be used in image display devices such as liquid crystal display devices or organic electroluminescent (organic EL) display devices. For example, by using it together with each color pixel (e.g., red, green, blue), it can be used for the purpose of shielding infrared light contained in the backlight (e.g., white light emitting diode (white LED)) of the display device to prevent malfunction of peripheral devices or for the purpose of forming infrared pixels in addition to forming each color display pixel.

[0535] The definition of a display device or the details of each display device are recorded, for example, in “Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)”, “Display Device (written by Junaki Ibuki, published by Sangyo Tosho Publishing Co., LTD. in 1989)”, etc. Furthermore, liquid crystal display devices are recorded, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Industrial Research Council in 1994)”. There is no particular limitation on the liquid crystal display devices to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “Next Generation Liquid Crystal Display Technology”.

[0536] The image display device may have a white organic EL element. As a white organic EL element, a series structure is preferred. The series structure of the organic EL element is recorded in Japanese Patent Publication No. 2003-45676, supervised by Akiyoshi Mikami, "The Forefront of Organic EL Technology Development - High Brightness / High Precision / Long Life / Technology Collection", TECHNICAL INFORMATION INSTITUTE CO., LTD., 326-328 pages, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has strong maximum luminous peaks in the blue region (430nm-485nm), the green region (530nm-580nm) and the yellow region (580nm-620nm). It is more preferred that in addition to these luminous peaks, it further has a maximum luminous peak in the red region (650nm-700nm).

[0537] <Infrared absorber>

[0538] The compound represented by formula (1a) described in the composition of the present invention (squarylium salt compound) can be preferably used as an infrared absorber. The preferred range of the infrared absorber represented by formula (1a) is the same as the preferred range of the above-mentioned squarylium salt compound.

[0539] The compound or infrared absorber represented by formula (1a) can be preferably used to form an infrared cut-off filter that shields light with a wavelength of 700 to 1000 nm, for example. In addition, it can also be used as an infrared cut-off filter for plasma display panels or solid-state imaging elements, an optical filter such as a heat-ray shielding film, a recordable compact disc (CD-R) or a photothermal conversion material in a flash melting fixing material. In addition, it can be used as an information display material in an anti-counterfeiting ink or an invisible barcode ink. In addition, it can be used to form an infrared transmission filter. In addition, if the compound or infrared absorber represented by formula (1a) is used in an infrared transmission filter, the transmitted light (infrared) is limited to infrared light on the long wavelength side.

[0540] Example

[0541] The present invention will be described in more detail below by giving examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, if not specifically indicated, "%" and "parts" are weight references.

[0542] The compound used as the infrared absorbing agent is a compound having the chemical structure described in the infrared absorbing agent described above.

[0543] <Measurement of Weight Average Molecular Weight (Mw)>

[0544] The weight average molecular weight (Mw) was measured as a polystyrene conversion value measured by gel permeation chromatography (GPC) by the following method.

[0545] Column type: TSKgel SuperHZ4000 (manufactured by TOSOH CORPORATION, 4.6 mm (inner diameter) × 15 cm)

[0546] Developing solvent: tetrahydrofuran

[0547] Column temperature: 40°C

[0548] Flow rate (sample injection volume): 60μL

[0549] Device name: High-speed GPC (HLC-8220GPC) manufactured by TOSOH CORPORATION

[0550] Calibration curve base resin: polystyrene resin

[0551] <Synthesis of Compounds>

[0552] (Synthesis Example 1) Synthesis of Compound 1

[0553] [Chemical formula 40]

[0554]

[0555] Synthesis of intermediate M1:

[0556] Palladium acetate (230mg, 1.0mmol), sodium tert-butoxide (3.9g, 40.4mmol) and tri-tert-butylphosphine (450mg, 2.0mmol) were added to 40cm3 of toluene and stirred at 60°C for 10 minutes. After cooling it to room temperature, 2,2'-dinaphthylamine (5.5g, 20.2mmol) and 2-bromo-4-hexylthiophene (5.0g, 20.2mmol) were added to heat and reflux for 3 hours. After the reaction solution was cooled, inorganic salts were removed by diatomaceous earth filtration, and toluene (Tol) was distilled under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: toluene / hexane), and the intermediate M1 (orange grease, 8.5g, yield 97%) was obtained by distilling the solvent under reduced pressure.

[0557] Synthesis of compound 1:

[0558] Intermediate M1 (8.5 g, 19.5 mmol) and squaric acid (0.92 g, 8.1 mmol) were azeotropically dehydrated in n-butanol / toluene (20 cc / 60 cc) and heated under reflux for 12 hours. After the reaction solution was cooled, the solvent was distilled under reduced pressure, and the residue was ultrasonically dispersed in chloroform / methanol. The precipitated solid was suction filtered to obtain the target compound 1 (green crystals, 5.9 g, yield 78%).

[0559] Identification information of compound 1:

[0560] MALDI TOF-MASS (time-of-flight mass spectrometry) Calc.for [M+H]+: 949.4, found: 949.3

[0561] NMR (400MHz, CDCl3): 0.91 (6H, t), 1.20 (8H, m), 1.32 (4H, m), 1.55 (4H, m), 3.22 (4H, t), 6.55 (2H, s), 7.44 (4H, d), 7.50 (8H, m), 7.73 (4H, m), 7.80-7.88 (12H, m)

[0562] (Synthesis Example 2) Synthesis of Compound 2

[0563] [Chemical formula 41]

[0564]

[0565] Synthesis of intermediate M2:

[0566] Intermediate M2 was synthesized in the same manner as Intermediate M1 except that 2,5-dibromothieno[3,2-b]thiophene was used instead of 2-bromo-4-hexylthiophene and di(4-octylphenyl)amine was used instead of 2,2'-dinaphthylamine.

[0567] Synthesis of intermediate M3:

[0568] Intermediate M2 (1.0 g, 1.6 mmol), palladium acetate (18 mg, 0.082 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthine (69 mg, 0.12 mmol, Xantphos), and triethylsilane (2.5 g, 21 mmol) were added to a 16 cm 3 The reaction mixture was heated under reflux for 7 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: toluene / hexane) to obtain intermediate M3 (yellow oily substance, 0.70 g, yield 82%).

[0569] Synthesis of compound 2:

[0570] Compound 2 was synthesized in the same manner as in the synthesis of Compound 1, except that Intermediate M3 was used instead of Intermediate M1.

[0571] Identification information of compound 2:

[0572] MALDI TOF-MASS Calc.for[M+H]+: 1141.6, found: 1141.6

[0573] (Synthesis Example 3) Synthesis of Compound 3

[0574] [Chemical formula 42]

[0575]

[0576] Synthesis of intermediate M4:

[0577] 2-Bromomethylthiophene (1.5 g, 8.6 mmol) and triethyl phosphite (1.44 g, 8.6 mmol) were heated at 160° C. for two hours to obtain Intermediate M4. The obtained Intermediate M4 was used directly in the next reaction without purification.

[0578] Synthesis of intermediate M5:

[0579] Intermediate M5 was synthesized by the method described in Dyes and Pigments, 2015, 120, 175-183.

[0580] Intermediate M6: To the intermediate M4 obtained above, 50 cm N,N-dimethylformamide (DMF) was added. 3 After cooling to 0°C with an ice bath, sodium methoxide (1.4 g, 25.8 mmol) was added and stirred for 30 minutes. A DMF solution of intermediate M5 (2.5 g, 8.6 mmol) was added dropwise to 20 cm 3 After the addition was completed, the ice bath was removed and the mixture was stirred at room temperature for 3 hours. Water was poured into the reaction solution, and the precipitated solid was filtered and then washed with methanol to obtain intermediate M6 (pale yellow crystals, 2.6 g, yield 82%).

[0581] Synthesis of compound 3:

[0582] In the synthesis of Compound 1, Compound 3 was synthesized in the same manner as Compound 1, except that Intermediate M6 was used instead of Intermediate M1.

[0583] Identification information of compound 3:

[0584] MALDI TOF-MASS Calc.for[M+H]+: 818.5, found: 818.4

[0585] (Synthesis Example 4) Synthesis of Compound 4

[0586] [Chemical formula 43]

[0587]

[0588] Synthesis of intermediate M7:

[0589] Intermediate M7 was synthesized in the same manner as Intermediate M2, except that 2-bromothiophene was used instead of 2-bromo-4-hexylthiophene.

[0590] Synthesis of intermediate M8:

[0591] Intermediate M8 was synthesized using Intermediate M7 as a raw material according to the method described in Chem. Eur. J. 2007, 13, 9637-9646.

[0592] Synthesis of intermediate M9:

[0593] Intermediate M9 was synthesized in the same manner as Intermediate M6, except that Intermediate M8 was used instead of Intermediate M5.

[0594] Synthesis of compound 4:

[0595] In the synthesis of Compound 1, Compound 4 was synthesized in the same manner as Compound 1, except that Intermediate M9 was used instead of Intermediate M1.

[0596] Identification data of compound 4: MALDI TOF-MASS Calc.for [M+H]+: 1245.6, found: 1245.7

[0597] (Synthesis Example 5) Synthesis of Compound 5

[0598] [Chemical formula 44]

[0599]

[0600] Synthesis of intermediate M10:

[0601] Intermediate M10 was synthesized using intermediate M7 as a raw material by the method described in J. Photochem. Photobio. A 2014, 294, 54-61. In the above synthesis scheme, NBS is the abbreviation of N-bromosuccinimide.

[0602] Synthesis of intermediate M11:

[0603] Intermediate M11 was synthesized using intermediate M10 as a raw material by the method described in EP2407465A1.

[0604] Synthesis of compound 5:

[0605] In the synthesis of Compound 1, Compound 5 was synthesized in the same manner as Compound 1, except that Intermediate M11 was used instead of Intermediate M1.

[0606] Identification data of compound 5: MALDI TOF-MASS Calc.for [M+H]+: 969.4, found: 969.4

[0607] (Synthesis Example 6) Synthesis of Compound 6

[0608] [Chemical formula 45]

[0609]

[0610] Synthesis of intermediate M12:

[0611] Intermediate M12 was synthesized in the same manner as Intermediate M1, except that p,p'-dimethylaniline was used instead of 2,2'-dinaphthylamine.

[0612] Synthesis of compound 6:

[0613] In the synthesis of Compound 1, Compound 6 was synthesized in the same manner as Compound 1, except that Intermediate M12 was used instead of Intermediate M1.

[0614] Identification information of compound 6:

[0615] MALDI TOF-MASS Calc.for[M+H]+: 805.4, found: 805.3

[0616] NMR (400MHz, CDCl3): 0.92 (6H, t), 1.18-1.27 (12H, m), 1.32 (4H, m), 2.36 (12H, s), 3.20 (4H, t), 6.33 (2H, s), 7.18 (16H, m)

[0617] <Maximum absorption wavelength>

[0618] Each compound obtained was dissolved in chloroform to prepare a solution with a concentration of 1 g / L. Next, the absorption spectrum of the solution in which each compound was dissolved was appropriately diluted so that the absorbance at the maximum absorption wavelength was in the range of 0.7 to 1.2, and the maximum absorption wavelength (λmax) was measured using UV-1800 manufactured by SHIMADZU CORPORATION. The maximum absorption wavelength (λmax) of each compound is shown in the following table.

[0619] <Solubility of Compound>

[0620] The solubility of each compound in each solvent (cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), toluene) at 25° C. was evaluated based on the following criteria.

[0621] A: The solubility of the compound in a solvent at 25°C is 2% by mass or more.

[0622] B: The solubility of the compound in a solvent at 25° C. is 1% by mass or more and less than 2% by mass.

[0623] C: The solubility of the compound in a solvent at 25° C. is 0.5% by mass or more and less than 1% by mass.

[0624] D: The solubility of the compound in a solvent at 25°C is less than 0.5% by mass.

[0625] [Table 2]

[0626]

[0627] Regarding the following compounds R-1 to R-3, the maximum absorption wavelength was measured in the same manner as for compounds 1 to 6, and the solubility was evaluated.

[0628] Compound R-1 is a compound described in DE4122563, and was synthesized by the method described in the document. Compound R-2 is a compound described in Japanese Patent Publication No. 2009-15114, and was synthesized by the method described in the document. Compound R-3 is a compound described in Chem. Eur. J., 2008, 14, 11082-11091, and was synthesized by the method described in the document.

[0629] [Chemical formula 46]

[0630]

[0631] Compounds 1 to 6 have maximum absorption wavelengths of 700 nm or longer and have excellent solubility in various solvents.

[0632] On the other hand, the maximum absorption wavelength of compound R-1 and compound R-2 is less than 700 nm. Moreover, the solubility of compound R-1 and R-3 is insufficient.

[0633] <Preparation of Near Infrared Absorbing Composition>

[0634] The following composition was mixed to prepare a near infrared absorbing composition.

[0635] <Composition 1>

[0636] Compounds shown in the following table: 2.3 parts

[0637] Resin 1: 12.9 parts

[0638] Crosslinking compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA): 12.9 parts

[0639] Photopolymerization initiator: IRGACURE-OXE01 [2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione], manufactured by BASF: 2.5 parts

[0640] Ultraviolet absorber: UV503 (DAITO CHEMICAL CO., LTD.): 0.5 parts

[0641] Surfactant: The following mixture (Mw = 14000): 0.04 parts

[0642] [Chemical formula 47]

[0643]

[0644] Inhibitor: p-methoxyphenol: 0.006 parts

[0645] Cyclohexanone: 49.6 parts

[0646] Propylene glycol monomethyl ether acetate: 19.3 parts

[0647] <Composition 2>

[0648] Compounds shown in the following table: 2.8 parts

[0649] Resin 2: 10.5 parts

[0650] Crosslinking compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA): 2.0 parts

[0651] Photopolymerization initiator: IRGACURE-OXE01 [2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione], manufactured by BASF: 2.2 parts

[0652] Ultraviolet absorber: UV503 (DAITO CHEMICAL CO., LTD.): 0.5 parts

[0653] Surfactant: MEGAFACE RS-72-K (DIC CORPORATION) 2.3 parts

[0654] Inhibitor: p-methoxyphenol: 0.001 parts

[0655] Cyclohexanone: 74.5 parts

[0656] Propylene glycol monomethyl ether acetate: 5.3 parts

[0657] <Composition 3>

[0658] Compounds shown in the following table: 2.8 parts

[0659] Resin 3 or Resin 4: 14.7 parts

[0660] Ultraviolet absorber: UV503 (DAITO CHEMICAL CO., LTD.): 0.5 parts

[0661] Surfactant: MEGAFACE RS-72-K (DIC CORPORATION) 2.3 parts

[0662] Cyclohexanone: 74.5 parts

[0663] Propylene glycol monomethyl ether acetate: 5.3 parts

[0664] Resin 1: Copolymer of benzyl methacrylate (BzMA) and methacrylic acid (MAA) (composition ratio (mass ratio): (BzMA / MAA) = (80 / 20), Mw = 15,000)

[0665] Resin 2: Copolymer of allyl methacrylate (Allyl-MA) and methacrylic acid (MAA) (composition ratio (mass ratio): (Allyl-MA / MAA) = (80 / 20), Mw = 15,000)

[0666] Resin 3: Polystyrene (Aldrich, Mw=15,000)

[0667] Resin 4: ARTON F4520 (JSR CORPORATION)

[0668] <Film production>

[0669] Each composition was applied on a glass substrate (1737 manufactured by Corning Incorporated) using a spin coater so that the film thickness after drying would be 1.0 μm, and then subjected to a heat treatment (pre-bake) for 120 seconds using a hot plate at 100° C.

[0670] After prebaking, compositions 1 and 2 were exposed using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) at 500 mJ / cm 2 Make an overall exposure.

[0671] Then, the glass substrate was subjected to spin immersion development for 60 seconds at 23° C. using a developer (CD-2060, manufactured by FUJIFILM Electronic Materials Co., LTD.), and then rinsed with pure water. The glass substrate after the rinse treatment was spin-dried, and then heated for 300 seconds using a hot plate at 200° C. (post-baking) to obtain a cured film.

[0672] In Examples 3 and 4, the films dried after the prebaking treatment were used and evaluated as they were.

[0673] <Evaluation of Coating Film>

[0674] The state of the obtained film was observed with the naked eye.

[0675] A: There is no precipitation of the compound.

[0676] B: There is precipitation of the compound.

[0677] <Maximum absorption wavelength of the film (λmax)>

[0678] The absorption spectrum of the obtained film was measured using a spectrophotometer UV-3100PC (manufactured by SHIMADZU CORPORATION), and the maximum absorption wavelength (λmax) of the film was measured.

[0679] <Evaluation of infrared shielding properties>

[0680] The transmittance of each film at a wavelength of 700 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.) The infrared shielding property was evaluated based on the following criteria. The results are shown in the following table.

[0681] A: Transmittance at wavelength 700nm ≤ 5%

[0682] B: 5% <Transmittance at wavelength 700nm ≤ 7%

[0683] C: 7% <Transmittance at wavelength 700nm ≤ 10%

[0684] D: 10% < Transmittance at wavelength 700nm

[0685] <Evaluation of Visible Transparency>

[0686] The transmittance of each film at a wavelength of 450 to 600 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.) The visible transparency was evaluated based on the following criteria. The results are shown in the following table.

[0687] A: 95% ≤ minimum transmittance at wavelength 450-600nm

[0688] B: 90% ≤ Minimum transmittance at wavelength 450-600nm < 95%

[0689] C: 80% ≤ Minimum transmittance at wavelength 450-600nm < 90%

[0690] D: The minimum transmittance at a wavelength of 450-600nm is <80%

[0691] <Evaluation of Heat Resistance>

[0692] The obtained films were heated at 200°C for 5 minutes to perform a heat resistance test on each film. The color difference ΔEab value of each film before and after the heat resistance test was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The heat resistance was evaluated based on the following criteria using the ΔEab value. In addition, a smaller ΔEab value indicates good heat resistance.

[0693] The ΔEab value is a value obtained by the following color difference formula based on the CIE 1976 (L*, a*, b*) space color system (THE COLOR SCIENCE ASSOCIATION 0F JAPAN, New Color Science Pamphlet (1976), p. 266).

[0694] ΔEab={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} 1 / 2

[0695] (Judgment Criteria)

[0696] A: ΔEab value <3

[0697] B: 3≤ΔEab value<5

[0698] C: 5≤ΔEab value<10

[0699] D: 10≤ΔEab value<20

[0700] E: 20 ≤ ΔEab value

[0701] <Evaluation of light resistance>

[0702] The obtained film was irradiated with 10,000 lux of light for 10 hours using a Xe lamp through an ultraviolet cut filter to perform a light resistance test. The color difference ΔEab value of each film before and after the light resistance test was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The light resistance was evaluated based on the following judgment criteria using the ΔEab value. In addition, a smaller ΔEab value indicates good light resistance.

[0703] (Judgment Criteria)

[0704] A: ΔEab value <3

[0705] B: 3≤ΔEab value<5

[0706] C: 5≤ΔEab value<10

[0707] D: 10≤ΔEab value<20

[0708] E: 20 ≤ ΔEab value

[0709] [Table 3]

[0710]

[0711] The above results show that the examples have excellent infrared shielding and visible transparency. In particular, Examples 1 to 9 using Compounds 1 to 6 have more excellent infrared shielding and visible transparency. Moreover, when forming a coating film, there is no precipitation of the compound, and the properties of the coating film are good. Moreover, the heat resistance and light resistance are also excellent.

[0712] On the other hand, in Comparative Examples 1 and 2, the infrared shielding property and the visible transparency were inferior.

[0713] Furthermore, in Examples 1 to 10, by further blending a coloring agent, filters having good transmittance other than specific visible light and infrared shielding properties and excellent heat resistance and light resistance were obtained.

[0714] Furthermore, a laminated film in which a dielectric multilayer film and a film obtained from the composition of Examples 1 to 10 were combined also exhibited a preferred effect.

Claims

1. A near infrared absorbing composition comprising a squarylium salt compound represented by the following formula (1) and having a maximum absorption wavelength of 700 nm or more and a resin, In the formula, Ar 1 and Ar 2 Each independently represents a group selected from the following divalent conjugated groups, R 1 ~R 4 Each independently represents an alkyl group having 8 to 20 carbon atoms, R 1 Optionally with R 2 or Ar 1 Bond to form a ring, R 3 Optionally with R 4 or Ar 2 Bond to form a ring, * indicates a connecting bond, Z indicates -CR 2 -、-CR=CR-、-SIR 2 -, -CO-, -S-, -SO-, -SO 2 -, R represents a hydrogen atom or a substituent, The divalent conjugated group has a substituent or is unsubstituted, When the divalent conjugated group has a substituent and / or when R has a substituent, the substituent of the divalent conjugated group and / or the substituent of R is selected from halogen atoms, cyano, nitro, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, -OR Z 1 、-COR Z 1 、-COOR Z 1 、-OCOR Z 1 、-NR Z 1 R Z 2 、-NHCOR Z 1 、-CONR Z 1 R Z 2 、-NHCONR Z 1 R Z 2 、-NHCOOR Z 1 、-SR Z 1 、-SO 2 R Z 1 、-SO 2 OR Z 1 、-NHSO 2 R Z 1 、-SO 2 NR Z 1 R Z 2 , a group represented by the following formula (W), R Z 1 and R Z 2 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group, and R Z 1 With R Z 2 are optionally bonded to form a ring, in, -COOR Z 1 R Z 1 When it is hydrogen, that is -COOR Z 1 In the case of a carboxyl group, the hydrogen atom is optionally dissociated, -SO 2 OR Z 1 R Z 1 When it is a hydrogen atom, that is, -SO 2 OR Z 1 When it is a sulfo group, the hydrogen atom is optionally dissociated, -S 1 -L 1 -T 1 (W) In formula (W), S 1 represents a single bond, an arylene group or a heteroarylene group, L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO 2 -、-OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group, T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group, S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group, 1 and T 1 The total number of carbon atoms contained is 5 or more, S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

2. The near infrared absorbing composition according to claim 1, in, The squarylium salt compound comprises Ar of formula (1): 1 and Ar 2 The plane has a π-conjugated plane with 16 to 54 atoms.

3. The near infrared absorbing composition according to claim 1 or 2, in, Selected from Ar 1 ,Ar 2 At least one of them has a group represented by the formula (W).

4. The near infrared absorbing composition according to claim 1 or 2, in, R 1 ~R 4 Each independently represents a linear or branched alkyl group having 8 to 20 carbon atoms.

5. The near infrared absorbing composition according to claim 1 or 2, in, According to formula (1), -NR 1 R 2 and-NR 3 R 4 The sandwiched portion has a π-conjugated plane with 16 to 54 atoms. 6 . A film formed from the near-infrared absorbing composition according to claim 1 . 7 . An infrared cut filter, comprising the near-infrared absorbing composition according to claim 1 . 8 . A solid-state imaging element comprising the infrared cut filter according to claim 7 .

9. An infrared absorbent represented by the following formula (1): In the formula, Ar 1 and Ar 2 Each independently represents a group selected from the following divalent conjugated groups, R 1 ~R 4 Each independently represents an alkyl group having 8 to 20 carbon atoms, R 1 Optionally with R 2 or Ar 1 Bond to form a ring, R 3 Optionally with R 4 or Ar 2 Bond to form a ring, * indicates a connecting bond, Z indicates -CR 2 -、-CR=CR-、-SIR 2 -, -CO-, -S-, -SO-, -SO 2 -, R represents a hydrogen atom or a substituent, The divalent conjugated group has a substituent or is unsubstituted, When the divalent conjugated group has a substituent and / or when R has a substituent, the substituent of the divalent conjugated group and / or the substituent of R is selected from halogen atoms, cyano, nitro, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, -OR Z 1 、-COR Z 1 、-COOR Z 1 、-OCOR Z 1 、-NR Z 1 R Z 2 、-NHCOR Z 1 、-CONR Z 1 R Z 2 、-NHCONR Z 1 R Z 2 、-NHCOOR Z 1 、-SR Z 1 、-SO 2 R Z 1 、-SO 2 OR Z 1 、-NHSO 2 R Z 1 、-SO 2 NR Z 1 R Z 2 , a group represented by the following formula (W), R Z 1 and R Z 2 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group, and R Z 1 With R Z 2 are optionally bonded to form a ring, in, -COOR Z 1 R Z 1 When it is hydrogen, that is -COOR Z 1 In the case of a carboxyl group, the hydrogen atom is optionally dissociated, -SO 2 OR Z 1 R Z 1 When it is a hydrogen atom, that is, -SO 2 OR Z 1 When it is a sulfo group, the hydrogen atom is optionally dissociated, -S 1 -L 1 -T 1 (W) In formula (W), S 1 represents a single bond, an arylene group or a heteroarylene group, L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO 2 -、-OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group, T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group, S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group, 1 and T 1 The total number of carbon atoms contained is 5 or more, S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

10. The infrared absorbent according to claim 9, in, R 1 ~R 4 Each independently represents a linear or branched alkyl group having 8 to 20 carbon atoms.

11. The infrared absorbent according to claim 9 or 10, in, According to formula (1), -NR 1 R 2 and-NR 3 R 4 The sandwiched portion has a π-conjugated plane with 16 to 54 atoms.

12. A compound having a maximum absorption wavelength of 700 nm or more, which is represented by the following formula (1): In the formula, Ar 1 and Ar 2 Each independently represents a group selected from the following divalent conjugated groups, R 1 ~R 4 Each independently represents an alkyl group having 8 to 20 carbon atoms, R 1 Optionally with R 2 or Ar 1 Bond to form a ring, R 3 Optionally with R 4 or Ar 2 Bond to form a ring, * indicates a connecting bond, Z indicates -CR 2 -、-CR=CR-、-SIR 2 -, -CO-, -S-, -SO-, -SO 2 -, R represents a hydrogen atom or a substituent, The divalent conjugated group has a substituent or is unsubstituted, When the divalent conjugated group has a substituent and / or when R has a substituent, the substituent of the divalent conjugated group and / or the substituent of R is selected from halogen atoms, cyano, nitro, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, -OR Z 1 、-COR Z 1 、-COOR Z 1 、-OCOR Z 1 、-NR Z 1 R Z 2 、-NHCOR Z 1 、-CONR Z 1 R Z 2 、-NHCONR Z 1 R Z 2 、-NHCOOR Z 1 、-SR Z 1 、-SO 2 R Z 1 、-SO 2 OR Z 1 、-NHSO 2 R Z 1 、-SO 2 NR Z 1 R Z 2 , a group represented by the following formula (W), R Z 1 and R Z 2 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group, and R Z 1 With R Z 2 are optionally bonded to form a ring, in, -COOR Z 1 R Z 1 When it is hydrogen, that is -COOR Z 1 In the case of a carboxyl group, the hydrogen atom is optionally dissociated, -SO 2 OR Z 1 R Z 1 When it is a hydrogen atom, that is, -SO 2 OR Z 1 When it is a sulfo group, the hydrogen atom is optionally dissociated, -S 1 -L 1 -T 1 (W) In formula (W), S 1 represents a single bond, an arylene group or a heteroarylene group, L 1 represents an alkylene group, an alkenylene group, an alkynylene group, -O-, -S-, or -NR L1 -, -CO-, -COO-, -OCO-, -CONR L1 -、-NR L1 CO-, -SO 2 -、-OR L2 - or a group consisting of these, R L1 represents a hydrogen atom or an alkyl group, R L2 represents an alkylene group, T 1 represents an alkyl group, a cyano group, a hydroxyl group, a formyl group, a carboxyl group, an amino group, a thiol group, a sulfo group, a phosphoryl group, a boryl group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a trialkylsilyl group or a trialkoxysilyl group, S 1 is a single bond, L 1 is an alkylene group, T 1 When L is an alkyl group, 1 and T 1 The total number of carbon atoms contained is 5 or more, S 1 When L represents an arylene group or a heteroarylene group, 1 and T 1 The total number of carbon atoms contained is 5 or more.

13. The compound according to claim 12, in, R 1 ~R 4 Each independently represents a linear or branched alkyl group having 8 to 20 carbon atoms.

14. The compound according to claim 12 or 13, in, According to formula (1), -NR 1 R 2 and-NR 3 R 4 The sandwiched portion has a π-conjugated plane with 16 to 54 atoms.

15. The compound according to claim 12, in, Selected from Ar 1 ,Ar 2 At least one of them has a group represented by the formula (W).

Images