Composition, film, near-infrared cut filter, pattern forming method, laminate, solid-state imaging element, infrared sensor, image display device, camera module, and compound

Abstract

The present invention provides a composition, a compound having a structure represented by formula (4-1), a film formed using the composition, a near-infrared cutoff filter, a pattern forming method, a laminate, a solid-state imaging element, an infrared sensor, an image display device, a camera module, and a novel compound, wherein the composition contains a pigment having a structure represented by formula (1), an organic solvent, and a curable compound, wherein the pigment having a structure represented by the above formula (1) has a solubility of 100 mg / L or less in propylene glycol methyl ether acetate at 25°C. In formula (1), L 1 represents an n-valent linking group, wherein n represents an integer from 2 to 10, and when n is 2, L 1 It may be a single bond, and Dye each independently represents a pigment structure having a maximum absorption wavelength in the wavelength range of 650nm to 2000nm. n ‑L 1 (1).

Description

Technical Field

[0001] The present invention relates to a composition, a film, a near-infrared cut filter, a pattern forming method, a laminate, a solid-state imaging element, an infrared sensor, an image display device, a camera module and a compound. Background Art

[0002] Pigment dispersion compositions such as curable compositions in which organic or inorganic pigments are dispersed contain polyfunctional monomers, photopolymerization initiators, alkali-soluble resins, and other components to form colored photosensitive compositions, and components such as color filters are manufactured using the colored photosensitive compositions by photolithography or the like.

[0003] As the above-mentioned pigment, it is known to use a squarylium compound having a dihydropyridine skeleton.

[0004] Furthermore, examples of conventional pigments and dyes include those described in International Publication No. 2018 / 043185 and International Publication No. 2016 / 194527.

[0005] International Publication No. 2018 / 043185 describes a composition comprising a near-infrared absorbing compound having a maximum absorption wavelength in the range of 650 to 1000 nm, an organic solvent and a resin, wherein the near-infrared absorbing compound is at least one selected from pyrrolopyrrole compounds, rylene compounds, oxocyanine compounds, squarylium compounds, crotonium compounds, zinc phthalocyanine compounds, cobalt phthalocyanine compounds, vanadium phthalocyanine compounds, copper phthalocyanine compounds, magnesium phthalocyanine compounds, naphthalocyanine compounds, pyrylium compounds, azulenium compounds, indigo compounds and pyrromethene compounds, and the solubility of the near-infrared absorbing compound in propylene glycol methyl ether acetate at 25° C. is 0.01 to 30 mg / L.

[0006] International Publication No. 2016 / 194527 describes a near-infrared absorbing dye multimer having a maximum absorption wavelength in the range of 700 to 1200 nm. Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] An object of one embodiment of the present invention is to provide a composition having excellent spectral characteristics of a cured film to be obtained.

[0009] Furthermore, another embodiment of the present invention aims to provide a film, a near infrared cut filter, a pattern forming method, a laminate, a solid-state imaging element, an infrared sensor, an image display device, and a camera module formed using the composition.

[0010] Another embodiment of the present invention aims to provide a novel compound.

[0011] Means for solving technical problems

[0012] The present invention includes the following aspects.

[0013] <1> A composition comprising:

[0014] A pigment having a structure represented by the following formula (1);

[0015] organic solvents; and

[0016] Curing compounds,

[0017] The solubility of the dye having a structure represented by the following formula (1) in propylene glycol methyl ether acetate at 25° C. is 100 mg / L or less.

[0018] (Dye) n -L 1 (1)

[0019] In formula (1), L 1 represents an n-valent linking group, wherein n represents an integer of 2 to 10, and when n is 2, L 1 It may be a single bond, and Dye each independently represents a dye structure having a maximum absorption wavelength in the wavelength range of 650 nm to 2,000 nm.

[0020] <2> The composition according to <1>, wherein

[0021] The dye having a structure represented by the above formula (1) is at least one compound selected from pyrrolopyrrole compounds, rylene compounds, oxocyanine compounds, squarylium compounds, crotonium compounds, vanadium phthalocyanine compounds, naphthalocyanine compounds, indigo compounds and pyrromethene compounds.

[0022] <3> The composition according to <1> or <2>, wherein

[0023] The dye having a structure represented by the above formula (1) is at least one compound selected from the group consisting of pyrrolopyrrole compounds, squarylium compounds, crotonium compounds, and pyrromethene compounds.

[0024] <4> The composition according to any one of <1> to <3>, wherein

[0025] In the above formula (1), L 1 It is a divalent to decavalent linking group having at least two ring structures selected from aliphatic rings, aromatic rings, and heterocyclic rings.

[0026] <5> The composition according to any one of <1> to <4>, wherein

[0027] The molecular weight of the dye having the structure represented by the above formula (1) is less than 4,000.

[0028] <6> The composition according to any one of <1> to <5>, wherein

[0029] In the above formula (1), L 1 The total number of carbon atoms contained in is 1 to 18.

[0030] <7> The composition according to any one of <1> to <6>, wherein

[0031] The volume average particle size of the pigment having the structure represented by the above formula (1) is 1 nm to 500 nm.

[0032] <8> The composition according to any one of <1> to <7>, wherein

[0033] In the above formula (1), n ​​is 2.

[0034] <9> The composition according to any one of <1> to <8>, wherein

[0035] In the above formula (1), n ​​is 2 and L 1 It is a group represented by the following formula (2) or the following formula (3).

[0036] *-X 1 -A 1 -X 2 -* Formula (2)

[0037] In the above formula (2), X 1 and X 2 Each independently represents a single bond, -O-, -S-, -NR 1A -, -CO-, -COO-, -OCOO-, -SO 2 NR 1A -、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, R 1A represents a hydrogen atom, an alkyl group or an aryl group, A 1 represents a single bond, an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure, and * represents the connection position with Dye, wherein A 1 When it is a single bond, X 1 and X 2 These two are not single bonds at the same time.

[0038] *-X3 -A 2 -L 2 -A 3 -X 4 -* Formula (3)

[0039] In the above formula (3), X 3 and X 4 each independently represents a single bond, -O-, -S-, -NR 2A -, -CO-, -COO-, -OCOO-, -SO 2 NR 2A -、-CONR 2A -、-OCONR 2A -or-NR 2A CONR 2A -, R 2A represents a hydrogen atom or an alkyl group,

[0040] L 2 Indicates a single bond, -O-, -S-, -NR 2B -, -CO-, -COO-, -OCOO-, -SO 2 NR 2B -、-CONR 2B -、-OCONR 2B -、-NR 2B CONR 2B -, an alkylene group, an alkenyl group, an alkynyl group, an aromatic ring structure, or a group composed of these having 1 to 6 carbon atoms, R 2B represents a hydrogen atom or an alkyl group, A 2 and A 3 Each independently represents an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure.

[0041] <10> The composition according to any one of <1> to <9>, further comprising a pigment derivative.

[0042] <11> The composition according to any one of <1> to <10>, wherein

[0043] The curable compound contains a polymerizable compound and further contains a photopolymerization initiator.

[0044] <12> The composition according to any one of <1> to <11>, comprising an alkali-soluble resin.

[0045] <13> A film comprising the composition according to any one of <1> to <12> or obtained by curing the composition.

[0046] <14> A near infrared cut filter comprising the film according to <13>.

[0047] <15> The near infrared cut filter according to <14>, further comprising a glass substrate.

[0048] <16> A pattern forming method, comprising:

[0049] A step of forming a composition layer on a support using the composition described in any one of <1> to <12>; and

[0050] A step of forming a pattern on the composition layer by photolithography or dry etching.

[0051] <17> A laminate comprising the film according to <13> and a color filter containing a color colorant.

[0052] <18> A solid-state imaging element comprising the film according to <13>.

[0053] <19> An image display device comprising the film according to <13>.

[0054] <20> A camera module comprising the film according to <13>.

[0055] <21> An infrared sensor comprising the film according to <13>.

[0056] <22> A pyrrolopyrrole compound represented by the following formula (4-1).

[0057] [Chemical formula 1]

[0058]

[0059] In formula (4-1), R 1a and R 1b Each independently represents an aryl or heteroaryl group, R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 With R 3 can be bonded to each other to form a ring, R 4 Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B or metal atom, R 4 Can be selected from R 1a , R 1b and R 3 At least one of them is covalently bonded or coordinately bonded, R 4A and R 4B Each independently represents a hydrogen atom or a substituent, L 3 It is a group represented by the following formula (2) or the following formula (3).

[0060] *-X 1 -A 1 -X 2 -* Formula (2)

[0061] In the above formula (2), X 1 and X 2 Each independently represents a single bond, -O-, -S-, -NR 1A -, -CO-, -COO-, -OCOO-, -SO 2 NR 1A -、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, R 1A represents a hydrogen atom, an alkyl group or an aryl group, A 1 represents a single bond, an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure, and * represents the connection position with Dye, wherein A 1 When it is a single bond, X 1 and X 2 These two are not single bonds at the same time.

[0062] *-X 3 -A 2 -L 2 -A 3 -X 4 -* Formula (3)

[0063] In the above formula (3), X 3 and X 4 each independently represents a single bond, -O-, -S-, -NR 2A -, -CO-, -COO-, -OCOO-, -SO 2 NR 2A -、-CONR 2A -、-OCONR 2A -or-NR 2A CONR 2A -, R 2A represents a hydrogen atom or an alkyl group,

[0064] L 2 Indicates a single bond, -O-, -S-, -NR 2B -, -CO-, -COO-, -OCOO-, -SO 2 NR 2B -、-CONR 2B -、-OCONR 2B -、-NR 2B CONR 2B-, an alkylene group, an alkenyl group, an alkynyl group, an aromatic ring structure, or a group composed of these having 1 to 6 carbon atoms, R 2B represents a hydrogen atom or an alkyl group, A 2 and A 3 Each independently represents an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure.

[0065] Effects of the Invention

[0066] According to one embodiment of the present invention, a composition having excellent spectral characteristics of the obtained cured film can be provided.

[0067] Furthermore, according to another embodiment of the present invention, a film, a near infrared cut filter, a pattern forming method, a laminate, a solid-state imaging element, an infrared sensor, an image display device, and a camera module formed using the composition can be provided.

[0068] According to another embodiment of the present invention, a novel compound is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 It is a schematic diagram showing one embodiment of the infrared sensor of the present invention. DETAILED DESCRIPTION

[0070] Hereinafter, the contents of the present invention will be described in detail.

[0071] In the present invention, "total solid content" refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, "solid content" refers to the components after removing the solvent as described above, for example, it can be solid or liquid at 25°C.

[0072] Regarding the marking of groups (atomic groups) in the present invention, the marking without description of substitution and unsubstituted includes both groups without substitution and 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).

[0073] In the present invention, "exposure" includes exposure using light and drawing using particle beams such as electron beams and ion beams unless otherwise specified. In addition, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other activating rays or radiation.

[0074] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0075] In the numerical ranges recorded in stages in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiments.

[0076] In the present invention, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0077] In the present invention, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ac represents an acetyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

[0078] In the present invention, the term "step" includes not only independent steps but also steps that achieve the intended effect of the process even if they cannot be clearly distinguished from other steps.

[0079] In the present invention, "mass %" has the same meaning as "weight %", and "parts by mass" has the same meaning as "parts by weight".

[0080] Furthermore, in the present invention, a combination of two or more preferred aspects is a more preferred aspect.

[0081] Unless otherwise specified, the transmittance in the present invention is the transmittance at 25°C.

[0082] In the present invention, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC).

[0083] (Composition)

[0084] The composition of the present invention contains a dye having a structure represented by the following formula (1), an organic solvent, and a curable compound. The solubility of the dye represented by the above formula (1) in propylene glycol methyl ether acetate at 25° C. is 100 mg / L or less.

[0085] (Dye) n -L 1 (1)

[0086] In formula (1), L 1 represents an n-valent linking group, wherein n represents an integer of 2 to 10, and when n is 2, L 1 It may be a single bond, and Dye each independently represents a dye structure having a maximum absorption wavelength in the wavelength range of 650 nm to 2,000 nm.

[0087] By using the composition of the present invention, a cured film having excellent spectral characteristics can be obtained.

[0088] In a cured film containing a pigment described in International Publication No. 2018 / 043185 or a pigment multimer described in International Publication No. 2016 / 194527 as a conventional pigment, spectral characteristics may be insufficient.

[0089] As a result of intensive studies, the present inventors have found that a cured film having excellent spectral characteristics can be obtained by using a composition containing a pigment represented by the above formula (1), an organic solvent and a curable compound, wherein the solubility of the pigment in propylene glycol methyl ether acetate at 25° C. is 100 mg / L or less.

[0090] Although the reason why the above-mentioned effect can be obtained is unclear, it can be speculated that the pigment having a structure represented by the above formula (1) contained in the composition of the present invention is easier to associate than the pigment described in International Publication No. 2018 / 043185 or the pigment polymer described in International Publication No. 2016 / 194527, or the amorphous component is reduced by adjusting the association state, so the width of the maximum absorption wavelength is narrowed and the spectral characteristics of the obtained film are excellent.

[0091] Furthermore, it is inferred that the pigment having a structure represented by the above formula (1) contained in the composition of the present invention has a specific connection structure, so the rigidity of the molecule is improved, and further, the solubility in propylene glycol methyl ether acetate is 100 mg / L or less, so the stability of the molecule itself with respect to light and heat is improved, and heat resistance and light resistance are also likely to be excellent.

[0092] Hereinafter, the details of each component contained in the composition of the present invention will be described.

[0093] <Dye having a structure represented by formula (1)>

[0094] The composition of the present invention contains a pigment having a structure represented by the above formula (1).

[0095] The solubility of the dye having a structure represented by the above formula (1) (hereinafter also referred to as “specific dye”) in propylene glycol methyl ether acetate (hereinafter also referred to as “PGMEA”) at 25° C. is 100 mg / L or less.

[0096] A dye having a structure represented by the above formula (1) can be preferably used as the infrared absorbing dye.

[0097] Furthermore, it is preferred that the coloring matter having the structure represented by the above formula (1) is a pigment. In the present invention, the pigment refers to a coloring matter that is insoluble in a solvent. Furthermore, the dye refers to a coloring matter that is soluble in a solvent.

[0098] In the present invention, the solubility of the dye having the structure represented by formula (1) (ie, specific dye) is measured by the following method to determine the solubility.

[0099] Under atmospheric pressure, about 100 mg (the accurately weighed value is X mg) of a pigment having a structure represented by formula (1) is added to 1 L of propylene glycol methyl ether acetate at 25° C. and stirred for 30 minutes. Then, the mixture is allowed to stand for 5 minutes and filtered. The filtrate is dried under reduced pressure at 80° C. for 2 hours and then accurately weighed (the accurately weighed value is Y mg). The solubility of the specific pigment in propylene glycol methyl ether acetate is calculated by the following formula.

[0100] PGMEA solubility of specific pigment (mg / L) = XY

[0101] The solubility of the pigment having a structure represented by formula (1) in PGMEA at 25°C is preferably 0.01 mg / L or more and 100 mg / L or less, more preferably 0.01 mg / L or more and 50 mg / L or less, further preferably 0.01 mg / L or more and 10 mg / L or less, and particularly preferably 0.01 mg / L or more and less than 10 mg / L, from the viewpoints of spectral characteristics, heat resistance and light resistance.

[0102] As a method of reducing the solubility of the dye having a structure represented by formula (1) in PGMEA, the following methods can be mentioned.

[0103] (1); Improve the planarity of the structure represented by formula (1). Specifically, the planarity of the structure represented by formula (1) can be improved. 1 At least one ring structure selected from an aliphatic ring, an aromatic ring and a heterocyclic ring is introduced.

[0104] (2) Introducing a urea structure, a triazine structure, or a structure having a hydrogen bonding group such as a hydroxyl group into the structure represented by formula (1).

[0105] From the viewpoint of reducing the solubility of the dye having a structure represented by formula (1) in PGMEA, L 1 It is a linking group having at least one ring structure selected from an aliphatic ring, an aromatic ring and a heterocyclic ring, more preferably a linking group having at least one aliphatic ring, an aromatic ring or a heterocyclic ring, and further preferably a linking group having at least two aliphatic rings, an aromatic ring or a heterocyclic ring.

[0106] The aliphatic ring, aromatic ring and heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, an alkenyl group, an aryl group, a monovalent heterocyclic group, a nitro group, a cyano group and the like. Of these, an alkyl group or a halogen atom is preferred, an alkyl group is more preferred, and an alkyl group having 1 to 4 carbon atoms is further preferred.

[0107] From the viewpoint of spectral characteristics, heat resistance and light resistance, the aliphatic ring, aromatic ring and heterocyclic ring are preferably unsubstituted or have an alkyl group or a halogen atom as a substituent, more preferably unsubstituted or have an alkyl group as a substituent, further preferably unsubstituted or have an alkyl group having 1 to 4 carbon atoms as a substituent, and particularly preferably unsubstituted.

[0108] In the pigment having a structure represented by the above formula (1), L 1 In view of spectral characteristics, heat resistance and light resistance, L is preferably 1 It is a divalent to 8-valent linking group, more preferably a divalent to 6-valent linking group, further preferably a divalent to 4-valent linking group, and particularly preferably a divalent or trivalent linking group.

[0109] In addition, L 1 The valence number n has the same meaning as that of n in the formula (1) described later.

[0110] In the dye having a structure represented by the above formula (1), n ​​represents an integer of 2 to 10. From the viewpoint of spectral characteristics, heat resistance and light resistance, n is an integer of 2 to 8, more preferably an integer of 2 to 6, further preferably an integer of 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0111] In the dye having a structure represented by the above formula (1), when n is 2, L 1 Can be a single key.

[0112] From the viewpoint of spectral characteristics, heat resistance and light resistance, it is preferred that L in formula (1) 1 A 2- to 10-valent linking group (preferably a 2- to 8-valent linking group, more preferably a 2- to 6-valent linking group, further preferably a 2- to 4-valent linking group, and particularly preferably a 2- or 3-valent linking group) having at least one ring structure selected from two or more aliphatic rings, aromatic rings, and heterocyclic rings; more preferably a 2- to 10-valent linking group (preferably a 2- to 8-valent linking group, more preferably a 2- to 6-valent linking group, further preferably a 2- to 4-valent linking group, and particularly preferably a 2- or 3-valent linking group) having at least one ring structure selected from two or more aliphatic rings and aromatic rings; further preferably a 2- to 10-valent linking group (preferably a 2- to 8-valent linking group, more preferably a 2- to 6-valent linking group, further preferably a 2- to 4-valent linking group, and particularly preferably a 2- or 3-valent linking group) having two or more aromatic rings.

[0113] From the viewpoint of spectral characteristics, heat resistance and light resistance, it is preferred that L in formula (1) 1 The total number of carbon atoms contained in (also referred to as "atoms with carbon atoms") is 24 or less, more preferably 1-18, and further preferably 9-18.

[0114] From the viewpoint of spectral characteristics, heat resistance and light resistance, in formula (1), it is preferred that n is 2 and L 1 It is a group represented by the following formula (2) or the following formula (3).

[0115] *-X 1 -A 1 -X 2 -* Formula (2)

[0116] In the above formula (2), X 1 and X 2 Each independently represents a single bond, -O-, -S-, -NR 1A -, -CO-, -COO-, -OCOO-, -SO 2 NR 1A -、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, R 1A represents a hydrogen atom, an alkyl group or an aryl group, A 1 represents a single bond, an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure, and * represents the connection position with Dye, wherein A 1 When it is a single bond, X 1 and X 2 These two are not single bonds at the same time.

[0117] In formula (2), X 1 and X 2 Each independently represents -NR 1A -、-SO 2 NR 1A -、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, preferably R 1A It is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrogen atom, a methyl group, a phenyl group, or a naphthyl group, and still more preferably a hydrogen atom or a phenyl group.

[0118] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (2), X is preferably 1 and X 2are independently a single bond, -O-, -NR 1A -、-COO-、-OCOO-、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, more preferably a single bond, -NR 1A -, -COO- or -OCOO-, and more preferably a single bond or -COO-.

[0119] In formula (2), A 1 represents a single bond, an aliphatic ring structure, an aromatic ring structure, or a heterocyclic structure.

[0120] The aliphatic ring in the aliphatic ring structure may be a monocyclic ring or a condensed aliphatic ring in which two or more aliphatic rings are condensed, but a monocyclic ring is preferred.

[0121] The number of ring members of the aliphatic ring is not particularly limited, but a 5- to 8-membered ring is preferred, a 5-membered ring or a 6-membered ring is more preferred, and a 6-membered ring is particularly preferred.

[0122] Examples of the aliphatic ring include a cyclopentane ring and a cyclohexane ring.

[0123] The heterocyclic ring in the heterocyclic structure may be a monocyclic ring, or may be a condensed heterocyclic ring formed by condensing two or more heterocyclic rings or a condensed heterocyclic ring and an aromatic ring, but is preferably a monocyclic ring.

[0124] The number of ring members in the heterocyclic ring is not particularly limited, but is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0125] The heterocyclic ring preferably has at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, more preferably has at least one heteroatom selected from a nitrogen atom and a sulfur atom, further preferably contains a nitrogen atom or a sulfur atom, and particularly preferably contains a nitrogen atom.

[0126] Examples of the heterocyclic ring include a pyridine ring, a pyrimidine ring, a thiophene ring, a furan ring, and a pyrrole ring.

[0127] The aromatic ring in the aromatic ring structure may be a monocyclic ring or a condensed aromatic ring formed by condensing two or more aromatic rings, but is preferably a monocyclic ring.

[0128] The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a monocyclic aromatic hydrocarbon ring, and still more preferably a benzene ring.

[0129] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (2), A is preferably 1 It is a single bond or an aromatic ring structure, and a benzene ring structure is more preferred.

[0130] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (2), X is preferably 1 and X 2 are independently a single bond, -O-, -NR 1A -、-COO-、-OCOO-、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A - and A 1 is a single bond or an aromatic ring structure, more preferably X 1 and X 2 are independently a single bond, -NR 1A -, -COO- or -OCOO- and A 1 is a single bond or a monocyclic aromatic ring structure, and more preferably X 1 and X 2 are independently a single bond or -COO- and A 1 It is a single bond or a benzene ring structure.

[0131] *-X 3 -A 2 -L 2 -A 3 -X 4 -* Formula (3)

[0132] In the above formula (3), X 3 and X 4 each independently represents a single bond, -O-, -S-, -NR 2A -, -CO-, -COO-, -OCOO-, -SO 2 NR 2A -、-CONR 2A -、-OCONR 2A -or-NR 2A CONR 2A -, R 2A represents a hydrogen atom or an alkyl group,

[0133] L 2 Indicates a single bond, -O-, -S-, -NR 2B -, -CO-, -COO-, -OCOO-, -SO 2 NR 2B -、-CONR 2B -、-OCONR 2B -、-NR 2B CONR 2B -, an alkylene group, an alkenyl group, an alkynyl group, an aromatic ring structure, or a group composed of these having 1 to 6 carbon atoms, R 2B represents a hydrogen atom or an alkyl group, A 2and A 3 Each independently represents an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure.

[0134] In formula (3), A 2 and A 3 The meanings of the aliphatic ring structure, aromatic ring structure and heterocyclic structure in formula (2) are the same as those of A in formula (2). 1 The aliphatic ring structure, aromatic ring structure and heterocyclic structure in have the same meanings.

[0135] In formula (3), X 3 and X 4 Each independently represents -NR 2A -、-SO 2 R 2A -、-CONR 2A -、-OCONR 2A -or-NR 2A CONR 2A -, preferably R 2A It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0136] In formula (3), L 2 Each independently represents -NR 2B -、-SO 2 R 2B -、-CONR 2B -、-OCONR 2B -or-NR 2B CONR 2B -, preferably R 2B It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0137] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (3), X is preferably 3 and X 4 are independently a single bond, -O-, -NR 2A -, -COO- or -CONR 2A -, more preferably a single bond, -O-, -NR 2A - or -COO-, more preferably a single bond or -COO-.

[0138] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (3), L is preferably 2 It is a single bond, -O-, -S- or -CO-, more preferably a single bond, -O- or -S-, further preferably a single bond.

[0139] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (3), A is preferably 2 and A 3 Each independently represents a single bond or an aromatic ring structure, more preferably a monocyclic aromatic ring structure, and still more preferably a benzene ring structure.

[0140] From the viewpoint of spectral characteristics, heat resistance and light resistance, in the above formula (3), X is preferably 3 and X 4 are independently a single bond, -O-, -NR 2A -, -COO- or -CONR 2A -, L 2 is a single bond, -O-, -S- or -CO- and A 2 and A 3 Each independently represents a single bond or an aromatic ring structure, and more preferably X 3 and X 4 are independently a single bond, -O-, -NR 2A -or-COO- and L 2 is a single bond, -O- or -S- and A 2 and A 3 Each of them is independently a monocyclic aromatic ring structure, and more preferably X 3 and X 4 are independently a single bond or -COO- and L 2 is a single bond and A 2 and A 3 Each independently represents a benzene ring structure.

[0141] In the dye having a structure represented by the above formula (1), Dye represents a dye structure having a maximum absorption wavelength in the wavelength range of 650 nm to 2,000 nm (hereinafter also referred to as "dye structure Dye").

[0142] In the present invention, Dye is "a pigment structure having a maximum absorption wavelength in the wavelength range of 650 nm to 2,000 nm" means that the compound having the pigment structure represented by Dye has a wavelength showing maximum absorbance in the wavelength range of 650 nm to 2,000 nm in the absorption spectrum in a solution.

[0143] The measurement solvent used in the measurement of the absorption spectrum in the solution of the compound with the pigment structure represented by Dye is as long as it is to dissolve the compound with the pigment structure represented by Dye, but from the viewpoint of solubility, chloroform, dimethylformamide, tetrahydrofuran, dichloromethane, etc. can be preferably cited. For example, in the case of a compound dissolved in chloroform, chloroform is used as a measurement solvent. In the case of a compound that is not dissolved in chloroform, dichloromethane is used. And, in the case of a compound that is not dissolved in any one of chloroform and dichloromethane, dimethylformamide is used. And, in the case of a compound that is not dissolved in any one of chloroform, dichloromethane and dimethylformamide, tetrahydrofuran is used.

[0144] The maximum absorption wavelength of the pigment structure Dye is preferably in the range of 700 nm to 1,200 nm, more preferably in the range of 750 nm to 1,200 nm, and even more preferably in the range of 750 nm to 1,000 nm.

[0145] As a dye structure Dye having a maximum absorption wavelength in the above-mentioned wavelength range, it is preferred to have a dye structure of at least one dye selected from pyrrolopyrrole dyes, polymethine dyes, diimmonium dyes, phthalocyanine dyes, naphthalocyanine dyes, reed dyes, dithiol complex dyes, triarylmethane dyes, pyrromethene dyes, methine azo dyes, anthraquinone dyes and dibenzofuranone dyes.

[0146] The polymethine dye may include cyanine dye, merocyanine dye, squaryl dye, crotonium dye, oxonol dye, etc., depending on the type of the bonded atomic group. Among these, the polymethine dye is preferably cyanine dye, squaryl dye and oxonol dye, and more preferably cyanine dye and squaryl dye.

[0147] The dye structure Dye preferably has a dye structure derived from at least one dye selected from pyrrolopyrrole dyes, cyanine dyes, squarylium dyes, diimmonium dyes, phthalocyanine dyes, naphthalocyanine dyes, and oxonocyanine dyes, and more preferably has a structure derived from squarylium dyes or pyrrolopyrrole dyes.

[0148] -Pyrrolopyrrole pigment structure-

[0149] As the structure derived from the pyrrolopyrrole dye (pyrrolopyrrole dye structure), a structure represented by the following formula (PP) is preferred.

[0150] [Chemical formula 2]

[0151]

[0152] In formula (PP), R 1a and R 1bEach independently represents an alkyl group, an aryl group or a heteroaryl group, and R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 With R 3 can be bonded to each other to form a ring, R 4 Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B or metal atom, R 4 Can be selected from R 1a , R 1b and R 3 At least one of them is covalently bonded or coordinately bonded, R 4A and R 4B Each independently represents a substituent, and the wavy line represents the same as L in formula (1). 1 The connecting part.

[0153] For details of formula (PP), reference may be made to paragraphs 0017 to 0047 of Japanese Patent Application Laid-Open No. 2009-263614, paragraphs 0011 to 0036 of Japanese Patent Application Laid-Open No. 2011-68731, and paragraphs 0010 to 0024 of International Publication No. 2015 / 166873, and these contents are incorporated into this specification.

[0154] In formula (PP), preferably R 1a and R 1b are each independently an aryl group or a heteroaryl group, more preferably an aryl group. 1a and R 1b The alkyl group, aryl group, and heteroaryl group represented may have a substituent or may be unsubstituted. As the substituent, the substituent T described below can be mentioned.

[0155] In formula (PP), R 2 and R 3 Each independently represents a hydrogen atom or a substituent. As the substituent, there can be mentioned the substituent T described below. Preferably R 2 and R 3 At least one of them is an electron withdrawing group, more preferably a cyano group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, further preferably a cyano group.

[0156] In formula (PP), R 2 represents an electron-withdrawing group (preferably a cyano group), preferably R 3represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. Furthermore, the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensations, and further preferably a monocyclic ring or a condensed ring with 2 to 4 condensations. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. Preferably, the heteroaryl group has one or more nitrogen atoms. The two R in formula (PP) 2 They may be the same or different from each other. 3 They can be the same or different from each other.

[0157] In formula (PP), preferably R 4 is a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or -BR 4A R 4B The group represented by -BR is more preferably a hydrogen atom, an alkyl group, an aryl group or a 4A R 4B The group represented by -BR 4A R 4B As R 4A and R 4B The substituent represented by is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and particularly preferably an aryl group. These groups may also have a substituent. The two R in formula (PP) 4 They may be the same or different from each other. 4A With R 4B They may be bonded to each other to form a ring.

[0158] When the dye structure Dye in formula (1) is a pyrrolopyrrole dye structure and n is 2, the dye represented by formula (1) is preferably a structure represented by the following formula (4-1).

[0159] The compound having a structure represented by the following formula (4-1), that is, the compound of the present invention, is a novel compound.

[0160] The compound of the present invention can be preferably used as a pigment or an infrared absorbing pigment, and can be more preferably used as an infrared absorbing pigment.

[0161] [Chemical formula 3]

[0162]

[0163] In formula (4-1), R 1a and R 1b Each independently represents an aryl or heteroaryl group, R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 With R3 can be bonded to each other to form a ring, R 4 Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B or metal atom, R 4 Can be selected from R 1a , R 1b and R 3 At least one of them is covalently bonded or coordinately bonded, R 4A and R 4B Each independently represents a hydrogen atom or a substituent, L 3 It is a group represented by the following formula (2) or the following formula (3).

[0164] R in formula (4-1) 1a , R 1b , R 2 , R 3 and R 4 The meanings of are respectively the same as R in formula (PP) 1a , R 1b , R 2 , R 3 and R 4 The meanings are the same and the preferred aspects are also the same.

[0165] *-X 1 -A 1 -X 2 -* Formula (2)

[0166] In the above formula (2), X 1 and X 2 Each independently represents a single bond, -O-, -S-, -NR 1A -, -CO-, -COO-, -OCOO-, -SO 2 NR 1A -、-CONR 1A -、-OCONR 1A -or-NR 1A CONR 1A -, R 1A represents a hydrogen atom, an alkyl group or an aryl group, A 1 represents a single bond, an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure, and * represents the connection position with Dye, wherein A 1 When it is a single bond, X 1 and X 2 These two are not single bonds at the same time.

[0167] X in formula (4-1) 1 , X 2 , R 1A and A 1The meanings of are respectively the same as those of X in the above formula (2) 1 , X 2 , R 1A and A 1 The meanings are the same and the preferred aspects are also the same.

[0168] *-X 3 -A 2 -L 2 -A 3 -X 4 -* Formula (3)

[0169] In the above formula (3), X 3 and X 4 each independently represents a single bond, -O-, -S-, -NR 2A -, -CO-, -COO-, -OCOO-, -SO 2 NR 2A -、-CONR 2A -、-OCONR 2A -or-NR 2A CONR 2A -, R 2A represents a hydrogen atom or an alkyl group,

[0170] L 2 Indicates a single bond, -O-, -S-, -NR 2B -, -CO-, -COO-, -OCOO-, -SO 2 NR 2B -、-CONR 2B -、-OCONR 2B -、-NR 2B CONR 2B -, an alkylene group, an alkenyl group, an alkynyl group, an aromatic ring structure, or a group composed of these having 1 to 6 carbon atoms, R 2B represents a hydrogen atom or an alkyl group, A 2 and A 3 Each independently represents an aliphatic ring structure, an aromatic ring structure or a heterocyclic structure.

[0171] X in formula (4-1) 3 , X 4 , R 2A , R 2B , L 2 , A 2 and A 3 The meanings of are respectively the same as those of X in the above formula (2) 3 , X 4 , R 2A , R 2B , L 2 , A 2 and A3 The meanings are the same and the preferred aspects are also the same.

[0172] The dye represented by formula (1) preferably has a structure represented by the following formula (4-2).

[0173] [Chemical formula 4]

[0174]

[0175] In formula (4-2), R 1a represents an aryl or heteroaryl group, R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 With R 3 can be bonded to each other to form a ring, R 4 Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B or metal atom, R 4 Can be selected from R 1a , R 1b and R 3 At least one of them is covalently bonded or coordinately bonded, R 4A and R 4B Each independently represents a hydrogen atom or a substituent, L 3 It is a group represented by the following formula (2) or the following formula (3).

[0176] R in formula (4-2) 1a , R 2 , R 3 and R 4 The meanings of are respectively the same as R in formula (PP) 1a , R 2 , R 3 and R 4 The meanings are the same and the preferred aspects are also the same.

[0177] L in formula (4-2) 3 The meaning is the same as L in formula (4-1) 3 The meanings are the same and the preferred aspects are also the same.

[0178] Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614 and compounds described in paragraphs 0037 to 0052 of JP-A-2011-68731, and the like, and the contents thereof are incorporated into the present specification.

[0179] -Squarein Pigment Structure-

[0180] As the squarylium dye structure, a structure derived from a compound represented by the following formula (SQ) is preferred.

[0181] [Chemical formula 5]

[0182]

[0183] In formula (SQ), A 1 and A 2 Each independently represents an aryl group, a heterocyclic group or a group represented by the following formula (Ax). 1 and A 2 At least one of them represents the same as L in formula (1) 1 Connecting group.

[0184] [Chemical formula 6]

[0185]

[0186] In formula (Ax), Z 1 represents a non-metallic atomic group forming a nitrogen-containing heterocyclic ring, R 2 represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a connecting bond. For details of formula (SQ), reference may be made to paragraphs 0020 to 0049 of Japanese Patent Publication No. 2011-208101, paragraphs 0043 to 0062 of Japanese Patent Publication No. 6065169, and paragraphs 0024 to 0040 of International Publication No. 2016 / 181987, which are incorporated herein by reference.

[0187] In addition, the cation in the formula (SQ) exists in a delocalized form as follows.

[0188] [Chemical formula 7]

[0189]

[0190] The squarylium dye is preferably a compound represented by the following formula (5).

[0191] [Chemical formula 8]

[0192]

[0193] In formula (5), ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring, and X A and X B Each independently represents a substituent, G A and G B Each independently represents a substituent, kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA and nB represent the maximum integer that can be substituted with ring A or ring B, respectively, and X A With GA , X B With G B can bond to each other to form a ring, G A and G B When there are multiple of each, they may be bonded to each other to form a ring structure. A , X B , G A and G B At least one of them represents the same as L in formula (1) 1 Connecting group.

[0194] G A and G B Each independently represents a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 、-COR 11 、-COOR 12 、-OCOR 13 、-NR 14 R 15 、-NHCOR 16 、-CONR 17 R 18 、-NHCONR 19 R 20 、-NHCOOR 21 、-SR 22 、-SO 2 R 23 、-SO 2 OR 24 、-NHSO 2 R 25 or -SO 2 NR 26 R 27 . R 10 ~R 27 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group. 12 R 12 In the case of a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or in the form of a salt. 2 OR 24 R 24 In the case of a hydrogen atom (ie, a sulfonic acid group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in a salt state.

[0195] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0196] The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group may be any of linear, branched, and cyclic, and is preferably a linear or branched alkyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and further preferably 2 to 8. The alkenyl group may be any of linear, branched, and cyclic, and is preferably a linear or branched alkenyl group. The number of carbon atoms of the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and further preferably 2 to 25. The alkynyl group may be any of linear, branched, and cyclic, and is preferably a linear or branched alkynyl group. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. 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 of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and further preferably 7 to 25.

[0197] The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed rings, and further preferably a monocyclic ring or a condensed ring with 2 to 4 condensed rings. The number of heteroatoms constituting the heteroaryl ring is preferably 1 to 3. The heteroatoms constituting the heteroaryl ring 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 heteroaryl ring is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. Examples of the heteroaryl group include a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoleline ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiadiazole ring.

[0198] The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent group T described below.

[0199] X A and X B Each independently represents a substituent. The substituent is preferably a group having active hydrogen, more preferably -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2 、-NHCOR X1 、-CONR X1 R X2 、-NHCONR X1 R X2 、-NHCOOR X1 、-NHSO 2 R X1 、-B(OH) 2 and -PO(OH) 2, more preferably -OH, -SH and -NR X1 R X2 . R X1 and R X2 Each independently represents a hydrogen atom or a substituent. As the substituent, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group can be mentioned. An alkyl group is preferably an alkyl group. The alkyl group is preferably a straight chain or a branched chain alkyl group. The details of the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the heteroaryl group are the same as those in G A and G B The meanings of the ranges described in the .

[0200] Ring A and Ring B each independently represent an aromatic ring or a heteroaromatic ring. The aromatic ring and the heteroaromatic ring may be a monocyclic ring or a condensed ring. Specific examples of the aromatic ring and the heteroaromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a tetraphenyl ring, ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyridine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thienyl ring, a chromene ring, a xanthene ring, a phenoxathiol ring, a phenothiazine ring and a phenazine ring, preferably a benzene ring or a naphthalene ring.

[0201] The aromatic ring and the heteroaromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include G A and G B The substituents described in .

[0202] X A With G A , X B With G B can bond to each other to form a ring, G A and G B When there are multiple G A Each other or G B They may also be bonded to each other to form a ring. As the ring, a 5-membered ring or a 6-membered ring is preferred. The ring may be a monocyclic ring or a polycyclic ring. A With G A , X B With G B , G A Each other or G B When they are bonded to each other to form a ring, they may be bonded to form a ring directly or through a divalent linking group selected from alkylene, -CO-, -O-, -NH-, -BR-, and a combination thereof. AWith G A , X B With G B , G A Each other or G B Each of them is bonded via -BR- to form a ring. R represents a hydrogen atom or a substituent. Examples of the substituent include G A and G B The substituents described in . Preferably, they are alkyl or aryl.

[0203] kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the maximum integer that can be substituted on ring A, and nB represents the maximum integer that can be substituted on ring B. Preferably, kA and kB are each independently 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

[0204] One embodiment of the squarylium dye is a compound represented by the following formula (6). This compound has excellent heat resistance.

[0205] [Chemical formula 9]

[0206]

[0207] In formula (6), R 1 and R 2 Each independently represents a substituent, R 3 and R 4 Each independently represents a hydrogen atom or an alkyl group, X 1 and X 2 Each independently represents an oxygen atom or -N(R 5 )-, R 5 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and Y 1 ~Y 4 Each independently represents a substituent, Y 1 With Y 2 and Y 3 With Y 4 can be bonded to each other to form a ring, Y 1 ~Y 4 When there are plural of each, they may be bonded to each other to form a ring; p and s each independently represent an integer of 0 to 3; and q and r each independently represent an integer of 0 to 2.

[0208] Among them, Y 1 ~Y 4 At least one of them represents the same as L in formula (1) 1 Connecting group.

[0209] R 1 , R 2 , Y 1 ~Y 4The substituent represented by may be G A and G B Preferably R 3 and R 4 Each independently represents a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0210] X 1 and X 2 Each independently represents an oxygen atom (-O-) or -N (R 5 )-.X 1 With X 2 They may be the same or different, but are preferably the same. 5 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. 5 is a hydrogen atom, an alkyl group or an aryl group. 5 The alkyl group, aryl group and heteroaryl group represented by the present invention may be an unsubstituted group or may have a substituent. As the substituent, the above-mentioned G A and G B The substituents described in . 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 a straight chain or a branched chain. The number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 12. The heteroaryl group may be a monocyclic ring or a polycyclic ring. 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 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.

[0211] -Structure of crotonium pigment-

[0212] As the crotonium dye structure, a structure derived from a compound represented by the following formula (CR) is preferred.

[0213] [Chemical formula 10]

[0214]

[0215] In formula (CR), A 3 and A 4 Each independently represents an aryl group, a heterocyclic group or a group represented by the following formula (Ax), wherein A 3 and A 4 At least one of them represents the same as L in formula (1) 1 Connecting group.

[0216] [Chemical formula 11]

[0217]

[0218] In formula (Ax), Z 1 represents a non-metallic atomic group forming a nitrogen-containing heterocyclic ring, R 2 represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a connecting bond. For details of formula (CR), reference can also be made to the compounds of Eur. J. Org. Chem. 2017, 3897-3911, and these contents are incorporated into this specification.

[0219] In the formula (CR), the cation exists in a delocalized form as follows.

[0220] [Chemical formula 12]

[0221]

[0222] -Pyrromethene pigment structure-

[0223] As the pyrromethene dye structure, a structure derived from a compound represented by the following formula (BDP) is preferred.

[0224] [Chemical formula 13]

[0225]

[0226] In the formula (BDP), Y represents CR 7 or N, R 7 represents a hydrogen atom or a substituent, R 1 ~R 6 Each independently represents a hydrogen atom or a substituent, R 1 With R 3 , R 3 With R 5 , R 2 With R 4 , R 4 With R 6 Can be connected to each other to form a ring structure, X 1 and X 2 Each independently represents a halogen atom, an oxygen atom, a hydroxyl group, an alkoxy group or an aryloxy group, and X 1 With X 2 Can bond with each other to form a ring structure, X 1 With R 5 Can bond to form a ring structure, X 2 With R 6 Can bond to form a ring structure.

[0227] Preferred R 5 and R 6 Each independently represents an aryl group or a heteroaryl group.

[0228] Preferred R 1 With R 3, R 2 With R 4 They are connected to each other to form a benzene ring or a naphthalene ring.

[0229] For details of formula (BDP), reference can be made to the compounds described in Chem. Soc. Rev., 2014, 43, 4778-4823, JP-A-2016-166284, JP-A-2018-123093, and JP-A-2019-77673, and these contents are incorporated into this specification.

[0230] Specific examples of the pigment having a structure represented by formula (1) include the following A-ppb-1 to A-ppb-36, A-sq-1 to A-sq-5, A-cr-1 to A-cr-5, A-bdp-1 to A-bdp-8, A-ryl-1, A-ryl-2, A-id-1, and A-id-2, but it goes without saying that the present invention is not limited to these pigments.

[0231] [Chemical formula 14]

[0232]

[0233] [Chemical formula 15]

[0234]

[0235] [Chemical formula 16]

[0236]

[0237] [Chemical formula 17]

[0238]

[0239] [Chemical formula 18]

[0240]

[0241] [Chemical formula 19]

[0242]

[0243] [Chemical formula 20]

[0244]

[0245] [Chemical formula 21]

[0246]

[0247] [Chemical formula 22]

[0248]

[0249] [Chemical formula 23]

[0250]

[0251] [Chemical formula 24]

[0252]

[0253] [Chemical formula 25]

[0254]

[0255] [Chemical formula 26]

[0256]

[0257] [Chemical formula 27]

[0258]

[0259] [Chemical formula 28]

[0260]

[0261] From the viewpoints of spectral characteristics, heat resistance and light resistance, the pigment having a structure represented by formula (1) is preferably at least one compound selected from pyrrolopyrrole compounds, rylene compounds, oxocyanine compounds, squaryl compounds, crokonium compounds, vanadium phthalocyanine compounds, naphthalocyanine compounds, indigo compounds and pyrromethene compounds, more preferably at least one compound selected from pyrrolopyrrole compounds, squaryl compounds, crokonium compounds and pyrromethene compounds, and more preferably a pyrrolopyrrole compound or a squaryl compound.

[0262] 〔Molecular weight〕

[0263] The molecular weight of the dye having a structure represented by the structure of formula (1) is preferably less than 4,000, more preferably less than 3,000, and further preferably less than 2,500.

[0264] 〔Volume average particle size〕

[0265] The volume average particle size of the pigment having a structure represented by the structure of formula (1) is preferably 1 nm to 500 nm, more preferably 1 nm to 300 nm, and further preferably 1 nm to 200 nm.

[0266] In the composition of the present invention, by using a pigment having a specific structure with a volume average particle diameter of 1nm to 500nm in a microparticle dispersion state, i.e., a specific pigment, there is an advantage of improving the durability of the pigment. If the volume average particle diameter is more than 1nm, the surface energy of the pigment particles becomes small, so it becomes difficult to aggregate, the dispersion of the pigment particles becomes easy, and it becomes easy to stably maintain the dispersed state, so it is preferred. In addition, if the volume average particle diameter of the pigment particles is less than 200nm, the influence of the scattering of the pigment particles becomes less, and the absorption spectrum becomes sharp, so it is preferred.

[0267] From the above viewpoints, the volume average particle size of the pigment having a structure represented by the structure of formula (1) is more preferably 10 nm to 200 nm, and further preferably 10 nm to 100 nm.

[0268] In the present invention, the volume average particle size of particles refers to the particle size of the fine particles themselves or, when additives such as a dispersant are attached to the fine particles, the particle size to which the additives are attached.

[0269] The volume average particle diameter of the particles can be measured using a NANOTRAC UPA particle size analyzer (UPA-EX150, product name, manufactured by Nikkiso Co., Ltd.) as a measuring device. 3 mL of the particle dispersion can be added to a measuring cell and measured according to a predetermined measuring method.

[0270] In addition, as parameters inputted at the time of measurement, the viscosity of the composition containing the pigment is used as the viscosity, and the density of the pigment which is the infrared absorbing pigment or the specific colored pigment is used as the density of the dispersed particles.

[0271] 〔Maximum absorption wavelength〕

[0272] The maximum absorption wavelength of the dye having the structure represented by formula (1) is preferably in the wavelength range of 650 nm or longer, more preferably in the wavelength range of 700 nm to 1,100 nm, and further preferably in the wavelength range of 760 nm to 950 nm.

[0273] The above-mentioned maximum absorption wavelength was measured using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies Japan, Ltd).

[0274] 〔Half-value width〕

[0275] In the wavelength-absorbance curve obtained when measuring the maximum absorption wavelength, the half-value width of the wavelength peak at the maximum absorption wavelength is preferably 2,000 cm -1 Below, more preferably 1,400cm -1 Below, more preferably 1,350cm -1 the following.

[0276] The lower limit of the half value width is not particularly limited, but is preferably 500 cm -1 above.

[0277] The half value width was measured using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies Japan, Ltd.), and the wavelength was converted into a wave number to calculate the half value width.

[0278] 〔Molar absorptivity〕

[0279] The molar absorption coefficient of the pigment having the structure represented by formula (1) at the maximum absorption wavelength is preferably 1.0×10 5 L / (mol·cm) or more, more preferably 1.5×10 5 L / (mol·cm) or more.

[0280] The above-mentioned molar absorption coefficient was measured using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies Japan, Ltd).

[0281] 〔content〕

[0282] The content of the pigment having a structure represented by formula (1) in the composition of the present invention is preferably 10% to 70% by mass, more preferably 15% to 60% by mass, and further preferably 20% to 50% by mass relative to the total solid content of the composition. The composition of the present invention can contain a combination of two or more pigments having a structure represented by formula (1). When containing two or more pigments having a structure represented by formula (1), the total amount is preferably within the above range.

[0283] The method for producing the dye having a structure represented by formula (1) is not particularly limited, and the dye can be produced appropriately with reference to a known production method.

[0284] For example, in the case where n is 2 in the pigment having a structure represented by formula (1) (i.e., in the case of a dimer pigment), as a method for synthesizing the pigment having a structure represented by formula (1), the following method (1) or method (2) can be cited as a synthesis method, but the synthesis method (1) is preferred from the viewpoint of ease of synthesis.

[0285] Method (1): A nucleophilic site is introduced into the dye structure represented by formula (1), and the dye is reacted with a polyfunctional electrophilic agent.

[0286] Examples of the nucleophilic site include OH, NHR (R represents a hydrogen atom or an alkyl group), and SH.

[0287] Examples of the polyfunctional electrophilic agent include polyfunctional carboxylic acids, polyfunctional carboxylic acid chlorides, polyfunctional carboxylic acid anhydrides, polyfunctional sulfone acid chlorides, polyfunctional isocyanates, polyfunctional alkyl halides (particularly p-xylene halide, etc.), and the like.

[0288] From the viewpoint of suppressing the decomposition of the dye during the binarization reaction, a highly reactive polyfunctional electrophilic reactant is preferred, and a polyfunctional carboxylic acid chloride, a polyfunctional sulfone acid chloride, or a polyfunctional isocyanate is more preferred.

[0289] As a specific example of method (1), there is mentioned a method of introducing one OH group as a nucleophilic site into the pyrrolopyrrole dye structure and reacting it with a difunctional carboxylic acid chloride as shown in the following scheme. In the following scheme, Et represents an ethyl group and Ph represents a phenyl group.

[0290] [Chemical formula 29]

[0291]

[0292] Furthermore, for example, there can be mentioned a method in which one OH group is introduced into the structure of a squarylium dye and then condensed with a difunctional carboxylic acid as in the following scheme.

[0293] In the process, EDC HCl refers to 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, DMAP refers to N,N-dimethyl-4-aminopyridine, and DMAc refers to dimethylacetamide.

[0294] [Chemical formula 30]

[0295]

[0296] Method (2): An electrophilic site is introduced into the dye structure represented by formula (1), and the dye is reacted with a polyfunctional nucleophilic reagent.

[0297] Examples of the electrophilic site include carboxylic acid, carboxylic acid chloride, carboxylic acid anhydride, sulfone acid chloride, isocyanate, and alkyl halide.

[0298] Examples of the polyfunctional nucleophilic site include polyfunctional alcohols, polyfunctional secondary or primary amines, and polyfunctional thiols.

[0299] As a specific example of method (2), a carboxylic acid (COOH) is introduced into the pyrrolopyrrole pigment structure and reacted with p-hydroquinone (HOC) as follows: 6 H 4 OH, C 6 H 4 represents 1,4-phenylene. ) is reacted.

[0300] [Chemical formula 31]

[0301]

[0302] In addition, as another synthesis method, a crotonium dye having two carboxylic acids (COOH) and p-hydroquinone (HOC) are reacted under the reaction conditions described in the following scheme in Chem. Sci. 2017, 8. 2710-2716. 6 H 4 OH, C 6 H 4 represents 1,4-phenylene. ) and a method of purifying by silica gel column chromatography.

[0303] [Chemical formula 32]

[0304]

[0305] In addition, a method for adjusting the crystal form of a pigment having a structure represented by formula (1) is described. As a method for adjusting the crystal form, a method of contacting a pigment having a structure represented by formula (1) with an organic solvent such as N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, etc. can be cited. At this time, in order to adjust the particle size of the pigment having a structure represented by formula (1), heating or cooling can be performed, and other solvents can also be added before filtering and screening.

[0306] <Other ingredients>

[0307] The composition of the present invention is preferably a composition that can obtain a film, and is preferably a curable composition that can obtain a cured film by final curing.

[0308] Furthermore, the composition of the present invention is preferably a composition capable of forming a pattern of a cured film by pattern exposure, for example. That is, the composition of the present invention is preferably a negative-type composition.

[0309] When the composition of the present invention is a negative-type composition, for example, an embodiment containing a polymerization initiator, a polymerizable compound, and an alkali-soluble resin is preferred.

[0310] When the composition of the present invention is a positive-type composition, for example, an embodiment including a photoacid generator, a polymer having a structural unit including a group in which an acid group is protected by an acid-decomposable group, and a polymer having a structural unit including a crosslinkable group can be mentioned.

[0311] Hereinafter, each component contained in the embodiment in which the composition of the present invention is a negative composition will be described.

[0312] In an embodiment in which the composition of the present invention is a positive-type composition, the components contained therein include those described in International Publication No. 2014 / 003111, and preferred embodiments are also the same.

[0313] <Resin>

[0314] From the viewpoint of film-forming properties, the composition of the present invention preferably contains a resin.

[0315] Furthermore, examples of the resin include a binder polymer, a dispersant, and the like.

[0316] From the viewpoint of film-forming property and dispersibility, the resin preferably contains a binder polymer.

[0317] Specific examples of the binder polymer include acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, polyurethane resins, etc. Among them, acrylic resins are preferably contained.

[0318] These resins may be used alone or in combination of two or more.

[0319] As the cyclic olefin resin, from the viewpoint of improving heat resistance, a norbornane resin can be preferably used.

[0320] Examples of commercially available norbornane resins include ARTON series manufactured by JSR CORPORATION CORPORATION (for example, ARTON F4520), etc. Examples of commercially available polyimide resins include Neoprim (registered trademark) series manufactured by MITSUBISHI GASCHEMICAL COMPANY, INC. (for example, C3450), etc.

[0321] Furthermore, as binder polymers, resins described in the examples of International Publication No. 2016 / 088645, resins described in Japanese Patent Publication No. 2017-57265, resins described in Japanese Patent Publication No. 2017-32685, resins described in Japanese Patent Publication No. 2017-75248, and resins described in Japanese Patent Publication No. 2017-66240 can also be used, and these contents are incorporated into this specification.

[0322] Furthermore, as the binder polymer, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, reference can be made to the description of U.S. Patent Application Publication No. 2017 / 0102610, the contents of which are incorporated into this specification.

[0323] The weight average molecular weight (Mw) of the binder polymer is preferably 2,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and further preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and further preferably 5,000 or more.

[0324] The content of the binder polymer is preferably 10% to 80% by mass, more preferably 15% to 60% by mass, relative to the total solid content of the composition. The above composition may contain only one resin or two or more. When containing two or more resins, the total amount is preferably within the above range.

[0325] -Dispersant-

[0326] Examples of the dispersant include polymer dispersants [for example, resins having an amino group (polyamide amine and its salts, etc.), oligoimide resins, polycarboxylic acids and its salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid copolymers, naphthalenesulfonic acid formalin condensates] and the like.

[0327] The polymer dispersants can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structures.

[0328] Furthermore, as the polymer dispersant, preferably, a resin having an acid value of 60 mgKOH / g or more (more preferably an acid value of 60 mgKOH / g or more and 300 mgKOH / g or less) can be used.

[0329] As terminal modified polymer, for example, polymers with phosphate groups at the terminal, polymers with sulfonic acid groups at the terminal, polymers with partial skeletons or heterocycles of organic pigments recorded in Japanese Unexamined Patent Publication No. 3-112992, Japanese Unexamined Patent Publication No. 2003-533455, etc., polymers with partial skeletons or heterocycles of organic pigments recorded in Japanese Unexamined Patent Publication No. 9-77994, etc., etc., can be enumerated. And, preferably, the dispersion stability of polymers introduced into the anchoring sites (partial skeletons or heterocycles of acidic groups, basic groups, organic pigments, etc.) on the pigment surface at the polymer terminal recorded in Japanese Unexamined Patent Publication No. 2007-277514 is also excellent.

[0330] Examples of the graft polymer include reaction products of poly(lower alkylene imine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, etc., reaction products of poly(allylamine) and polyester described in JP-A-10-339949, JP-A-2009-258668, etc. Copolymers of macromonomers and nitrogen atom monomers as described in Japanese Patent Publication No. 04-37986, etc., graft polymers having a partial skeleton or heterocyclic ring of an organic pigment as described in Japanese Patent Publication No. 2003-238837, Japanese Patent Publication No. 2008-9426, Japanese Patent Publication No. 2008-81732, etc., copolymers of macromonomers and acid group-containing monomers as described in Japanese Patent Publication No. 2010-106268, etc.

[0331] As the macromonomer used when producing the graft polymer by free radical polymerization, a known macromonomer can be used, and examples thereof include AA-6 (polymethyl methacrylate having a methacryloyl terminal group), AS-6 (polystyrene having a methacryloyl terminal group), AN-6S (a copolymer of styrene and acrylonitrile having a methacryloyl terminal group), AB-6 (polybutyl acrylate having a methacryloyl terminal group), PLACCEL FM5 (a product containing 5 molar equivalents of ε-caprolactone of 2-hydroxyethyl methacrylate) and FA10L (a product containing 10 molar equivalents of ε-caprolactone of 2-hydroxyethyl acrylate) manufactured by TOAGOSEI CO., LTD., and polyesters described in Japanese Patent Application Publication No. 2-272009. Among these, from the viewpoint of the dispersibility and dispersion stability of the pigment dispersion and the developability of the composition formed by using the pigment dispersion, a polyester macromonomer having excellent flexibility and solvent affinity is particularly preferred, and the polyester macromonomer represented by the term “polyester macromonomer” described in JP-A-2-272009 is most preferred.

[0332] As the block polymer, block polymers described in JP-A-2003-49110, JP-A-2009-52010, and the like are preferred.

[0333] The resin (dispersant) can also be obtained as a commercial product, and specific examples thereof include BYK Chemie GmbH's "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA's "EFKA4047, 4050 to 4165 (polyurethane series), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Inc.'s "AJISPER PB821, PB822, PB880, PB881", KYOEISHA CHEMICAL CO., LTD. "FLOREN TG-710 (amine ester oligomer)", "POLYFLOW No.50E, No.300 (acrylic copolymer)", Kusumoto Chemicals, Ltd. "DISPARON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation "DEMOL (registered trademark) RN, N (naphthalenesulfonic acid formalin condensation product), MS, C, SN-B (aromatic sulfonic acid formalin condensation product)", "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearamide acetate)", "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000, 38500 (graft-type polymer)" manufactured by Lubrizol Japan Limited, "NIKKOR T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko Chemicals Co., Ltd., "Hinoact T-8000E" manufactured by Kawaken Fine Chemicals Co., Ltd., Shin-Etsu Chemical Co., Ltd.'s "Organosiloxane Polymer KP341", MORISHITA & CO., LTD.'s "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", SAN NOPCO LIMITED's "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100", ADEKA Corporation's "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" and Sanyo Chemical Industries, Ltd.'s "IONET S-20", etc.

[0334] These resins can be used alone or in combination of two or more. In addition, the alkali-soluble resin described later can also be used as a dispersant. As alkali-soluble resins, (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. and acidic cellulose derivatives with carboxylic acid groups on the side chains, resins of polymers modified with anhydride to have hydroxyl groups can be cited, but (meth) acrylic acid copolymers are particularly preferred. In addition, the alkali-soluble resins containing polymerizable groups recorded in the N-substituted maleimide monomer copolymers described in Japanese Unexamined Patent Publication No. 10-300922, the ether dimer copolymers described in Japanese Unexamined Patent Publication No. 2004-300204, and Japanese Unexamined Patent Publication No. 7-319161 are also preferred.

[0335] Among these, as the above-mentioned resin, from the viewpoint of dispersibility, it is preferred to contain a resin having a polyester chain, and it is more preferred to contain a resin having a polycaprolactone chain. In addition, from the viewpoint of dispersibility, transparency, and suppression of film defects caused by foreign matter, it is preferred that the above-mentioned resin (preferably an acrylic resin) contains a structural unit having an ethylenically unsaturated group.

[0336] The ethylenically unsaturated group is not particularly limited, but a (meth)acryloyl group is preferred.

[0337] Furthermore, when the resin has an ethylenically unsaturated group, particularly a (meth)acryloyl group, in a side chain, the resin preferably contains a divalent linking group having an alicyclic structure between the main chain and the ethylenically unsaturated group.

[0338] When the compound having a partial structure represented by formula (1) and a pigment, dye or pigment derivative other than the compound having a partial structure represented by formula (1) are contained, the content of the dispersant is preferably 1 to 100 parts by mass, more preferably 5 to 90 parts by mass, and even more preferably 10 to 80 parts by mass, based on 100 parts by mass of the total content of the compound having a partial structure represented by formula (1) and the pigment, dye and pigment derivative other than the compound having a partial structure represented by formula (1).

[0339] -Alkali soluble resin-

[0340] The composition of the present invention preferably contains an alkali-soluble resin.

[0341] From the viewpoint of developability, the composition of the present invention preferably contains an alkali-soluble resin as a binder polymer.

[0342] As the alkali-soluble resin, it can be appropriately selected from linear organic high molecular polymers and alkali-soluble resins having at least one group promoting alkali solubility in the molecule (preferably a molecule with an acrylic copolymer or a styrene copolymer as the main chain). From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred, and from the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred.

[0343] As the group promoting alkali solubility (hereinafter also referred to as acid group), for example, carboxyl group, phosphoric acid group, sulfonic acid group, phenolic hydroxyl group, etc. can be cited, but it is preferably soluble in organic solvents and can be developed by weak alkaline aqueous solution, and (meth) acrylic acid can be cited as a preferred group. These acid groups can be only one kind or two or more kinds. As alkali-soluble resins, reference can be made to the records of paragraphs 0558 to 0571 of Japanese Patent Publication No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding U.S. Patent Application Publication No. 2012 / 0235099), and these contents are incorporated into this specification.

[0344] It is also preferred that the alkali-soluble resin is a resin having a structural unit represented by the following formula (ED).

[0345] [Chemical formula 33]

[0346]

[0347] In formula (ED), R E1 and R E2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and z represents 0 or 1.

[0348] As R E1 and R E2 The hydrocarbon group having 1 to 25 carbon atoms represented by is not particularly limited, and examples thereof include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, 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 these, primary or secondary hydrocarbon groups that are difficult to be separated by acid or heat, such as methyl, ethyl, cyclohexyl, and benzyl, are preferred from the viewpoint of heat resistance.

[0349] In addition, R E1 and R E2 The substituents may be of the same type or different types.

[0350] Examples of compounds forming the structural unit represented by formula (ED) include 2,2'-[oxybis(methylene)]bis-2-acrylate dimethyl ester, 2,2'-[oxybis(methylene)]bis-2-acrylate diethyl ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(n-propyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(n-butyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(tert-butyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(isobutyl) ester, etc. Among these, 2,2'-[oxybis(methylene)]bis-2-acrylate dimethyl ester is particularly preferred.

[0351] The above-mentioned alkali-soluble resin may have a structural unit other than the structural unit represented by formula (ED).

[0352] As the monomers forming the above structural units, it is also preferred to contain, as copolymerization components, aryl (meth)acrylates, alkyl (meth)acrylates, and polyethyleneoxy (meth)acrylates that impart oil solubility, from the viewpoint of ease of handling, such as solubility in a solvent, and aryl (meth)acrylates or alkyl (meth)acrylates are more preferred.

[0353] Furthermore, from the viewpoint of alkali developability, it is preferred that the copolymerization component contain a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid containing an acidic group, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, or a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, and (meth)acrylic acid is more preferred.

[0354] Preferred examples of the alkali-soluble resin include resins having a structural unit represented by formula (ED), a structural unit composed of benzyl methacrylate, and a structural unit composed of at least one monomer selected from methyl methacrylate and methacrylic acid.

[0355] Regarding the resin having the structural unit represented by the formula (ED), reference can be made to the description in paragraphs 0079 to 0099 of JP-A-2012-198408, the contents of which are incorporated herein.

[0356] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000. The lower limit is more preferably 5,000 or more, and further preferably 7,000 or more. The upper limit is more preferably 45,000 or less, and further preferably 43,000 or less.

[0357] The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

[0358] In addition, the acid value in the present invention is measured by the following method.

[0359] The acid value indicates the mass of potassium hydroxide required to neutralize the acidic components per 1g of solid content. The sample to be measured is dissolved in a mixed solvent of tetrahydrofuran / water = 9 / 1 (mass ratio), and the obtained solution is neutralized and titrated with a 0.1 mol / L sodium hydroxide aqueous solution at 25°C using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The inflection point of the titration pH curve is used as the titration endpoint, and the acid value is calculated by the following formula.

[0360] A=56.11×Vs×0.1×f / w

[0361] A: Acid value (mgKOH / g)

[0362] Vs: The amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)

[0363] f: titration of 0.1 mol / l sodium hydroxide aqueous solution

[0364] w: Measured sample mass (g) (converted into solid content)

[0365] <Curing compound>

[0366] From the viewpoint of heat resistance and light resistance, the composition of the present invention contains a curable compound.

[0367] As the curable compound that can be used in the present invention, a polymerizable compound is preferred, an ethylenically unsaturated compound is more preferred, and a compound having a terminal ethylenically unsaturated group is particularly preferred.

[0368] As these compound groups, known compound groups can be used without particular limitation.

[0369] These, for example, have the chemical forms of monomers, prepolymers, i.e., dimers, trimers and oligomers or mixtures thereof and copolymers thereof. As examples of monomers and copolymers thereof, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited. Preferably, esters of unsaturated carboxylic acids and aliphatic polyol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds can be used. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups and monofunctional or polyfunctional isocyanates or epoxies and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids can also be preferably used. Also preferred are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines, or thiols, and further substitution reaction products of unsaturated carboxylic acid esters or amides having a halogen group or a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, or thiols. Also preferred are, in place of the above-mentioned unsaturated carboxylic acid, a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether, or the like.

[0370] Specific examples of the monomer of the ester of an aliphatic polyol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO-modified triacrylate, and the like.

[0371] Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, and bis[p-(methacryloyloxyethoxy)phenyl]dimethylmethane.

[0372] Furthermore, it is also preferred that the carbamate produced by the addition reaction of an isocyanate group and a hydroxyl group is an addition polymerizable compound. Specific examples thereof include vinyl carbamate compounds containing two or more polymerizable vinyl groups in one molecule of a vinyl monomer containing a hydroxyl group represented by the following general formula (I) added to a polyisocyanate compound having two or more isocyanate groups in one molecule as described in Japanese Patent Gazette No. 48-41708.

[0373] CH 2 =C(R)COOCH 2 CH(R')OH (I)

[0374] (wherein, R and R' represent H or CH 3 . )

[0375] Also preferred are urethane acrylates described in Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, Japanese Patent Application Laid-Open No. 2-16765, or urethane compounds having an oxirane skeleton as described in Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Application Laid-Open No. 62-39417, Japanese Patent Application Laid-Open No. 62-39418. In addition, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, Japanese Patent Application Laid-Open No. 1-105238, a composition having a very excellent photosensitivity can be obtained.

[0376] Examples of the curable compound include compounds described in paragraphs 0178 to 0190 of JP-A-2007-277514.

[0377] Furthermore, as the curable compound, the epoxy compound described in JP-A-2015-187211 may be used.

[0378] The content of the curable compound in the composition is preferably 1% to 90% by mass, more preferably 5% to 80% by mass, and further preferably 10% to 70% by mass relative to the total solid content of the composition. If the content of the curable compound is within the above range, the curability of the composition is excellent.

[0379] Particularly, when the composition of the present invention is used for forming a color pattern of a color filter, the content is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and further preferably 10 to 35% by mass within the above content range.

[0380] <Polymerization initiator>

[0381] The composition of the present invention preferably further comprises a polymerization initiator, and more preferably further comprises a photopolymerization initiator.

[0382] Furthermore, in the composition of the present invention, the curable compound contains a polymerizable compound and particularly preferably further contains a photopolymerization initiator.

[0383] As the photopolymerization initiator, there is no particular limitation as long as it has the ability to initiate polymerization of a polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitized to light in the ultraviolet region to the visible region is preferred. In addition, it can be a compound that generates active free radicals by reacting with a photoexcited sensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0384] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and still more preferably an oxime compound. Regarding the photopolymerization initiator, reference can be made to the description in paragraphs 0065 to 0111 of JP-A-2014-130173 and paragraphs 0274 to 0306 of JP-A-2013-29760, and these contents are incorporated into the present invention.

[0385] Commercially available products of α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Commercially available products of α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Commercially available products of acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF).

[0386] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-66385, the compounds described in Japanese Patent Application Publication No. 2000-80068, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2006-342166, the compounds described in Japanese Patent Application Publication No. 2017-19766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, etc. Specific examples of oxime compounds 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. Commercially available products of oxime compounds may also be preferably used: IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, and IRGACURE OXE04 (all manufactured by BASF). In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLSNCI-930, ADEKA OPTOMER N-1919 (photopolymerization initiator 2 in JP-A-2012-14052) (these are manufactured by ADEKA Corporation) can be mentioned.

[0387] Furthermore, as oxime compounds other than the above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone site, compounds described in Japanese Patent Publication No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced at the pigment site, ketone oxime compounds described in International Publication No. 2009 / 131189, compounds described in U.S. Patent No. 7556910 in which a triazine skeleton and an oxime skeleton are contained in the same molecule, compounds described in Japanese Patent Publication No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, etc. can also be used.

[0388] In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into the present invention.

[0389] In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples thereof include compounds OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0390] In the present invention, as the photopolymerization initiator, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505.

[0391] In the present invention, as a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds (C-3) described in Japanese Patent Application Publication No. 2013-164471. This content is incorporated into the present invention.

[0392] In the present invention, as a photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group is set as a dimer. As specific examples of oxime compounds having a nitro group, there can be cited the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012, paragraphs 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071, ADEKAARKLSNCI-831 (manufactured by ADEKA Corporation), etc.

[0393] Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited to these.

[0394] [Chemical formula 34]

[0395]

[0396] [Chemical formula 35]

[0397]

[0398] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and preferably has a high absorbance at wavelengths of 365 nm and 405 nm.

[0399] From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and further preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured at a concentration of 0.01 g / L using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) and an ethyl acetate solvent.

[0400] In the present invention, as a photopolymerization initiator, a photopolymerization initiator having two or more functions may also be used. Specific examples of these photopolymerization initiators include dimers of oxime compounds described in paragraphs 0417 to 0412 of Japanese Patent Table 2010-527339, Japanese Patent Table 2011-524436, International Publication No. 2015 / 004565, Japanese Patent Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, or compounds (E) and (G) described in Japanese Patent Table 2013-522445, and Cmpd1 to 7 described in International Publication No. 2016 / 034963.

[0401] The polymerization initiator may be used alone or in combination of two or more.

[0402] The content of the polymerization initiator in the composition is preferably 0.1% to 50% by mass, more preferably 0.5% to 30% by mass, and particularly preferably 1% to 20% by mass relative to the total solid content of the composition. Within this range, good sensitivity and pattern forming properties can be obtained.

[0403] <Coloring agent>

[0404] The composition of the present invention may contain a colorant. In the present invention, the colorant refers to a colorant other than a white colorant and a black colorant. The colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.

[0405] In the present invention, chromatic colorants and black colorants are also collectively referred to as visible colorants.

[0406] As the color coloring agent, red coloring agent, green coloring agent, blue coloring agent, yellow coloring agent, purple coloring agent and orange coloring agent can be mentioned. The color coloring agent can be a pigment or a dye. Pigments and dyes can be used in combination. In addition, the pigment can be any one of an inorganic pigment or an organic pigment. In addition, a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced by an organic chromophore can also be used in the pigment. By replacing an inorganic pigment or an organic-inorganic pigment by an organic chromophore, hue design can be easily performed.

[0407] The average primary particle size of the pigment is preferably 1 nm to 200 nm. The lower limit is more preferably 5 nm or more, and further preferably 10 nm or more. The upper limit is more preferably 180 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less. If the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the composition is good. In addition, regarding the primary particle size of the pigment in the present invention, the primary particles of the pigment are observed under a transmission electron microscope and can be obtained from the obtained image photograph. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present invention refers to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0408] The color colorant preferably contains a pigment. The content of the pigment in the color colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of the pigment include the following.

[0409] Colorimetric Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 1 29, 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, 215, 228 (straight-chain quinoline yellow dimer described in International Publication No. 2013 / 098836), 231, 232 (methine series), 233 (quinoline series), etc. (the above are yellow pigments),

[0410] CI Pigment Orange (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),

[0411] CI Pigment Red (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, 294 (xanthene series, Organo Ultramarine (organic ultramarine), Bluish Red (blue red)), 295 (monoazo series), 296 (diazo series), etc. (the above are red pigments),

[0412] CI Pigment Green (pigment green) 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments),

[0413] CI Pigment Violet (Pigment Violet) 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series), etc. (the above are purple pigments),

[0414] CI Pigment Blue (Pigment Blue) 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (methine series), etc. (the above are blue pigments).

[0415] Furthermore, as green pigments, zinc phthalocyanine halides having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. As specific examples, compounds described in International Publication No. 2015 / 118720 can be cited. Furthermore, as green pigments, compounds described in the specification of Chinese Patent Application No. 106909027, phthalocyanine compounds having phosphate ester as a ligand described in International Publication No. 2012 / 102395, and the like can also be used.

[0416] Furthermore, as a green colorant, a green colorant described in Japanese Patent Application Publication No. 2019-8014 or Japanese Patent Application Publication No. 2018-180023 may be used.

[0417] Furthermore, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment, and specific examples thereof include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0418] Furthermore, as yellow pigments, Japanese Patent Laid-Open No. 2018-203798, Japanese Patent Laid-Open No. 2018-62578, Japanese Patent No. 6432077, Japanese Patent No. 6432076, Japanese Patent Laid-Open No. 2018-155881, Japanese Patent Laid-Open No. 2018-111757, Japanese Patent Laid-Open No. 2018-40835, Japanese Patent Laid-Open No. 2017-197640, Japanese Patent Laid-Open No. 2016-145282, Japanese Patent Laid-Open No. 2014-85565, Japanese Patent Laid-Open No. 2014-21139, Japanese Patent Laid-Open No. 2013-209614, Japanese Patent Laid-Open No. 2013-219615, Japanese Patent Laid-Open No. 2013-209616, Japanese Patent Laid-Open No. 2013-209617, Japanese Patent Laid-Open No. 2013-209618, Japanese Patent Laid-Open No. 2013-209619 ...9, Japanese Patent Laid-Open No. 2013-209619, Japanese Patent Laid-Open No. 2013-209619, Japanese Patent Laid-Open No. 2013-209619, Japanese Patent Laid-Open No. 2013 Quinoline yellow pigment described in Japanese Patent Application No. 013-209435, Japanese Patent Application No. 2013-181015, Japanese Patent Application No. 2013-61622, Japanese Patent Application No. 2013-54339, Japanese Patent Application No. 2013-32486, Japanese Patent Application No. 2012-226110, Japanese Patent Application No. 2008-74987, Japanese Patent Application No. 2008-81565, Japanese Patent Application No. 2008-74986, Japanese Patent Application No. 2008-74985, Japanese Patent Application No. 2008-50420, Japanese Patent Application No. 2008-31281 or Japanese Patent Application No. 48-32765. Furthermore, pigments described in Japanese Patent No. 6443711 can also be used.

[0419] Furthermore, as yellow pigments, quinoline yellow compounds described in paragraphs 0011 to 0034 of JP-A-2013-54339, quinoline yellow compounds described in paragraphs 0013 to 0058 of JP-A-2014-26228, yellow pigments described in JP-A-2019-8014, and the like can also be used.

[0420] Furthermore, as a yellow pigment, a compound described in Japanese Patent Application Laid-Open No. 2018-062644 can also be used. This compound can also be used as a pigment derivative.

[0421] In addition, as described in Japanese Patent Application Laid-Open No. 2018-155881, CI Pigment Yellow 129 may be added to improve weather resistance.

[0422] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure as described in Japanese Patent Publication No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, naphthol azo compounds described in Japanese Patent Publication No. 2012-229344, etc. can also be used. In addition, as red pigments, compounds having a structure in which an aromatic ring group formed by introducing a group bonded with an oxygen atom, a sulfur atom or a nitrogen atom into an aromatic ring and a diketopyrrolopyrrole skeleton are bonded can also be used.

[0423] In the present invention, dyes can also be used in colorants. There is no particular limitation on the dyes, and known dyes can be used. For example, pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridine quinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole methine azo, xanthene, phthalocyanine, benzopyran, indigo, pyrrole methylene and other dyes can be cited. In addition, thiazole compounds described in Japanese Patent Publication No. 2012-158649, azo compounds described in Japanese Patent Publication No. 2011-184493, and azo compounds described in Japanese Patent Publication No. 2011-145540 can also be preferably used. Furthermore, as the yellow dye, quinoline yellow compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinoline yellow compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can also be used.

[0424] When the composition of the present invention contains a colorant, the content of the colorant is preferably 1% to 50% by mass relative to the total solid content of the composition. When the composition of the present invention contains two or more colorants, the total amount of these colorants is preferably within the above range.

[0425] <Colorants that transmit near infrared rays and block visible light>

[0426] The composition of the present invention may also contain a colorant (hereinafter also referred to as a visible light blocking colorant) that transmits near infrared light (light with a wavelength in the near infrared region) and blocks visible light (light with a wavelength in the visible region). A composition containing a visible light blocking colorant can be preferably used as a composition for forming a near infrared transmission filter.

[0427] In the present invention, the colorant that blocks visible light is preferably a colorant that absorbs light in the wavelength range of purple to red. In addition, the colorant that blocks visible light in the present invention is preferably a colorant that blocks light in the wavelength range of 450nm to 650nm. In addition, the colorant that blocks visible light is preferably a colorant that transmits light in the wavelength range of 900nm to 1,300nm. In the present invention, it is preferred that the colorant that blocks visible light satisfies at least one of the following requirements (A) and (B).

[0428] (A): Two or more chromatic colorants are contained, and black is formed by the combination of the two or more chromatic colorants.

[0429] (B): Contains an organic black colorant.

[0430] As color coloring agents, the above-mentioned coloring agents can be cited. As organic black coloring agents, for example, bisbenzofuranone compounds, methine azo compounds, perylene compounds, azo compounds, etc. can be cited, preferably bisbenzofuranone compounds and perylene compounds. As bisbenzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. can be cited, for example, they can be obtained as "Irgaphor Black" manufactured by BASF. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821, CI Pigment Black 31, 32, etc. can be cited. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664. For example, it is available as "Phthalocyanine Black A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0431] As a combination of color colorants when forming black by combining two or more color colorants, the following aspects are mentioned, for example.

[0432] (1) A form containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.

[0433] (2) A form containing a yellow colorant, a blue colorant, and a red colorant.

[0434] (3) A form containing a yellow colorant, a purple colorant, and a red colorant.

[0435] (4) A method containing a yellow colorant and a purple colorant.

[0436] (5) A form containing a green colorant, a blue colorant, a purple colorant, and a red colorant.

[0437] (6) A form containing a purple colorant and an orange colorant.

[0438] (7) A form containing a green colorant, a purple colorant and a red colorant.

[0439] (8) A form containing a green colorant and a red colorant.

[0440] As the ratio (mass ratio) of each coloring agent, for example, the following ratios are preferable.

[0441] [Chemical formula 36]

[0442] 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

[0443] In the above No. 1, the yellow colorant is more preferably 0.1 to 0.3, the blue colorant is more preferably 0.1 to 0.5, the purple colorant is more preferably 0.01 to 0.2, and the red colorant is more preferably 0.1 to 0.5. In the above No. 2, the yellow colorant is more preferably 0.1 to 0.3, the blue colorant is more preferably 0.1 to 0.5, and the red colorant is more preferably 0.1 to 0.5.

[0444] The composition may contain only one type of visual colorant, or may contain two or more types.

[0445] The content of the visible colorant is preferably 0.1% by mass to 70% by mass, more preferably 0.5% by mass to 60% by mass, and further preferably 1% by mass to 50% by mass, based on the total mass of the composition.

[0446] <Pigment derivatives>

[0447] The composition may contain a pigment derivative. Examples of the pigment derivative include compounds in which at least one group selected from an acid group, a basic group, and a hydrogen bonding group is bonded to a dye skeleton.

[0448] Examples of the acid group include sulfonic acid group, carboxyl group, phosphoric acid group, boric acid group, sulfonimide group, sulfonamide group, and salts thereof and desalted structures of these salts. Examples of the atom or atomic group constituting the salt include alkali metal ions (Li + 、Na + , K + etc.), alkaline earth metal ions (Ca 2+ Mg 2+ The desalted structure of the above salts includes a group of atoms or atomic groups that are separated from the above salts to form salts. For example, the desalted structure of a salt of a carboxyl group is a carboxylate group (-COO - ).

[0449] As the basic group, amino, pyridyl, and salts thereof and desalted structures of these salts can be cited. As the atom or atomic group constituting the salt, hydroxide ion, halide ion, carboxylate ion, sulfonate ion, phenol ion, etc. can be cited. And, as the desalted structure of the above-mentioned salt, a group of the atom or atomic group that is separated from the above-mentioned salt to form the salt can be cited.

[0450] The hydrogen bonding group refers to a group that interacts via a hydrogen atom. Specific examples of the hydrogen bonding group include an amide group, a hydroxyl group, -NHCONHR, -NHCOOR, -OCONHR, etc. Preferably, R is an alkyl group or an aryl group.

[0451] Examples of the pigment derivative include compounds represented by formula (B1).

[0452] [Chemical formula 37]

[0453]

[0454] In formula (B1), P represents a pigment skeleton, L represents a single bond or a linking group, X represents an acid group, a basic group or a hydrogen bonding group, m represents an integer greater than 1, and n represents an integer greater than 1. When m is greater than 2, multiple L and X may be different from each other, and when n is greater than 2, multiple X may be different from each other.

[0455] As the dye skeleton represented by P, at least one selected from a squaric acid dye skeleton, a crotonium dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a quinacridone dye skeleton, an anthraquinone dye skeleton, a dianthraquinone dye skeleton, a benzisoindole dye skeleton, a thiazine indigo dye skeleton, an azo dye skeleton, a quinoline yellow dye skeleton, a phthalocyanine dye skeleton, a naphthalocyanine dye skeleton, a dioxazine dye skeleton, a perylene dye skeleton, a pyrene dye skeleton, a benzimidazolone dye skeleton, a benzothiazole dye skeleton, a benzimidazole dye skeleton, and a benzoxazole dye skeleton is preferred. At least one selected from a squaric acid dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a quinacridone dye skeleton, and a benzimidazolone dye skeleton is further preferred. A squaric acid dye skeleton or a pyrrolopyrrole dye skeleton is particularly preferred.

[0456] The linking group represented by L is preferably a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, and may be unsubstituted or further substituted. Examples of the substituent include the substituent T described below.

[0457] Examples of the acid group, basic group, and hydrogen bonding group represented by X include the groups described above.

[0458] When a pigment type compound is used as a near-infrared absorbing pigment, it is also preferred that the pigment derivative is a compound having a maximum absorption wavelength in the range of 700nm to 1,200nm, a compound having a maximum absorption wavelength in the range of 700nm to 1,100nm, and a compound having a maximum absorption wavelength in the range of 700nm to 1,000nm. In the pigment derivative having a maximum absorption wavelength in the above wavelength range, the expansion of the π plane can easily approach the near-infrared absorbing pigment, improve the adsorption of the near-infrared absorbing pigment, and thus easily obtain a more excellent dispersion stability. In addition, the pigment derivative is also preferably a compound containing an aromatic ring, and more preferably a compound containing a structure formed by condensation of two or more aromatic rings. In addition, the pigment derivative is also preferably a compound having a π conjugated plane, and more preferably a compound having a π conjugated plane with the same structure as the π conjugated plane contained in the near-infrared absorbing pigment. In addition, the number of π electrons contained in the π conjugated plane of the pigment derivative is preferably 8 to 100. The upper limit is preferably 90 or less, and more preferably 80 or less. The lower limit is preferably 10 or more, more preferably 12 or more. Furthermore, the pigment derivative is also preferably a compound having a π-conjugated plane including a partial structure represented by the following formula (SQ-a).

[0459] [Chemical formula 38]

[0460]

[0461] In the above formula (SQ-a), the wavy line portion indicates a bonding position with other structures.

[0462] The pigment derivative is also preferably a compound represented by the following formula (Syn 1).

[0463] [Chemical formula 39]

[0464]

[0465] In formula (Syn1), Rsy 1 and Rsy 2 Each independently represents an organic group, L 1 A represents a single bond or a p1+1 valence group. 1 represents a sulfonic acid group, a carboxyl group, a phosphoric acid group, a boric acid group, a sulfonimide group, a sulfonamide group, an amino group, a pyridyl group, a group selected from the salts thereof or the desalted structures thereof, and p1 and q1 each independently represent an integer greater than 1. When p1 is 2 or greater, a plurality of A 1 They may be the same or different. When q1 is 2 or more, multiple L 1 and A 1 It can be the same or different.

[0466] As Rsy of formula (Syn1) 1 and Rsy 2 Examples of the organic group include an aryl group, a heteroaryl group, and a group represented by the following formula (R1).

[0467] [Chemical formula 40]

[0468]

[0469] In formula (R1), X 11 Represents a ring structure, A 11 Indicates O or NR 51 , R 46 ~R 51 Each independently represents a hydrogen atom or a substituent, R 47 With R 48 They may be bonded to each other to form a ring, and * represents a bonding bond.

[0470] As L in formula (Syn1) 1 Examples of the p1+1 valent group represented by include a hydrocarbon group, a heterocyclic group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2 -、-NR L -、-NR L CO-、-CONR L -、-NR L SO2 -、-SO 2 NR L - and groups consisting of these combinations. L represents a hydrogen atom, an alkyl group or an aryl group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the hydrocarbon group include an alkylene group, an arylene group or a group obtained by removing one or more hydrogen atoms from these groups. 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 be any of a linear, branched or cyclic group. Furthermore, the cyclic alkylene group may be any of a monocyclic or 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. The heterocyclic group is a monocyclic ring or a condensed ring having a condensation number of preferably 2 to 4. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. The hydrocarbon group and the heterocyclic group may have a substituent. As the substituent, there can be mentioned the groups exemplified in the substituent T described later. L The number of carbon atoms in the alkyl group represented 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, but is preferably linear or branched, and more preferably linear. L The alkyl group represented by may further have a substituent. As the substituent, the substituent T described below can be mentioned. L The number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. L The aryl group represented may further have a substituent. As the substituent, the substituent T described below can be mentioned.

[0471] -Substituent T-

[0472] Examples of the substituent T include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, -ORt 1 、-CORt 1 、-COORt 1 、-OCORt 1 、-NRt 1 R 2 、-NHCORt 1 、-CONRt 1 R 2 、-NHCONRt 1 R 2 、-NHCOORt 1 、-SRt 1 、-SO 2 R 1 、-SO 2O 1 、-NHSO 2 R 1 or -SO 2 NlUT 1 R 2 . Rt 1 and Rt 2 Rt represents independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. 1 With Rt 2 They may be bonded to form a ring.

[0473] Specific examples of the pigment derivatives include compounds having the following structures. Also, Japanese Patent Laid-Open No. 56-118462, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 1-217077, Japanese Patent Laid-Open No. 3-9961, Japanese Patent Laid-Open No. 3-26767, Japanese Patent Laid-Open No. 3-153780, Japanese Patent Laid-Open No. 3-45662, Japanese Patent Laid-Open No. 4-285669, Japanese Patent Laid-Open No. 6 The compounds described in Japanese Patent Application No. 0005-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 00063, Japanese Patent Application Laid-Open No. 000195326, paragraphs 0086 to 0098 of International Publication No. 2011 / 024896, and paragraphs 0063 to 0094 of International Publication No. 2012 / 102399.

[0474] In addition, as pigment derivatives, compounds described in Japanese Patent Application Laid-Open No. 2015-172732 (metal salt of quinoline yellow compound having a sulfonic acid group), Japanese Patent Application Laid-Open No. 2014-199308, Japanese Patent Application Laid-Open No. 2014-85562, Japanese Patent Application Laid-Open No. 2014-35351 or Japanese Patent Application Laid-Open No. 2008-81565 can also be used, and these contents are incorporated into this specification.

[0475] In addition, Ph represents a phenyl group.

[0476] [Chemical formula 41]

[0477]

[0478] [Chemical formula 42]

[0479]

[0480] [Chemical formula 43]

[0481]

[0482] [Chemical formula 44]

[0483]

[0484] [Chemical formula 45]

[0485]

[0486] [Chemical formula 46]

[0487]

[0488] [Chemical formula 47]

[0489]

[0490] [Chemical formula 48]

[0491]

[0492] [Chemical formula 49]

[0493]

[0494] [Chemical formula 50]

[0495]

[0496] When the composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the compound having a structure represented by formula (1) and the pigment in the above-mentioned colorant. Only one type of the pigment derivative may be used, or two or more types may be used simultaneously.

[0497] <Polymerization inhibitor>

[0498] From the viewpoint of storage stability, the composition of the present invention preferably contains a polymerization inhibitor.

[0499] The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.

[0500] Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, first cerium salts, etc.), 2,2,6,6-tetramethylpiperidin-1-oxyl, etc. In addition, the polymerization inhibitor can also function as an antioxidant.

[0501] The polymerization inhibitor may be used alone or in combination of two or more.

[0502] From the viewpoint of storage stability, the content of the polymerization inhibitor is preferably 0.1 ppm to 1,000 ppm, more preferably 1 ppm to 500 ppm, and particularly preferably 1 ppm to 100 ppm, based on the total solid content of the composition.

[0503] <Solvent>

[0504] The composition of the present invention may contain a solvent.

[0505] Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and alkyl 3-oxypropionates such as methyl 3-methoxypropionate and ethyl 3-methoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate). ethyl propionate) and 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate and propyl 2-oxopropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate) and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.;

[0506] Ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; aromatic hydrocarbons include toluene, xylene, etc. Among them, from the perspective of environmental protection, there is a case where the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents are reduced (for example, relative to the total mass of the organic solvent, it can be set to 50 mass ppm (parts per million) or less, it can be set to 10 mass ppm or less, and it can be set to 1 mass ppm or less.).

[0507] Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, and the like are preferred.

[0508] The solvent may be used alone or in combination of two or more.

[0509] In the present invention, it is preferred to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, organic solvents of the mass ppt (parts per trillion) level may also be used, and these organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0510] As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation or thin film distillation, etc.) or filtering using a filter can be cited. The filter pore size of the filter used in the filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0511] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may contain only one type or multiple types.

[0512] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0513] The total solid content of the composition of the present invention may be changed depending on the coating method and the presence or absence of a solvent, but is preferably 1% by mass to 100% by mass, for example. The lower limit is more preferably 10% by mass or more.

[0514] <Sensitizer>

[0515] The composition of the present invention may contain a sensitizer for the purpose of increasing the generation efficiency of polymerization initiators such as free radicals and cations of the polymerization initiator and extending the photosensitive wavelength. As the sensitizer that can be used in the present invention, it is preferred that the above-mentioned photopolymerization initiator is sensitized by an electron transfer mechanism or an energy transfer mechanism.

[0516] Examples of the sensitizer include compounds listed below and having an absorption wavelength in the wavelength range of 300 nm to 450 nm.

[0517] Preferred examples of the sensitizer include compounds belonging to the following classes and having an absorption wavelength in the range of 330 nm to 450 nm.

[0518] For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (e.g., fluorescent yellow, eosin, erythrosine, rose red B, rose Bengal), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), anthocyanins (e.g., thiacarbocyanine, oxacarbocyanine), merocyanidins (e.g., merocyanidin, carbomerocyanine), phthalocyanines, thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinone), and squaric acids. (e.g., squaric acid), acridine orange, coumarins (e.g., 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styrene, pyrylium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, michler's ketone and other aromatic ketone compounds, N-aryl oxazolidinone and other heterocyclic compounds, etc. Further examples include compounds described in European Patent No. 568,993, U.S. Patent Nos. 4,508,811 and 5,227,227, Japanese Patent Application Laid-Open Nos. 2001-125255 and 11-271969.

[0519] The sensitizer may be used alone or in combination of two or more.

[0520] The content of the sensitizer in the composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total solid content of the composition, from the viewpoint of light absorption efficiency in the deep part and initial decomposition efficiency.

[0521] <Co-sensitizer>

[0522] The composition of the present invention may contain a co-sensitizer. The co-sensitizer has the function of further improving the sensitivity to the active radiation of the sensitizing dye or the initiator or suppressing the polymerization inhibition of the polymerizable compound by oxygen.

[0523] Examples of the co-sensitizer include compounds described in paragraphs 0233 to 0241 of JP-A-2007-277514.

[0524] From the viewpoint of improving the polymerization growth rate and the curing rate based on the balance of chain transfer, the content of these co-sensitizers is preferably in the range of 0.1% by mass to 30% by mass, more preferably in the range of 0.5% by mass to 25% by mass, and further preferably in the range of 1% by mass to 20% by mass, relative to the mass of the total solid content of the composition.

[0525] <Other ingredients>

[0526] The composition of the present invention may contain various additives such as fluorine-based organic compounds, thermal inhibitors, photopolymerization initiators, other fillers, alkali-soluble resins and polymer compounds other than dispersants, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors as needed.

[0527] Examples of other components include compounds described in paragraphs 0238 to 0249 of JP-A-2007-277514.

[0528] <Preparation of Composition>

[0529] The composition of the present invention can be prepared by mixing the above-mentioned components. In addition, the mixture is preferably filtered with a filter for the purpose of removing foreign matter or reducing defects.

[0530] As a filter, if it is a filter suitable for filtering purposes in the past, it can be used without special restrictions. For example, filters using fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (such as nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (including high-density and ultra-high molecular weight), etc. can be cited. Among these raw materials, polypropylene (including high-density polypropylene) or nylon is preferred.

[0531] The pore size of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, and further preferably 0.05 μm 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 steps can be reliably removed. In addition, it is also preferred to use a fibrous filter material. Examples of the filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) filter elements manufactured by ROKI TECHNO CO., LTD. can be used.

[0532] When using filters, different filters may be combined. In this case, filtering using the first filter may be performed once or twice or more.

[0533] Furthermore, a first filter having a different pore size within the above range may be combined. Here, the pore size can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD. (DFA4201NXEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Japan Microlis Co., Ltd.) or KITZ MICRO FILTER CORPORATION.

[0534] <Application of the composition>

[0535] Since the composition of the present invention can be formed into a liquid state, for example, the composition of the present invention can be applied to a substrate or the like and dried to easily produce a film.

[0536] When forming a film by coating, the viscosity of the composition of the present invention at 25° C. is preferably 1 mPa·s to 100 mPa·s from the viewpoint of coating properties. The lower limit is more preferably 2 mPa·s or more, and further preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, further preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

[0537] The viscosity in the present invention is measured at 25° C. using a viscometer manufactured by TOKI SANGYO CO., LTD. (product name: VISCOMETER TV-22).

[0538] The use of the composition of the present invention is not particularly limited. For example, it can be preferably used in the formation of an infrared cut-off filter, etc. For example, it can be preferably used in an infrared cut-off filter in the light-receiving side of a solid-state imaging element (for example, an infrared cut-off filter for a wafer-level lens, etc.), an infrared cut-off filter in the back side (opposite to the light-receiving side) of a solid-state imaging element, etc. In particular, it can be preferably used as an infrared cut-off filter in the light-receiving side of a solid-state imaging element. In addition, relative to the composition of the present invention, it also contains a colorant that blocks visible light, so it is also possible to form an infrared transmission filter that can transmit infrared rays above a predetermined wavelength. For example, it is also possible to form an infrared transmission filter that blocks to wavelengths of 400nm to 850nm and can transmit infrared rays above a wavelength of 850nm.

[0539] Furthermore, it is preferred that the composition of the present invention be stored in a storage container.

[0540] Furthermore, as a container, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multilayer bottle having an inner wall composed of six layers of six types of resin or a bottle having a seven-layer structure of six types of resin. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[0541] <Film>

[0542] The film of the present invention is a film formed by the composition of the present invention or curing the above-mentioned composition. In addition, when the composition contains a solvent, it can be dried. The film of the present invention can be preferably used as an infrared cut-off filter. In addition, it can also be used as a heat ray shielding filter or an infrared transmission filter. The film of the present invention can also be laminated on a support and used, and can also be peeled off from a support and used. The film of the present invention can have a pattern or a film (flat film) without a pattern.

[0543] The “drying” in the present invention only requires the removal of at least a portion of the solvent, and does not require the complete removal of the solvent. The amount of solvent to be removed can be set as desired.

[0544] The curing may be performed to increase the hardness of the film, but curing by polymerization is preferred.

[0545] The thickness of the film of the present invention can be appropriately adjusted according to the purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the thickness of the film is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0546] The film of the present invention preferably has a maximum absorption wavelength in the range of 650 nm to 1,500 nm, more preferably in the range of 680 nm to 1,300 nm, and even more preferably in the range of 700 nm to 850 nm.

[0547] When the film of the present invention is used as an infrared cut filter, the film of the present invention preferably satisfies at least one of the following conditions (1) to (4), and more preferably satisfies all of the conditions (1) to (4).

[0548] (1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.

[0549] (2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

[0550] (3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

[0551] (4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

[0552] The film of the present invention can also be used in combination with a color filter comprising a colorant. The color filter can be manufactured using a coloring composition comprising a colorant. As the coloring composition, the coloring composition described in the column of the composition of the present invention can be cited. The coloring composition can also contain resins, polymerizable compounds, polymerization initiators, surfactants, solvents, inhibitors, ultraviolet light absorbers, etc. Regarding the details of these, the above materials can be cited, and these can be used.

[0553] When the film of the present invention is used in combination with a color filter, it is preferred that a color filter is disposed on the optical path of the light of the film of the present invention. For example, the film of the present invention can be stacked with a color filter and used as a laminate. In the laminate, the film of the present invention and the color filter can be adjacent to each other in the thickness direction or not. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention can be formed on a support different from the support formed with the color filter, or other components (for example, microlenses, planarization layers, etc.) constituting a solid-state imaging element can be between the film of the present invention and the color filter.

[0554] In addition, in the present invention, an infrared cut filter refers to a filter that allows light of wavelengths in the visible region (visible light) to pass through and blocks at least a portion of light of wavelengths in the infrared region (infrared light). The infrared cut filter can completely pass light of wavelengths in the visible region, or can pass light of a predetermined wavelength region in the light of wavelengths in the visible region and block light of the predetermined wavelength region. Furthermore, in the present invention, a color filter refers to a filter that allows light of a predetermined wavelength region in the light of wavelengths in the visible region to pass through and blocks light of the predetermined wavelength region. Furthermore, in the present invention, an infrared transmission filter refers to a filter that blocks visible light and allows at least a portion of infrared light to pass through.

[0555] The film of the present invention can be used in various devices such as solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.

[0556] <Method for producing film>

[0557] Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through the step of applying the composition of the present invention.

[0558] In the method for manufacturing the film of the present invention, the composition is preferably applied to a support. As a support, for example, a substrate formed of materials such as silicone, alkali-free glass, soda glass, Pyrex glass (registered trademark) glass, and quartz glass can be cited. Organic films or inorganic films can be formed in these substrates. As a material for the organic film, for example, the above-mentioned resin can be cited. In addition, as a support, a substrate formed of the above-mentioned resin can also be used. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the support. In addition, a black matrix is ​​sometimes formed on the support to isolate each pixel. In addition, on the support, a primer layer can be provided as needed, and in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or make the surface of the support such as the substrate flat. In addition, when a glass substrate is used as a support, it is preferred to form an inorganic film on the glass substrate, or to use the glass substrate by dealkalization treatment. According to this method, a film that further suppresses the generation of foreign matter can be easily manufactured.

[0559] As a coating method of the composition, a known method can be used. For example, a drop method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit spin coating method; a pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle jetting, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.; a transfer method using a mold, etc.; a nanoimprint method, etc. There is no particular limitation on the applicable method in inkjet, and examples thereof include the method described in "Inkjet that can be promoted and used - Infinite possibilities appearing in patents -, published in February 2005, Sumitbe TechonResearch Co., Ltd." (especially pages 115 to 133), Japanese Patent Gazette No. 2003-262716, Japanese Patent Gazette No. 2003-185831, Japanese Patent Gazette No. 2003-261827, Japanese Patent Gazette No. 2012-126830, Japanese Patent Gazette No. 2006-169325, etc.

[0560] The composition layer formed by applying the composition can be dried (prebaked). In the case of forming a pattern by a low-temperature process, prebaking is not required. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit is, for example, preferably set to above 50°C, and more preferably set to above 80°C. By performing the prebaking at a temperature below 150°C, for example, when a photoelectric conversion film of an image sensor is formed from organic raw materials, these characteristics can be further effectively maintained.

[0561] The pre-baking time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and further preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.

[0562] The film production method of the present invention may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using photolithography or a pattern forming method using dry etching.

[0563] That is, the present invention includes a pattern forming method including: a step of forming a composition layer on a support using the composition of the present invention; and a step of forming a pattern on the composition layer by photolithography or dry etching.

[0564] When the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the step of forming a pattern will be described in detail.

[0565] - When patterning is performed by photolithography -

[0566] The pattern forming method using photolithography preferably includes the following steps: an exposure step, exposing the composition layer formed by applying the composition of the present invention in a pattern; and a development step, developing and removing the composition layer of the unexposed portion to form a pattern. If necessary, a step of baking the developed pattern (post-baking step) may be provided. The following is a description of each step.

[0567] <<Exposure steps>>

[0568] In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer is exposed through a mask having a predetermined mask pattern using an exposure device such as a stepper, so that the composition layer can be pattern-exposed. Therefore, the exposed portion can be cured. As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferred, and i-rays are more preferred. The irradiation amount (exposure amount) is, for example, preferably 0.03 J / cm 2 ~2.5J / cm 2 , more preferably 0.05 J / cm 2 ~1.0J / cm 2 , especially preferably 0.08 J / cm 2 ~0.5J / cm 2The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can be performed in a low oxygen environment 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 environment 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, preferably from 1,000 W / m 2 ~100,000W / m 2 (For example, 5,000W / m 2 、15,000W / m 2 、35,000W / m 2 The oxygen concentration and exposure illuminance can be appropriately combined, for example, the oxygen concentration can be 10% by volume and the illuminance can be 10,000 W / m 2 , oxygen concentration 35 volume % and illumination 20,000 W / m 2 wait.

[0569] <<Development Step>>

[0570] Next, the composition layer of the unexposed portion in the composition layer after exposure is developed and removed to form a pattern. The development and removal of the composition layer of the unexposed portion can be performed using a developer. Therefore, the composition layer of the unexposed portion in the exposure step is dissolved by the developer, and only the photocured portion remains on the support. As the developer, an alkaline developer that does not damage the solid-state imaging element or circuit of the substrate is preferred. The temperature of the developer is preferably 20°C to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve the residue removability, the following steps can be repeated multiple times, that is, the developer is thrown off every 60 seconds, and a new developer is supplied.

[0571] As the alkali agent used in the developer, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate and other inorganic alkaline compounds can be cited. The developer can preferably use an alkaline aqueous solution diluted with pure water. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. In addition, the developer can also use a surfactant. As an example of a surfactant, the surfactant described in the above composition can be cited, preferably a nonionic surfactant. From the perspective of convenient transfer or storage, the developer can be temporarily prepared as a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and can be set in the range of 1.5 to 100 times, for example. In addition, when using a developer including these alkaline aqueous solutions, it is preferred to wash (rinse) with pure water after development.

[0572] After development, after drying, a heat treatment (post-baking) can also be performed. Post-baking is a heat treatment after development for completely curing the film. In the case of post-baking, the post-baking temperature is preferably, for example, 100°C to 240°C. From the viewpoint of film curing, 200°C to 230°C is more preferred. In addition, when an organic electroluminescent (organic EL) element is used as a light source or a photoelectric conversion film of an image sensor is formed from an organic raw material, 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 50°C or more, for example. Regarding post-baking, the developed film can be post-baked in a continuous or intermittent manner using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in a manner that meets the above conditions. In addition, when a pattern is formed by a low-temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.

[0573] -When patterning is performed by dry etching-

[0574] The pattern formation using the dry etching method can be performed by the following method, that is, the composition layer formed by coating the composition on a support body is cured to form a cured layer, and then a patterned photoresist layer is formed on the cured layer, and then the patterned photoresist layer is used as a mask to dry-etch the cured layer using an etching gas. When forming the photoresist layer, it is preferred to further perform a pre-baking treatment. In particular, as a photoresist formation process, it is preferred to perform a heating treatment after exposure and a heating treatment after development (post-baking treatment). Regarding the pattern formation using the dry etching method, reference can be made to the records of paragraphs 0010 to 0067 of Japanese Patent Gazette No. 2013-64993, and the contents are incorporated into this specification.

[0575] <Optical filter and laminate>

[0576] The optical filter of the present invention has the film of the present invention.

[0577] The optical filter of the present invention can be preferably used as an infrared cut filter or an infrared transmission filter, and can be more preferably used as an infrared cut filter.

[0578] Furthermore, an embodiment including the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferred embodiment of the optical filter of the present invention.

[0579] Furthermore, the laminated body of the present invention is a laminated body comprising the film of the present invention and a color filter containing a color colorant.

[0580] The infrared cut filter of the present invention has the film of the present invention.

[0581] In addition, the infrared cut filter of the present invention may be a filter that cuts off only infrared rays of a portion of the wavelength in the infrared region, or may be a filter that cuts off the entire infrared region. As a filter that cuts off only infrared rays of a portion of the wavelength in the infrared region, for example, a near-infrared cut filter can be cited. In addition, as near-infrared rays, infrared rays with a wavelength of 750nm to 2,500nm can be cited.

[0582] The infrared cut filter of the present invention is preferably a filter that cuts off infrared rays in the wavelength range of 750 nm to 1,000 nm, more preferably a filter that cuts off infrared rays in the wavelength range of 750 nm to 1,200 nm, and even more preferably a filter that cuts off infrared rays in the wavelength range of 750 nm to 1,500 nm.

[0583] The infrared cut filter of the present invention may have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, a substrate (for example, a glass substrate), and the like in addition to the above-mentioned films.

[0584] The infrared cut filter of the present invention also has at least a layer containing copper or a dielectric multilayer film, so it is easy to obtain an infrared cut filter with a wide viewing angle and excellent infrared shielding properties. In addition, the infrared cut filter of the present invention also has an ultraviolet absorption layer, so it is possible to form an infrared cut filter with excellent ultraviolet shielding properties. As an ultraviolet absorption layer, for example, the absorption layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015 / 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.

[0585] As the copper-containing layer, a glass substrate formed of copper-containing glass (copper-containing glass substrate) or a layer containing a copper complex (copper-containing complex layer) can also be used. As the copper-containing glass substrate, copper-containing phosphate glass, copper-containing fluorophosphate glass, etc. can be mentioned. As commercially available products of copper-containing glass, NF-50 (manufactured by AGC TECHNO GLASS CO., LTD.), BG-60, BG-61 (the above are manufactured by Schott AG), CD5000 (manufactured by HOYA GROUP), etc. can be mentioned.

[0586] The infrared cut filter of the present invention can be used in various devices such as solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.

[0587] An aspect in which the infrared cut filter of the present invention has pixels (patterns) of a film obtained using the composition of the present invention and at least one pixel (pattern) selected from red, green, blue, magenta, yellow, cyan, black and colorless is also a preferred aspect.

[0588] The method for producing the optical filter of the present invention is not particularly limited, but preferably comprises the steps of applying the composition of the present invention on a support to form a composition layer, exposing the composition layer in a pattern, and developing and removing unexposed portions to form a pattern.

[0589] Furthermore, the method for manufacturing the optical filter of the present invention preferably includes the steps of applying the composition of the present invention to a support to form a composition layer and curing the composition to form a layer, forming a photoresist layer on the above layer, patterning the photoresist layer by exposing and developing to obtain a photoresist pattern, and dry etching the layer using the photoresist pattern as an etching mask.

[0590] As each step in the method for producing the optical filter of the present invention, each step in the method for producing the film of the present invention can be referred to.

[0591] <Solid-state imaging device>

[0592] The solid-state imaging device of the present invention has the film of the present invention. The structure of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and can function as a solid-state imaging device. For example, the following structures can be cited.

[0593] The structure is as follows: a transfer electrode composed of a plurality of photodiodes and polysilicon etc. constituting a light-receiving area of ​​a solid-state imaging element is provided on a support body, a light-shielding film containing tungsten etc. with only the light-receiving portion of the photodiode opened is provided on the photodiode and the transfer electrode, a device protection film containing silicon nitride etc. formed in a manner covering the entire light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film, and a film of the present invention is provided on the device protection film. Furthermore, it may be a structure having a focusing mechanism (e.g., a microlens etc., the same below) on the device protection film and on the lower side (close to the support body side) of the film of the present invention, a structure having a focusing mechanism on the film of the present invention, and the like. Furthermore, the color filter used in the solid-state imaging element may have a structure in which a film forming each pixel is buried in a space divided into, for example, a grid shape by a partition wall. In this case, it is preferred that the refractive index of the partition wall is lower than the refractive index of each pixel. Examples of imaging devices having such a configuration include those described in Japanese Patent Application Laid-Open Nos. 2012-227478 and 2014-179577.

[0594] <Image display device>

[0595] The image display device of the present invention has the film of the present invention. As the image display device, a liquid crystal display device or an organic electroluminescent (organic EL) display device can be cited. The definition or details of the image display device are recorded in, for example, "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 1990)" and the like. In addition, regarding the liquid crystal display device, it is recorded in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". The image display device can have a white organic EL element. As a white organic EL element, a tandem structure is preferred. The series structure of organic EL elements is described in Japanese Patent Publication No. 2003-45676, supervised by Akiyoshi Mikami, "The Frontier of Organic EL Technology Development - High Brightness, High Precision, Long Life, Technical Secrets Collection", Technical Information Association, pp. 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430nm-485nm), the green region (530nm-580nm) and the yellow region (580nm-620nm). In addition to these emission peaks, it is further preferred to have a maximum emission peak in the red region (650nm-700nm).

[0596] <Infrared sensor>

[0597] The infrared sensor of the present invention has the film of the present invention. The structure of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, one embodiment of the infrared sensor of the present invention will be described using drawings.

[0598] Figure 1 In the figure, reference numeral 110 denotes a solid-state imaging element. An imaging region provided on the solid-state imaging element 110 includes an infrared cut filter 111 and an infrared transmission filter 114. In addition, a color filter 112 is stacked on the infrared cut filter 111. A microlens 115 is arranged on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed in a manner covering the microlens 115.

[0599] The infrared cut filter 111 can be formed using the composition of the present invention. The spectral characteristics of the infrared cut filter 111 can be selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.

[0600] The color filter 112 is a color filter formed with pixels that transmit and absorb light of a predetermined wavelength in the visible region, and is not particularly limited, and a color filter for forming pixels known in the past can be used. For example, a color filter formed with pixels of red (R), green (G), and blue (B) can be used. For example, the records of paragraphs 0214 to 0263 of Japanese Patent Publication No. 2014-43556 can be referenced, and the contents are incorporated into this specification.

[0601] The infrared transmission filter 114 can select its characteristics according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850nm, the maximum value of the transmittance in the thickness direction of the film of the infrared transmission filter 114 in the wavelength range of 400nm to 650nm is preferably 30% or less, more preferably 20% or less, further preferably 10% or less, and particularly preferably 0.1% or less. The transmittance preferably satisfies the above conditions in all regions of the wavelength range of 400nm to 650nm.

[0602] The minimum value of the transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of wavelengths of 800 nm or more (preferably 800 nm to 1,300 nm) is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. The transmittance preferably satisfies the above conditions in a part of the range of wavelengths of 800 nm or more, and more preferably satisfies the above conditions in the wavelength corresponding to the emission wavelength of the infrared LED.

[0603] The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. As long as the film thickness is within the above range, the film can satisfy the above spectral characteristics.

[0604] A method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is described below.

[0605] The film thickness was measured using a probe-type surface profile measuring instrument (DEKTAK150 manufactured by ULVAC, INC.) on a substrate having a film after drying.

[0606] The spectral characteristics of the film are values ​​obtained by measuring transmittance in a wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

[0607] Furthermore, for example, when the emission wavelength of the infrared LED is 940nm, the transmittance of light in the thickness direction of the film of the infrared transmission filter 114 in the wavelength range of 450nm to 650nm is less than 20% at a maximum value, the transmittance of light at a wavelength of 835nm in the thickness direction of the film is less than 20%, and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1,000nm to 1,300nm is preferably greater than 70%.

[0608] Figure 1 In the infrared sensor shown, an infrared cut filter (other infrared cut filter) different from the infrared cut filter 111 may be further configured on the flattening layer 116. As other infrared cut filters, a layer containing copper or at least a dielectric multilayer film may be cited. The details of these may be cited as above. In addition, as other infrared cut filters, a dual-bandpass filter may be used.

[0609] Furthermore, the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present invention can be used in appropriate combination according to the light source used.

[0610] (Camera Module)

[0611] A camera module of the present invention includes a solid-state imaging element and the infrared cut filter of the present invention.

[0612] Furthermore, the camera module of the present invention preferably further includes a lens and a circuit for processing an image obtained from the solid-state imaging element.

[0613] The solid-state imaging element used in the camera module of the present invention may be the solid-state imaging element of the present invention described above, or may be a known solid-state imaging element.

[0614] Furthermore, as the lens used in the camera module of the present invention and the circuit for processing the image obtained from the solid-state imaging element, known lenses and circuits can be used.

[0615] As an example of a camera module, the camera module described in Japanese Patent Application Laid-Open No. 2016-6476 or Japanese Patent Application Laid-Open No. 2014-197190 can be referred to, and the contents thereof are incorporated into this specification.

[0616] The film of the present invention can be used as a heat insulating material or a heat storage material. In addition, the composition of the present invention can also be used for coatings, inkjet inks, anti-counterfeiting inks, and the like.

[0617] Example

[0618] Hereinafter, the present invention will be described in detail by way of Examples, but the present invention is not limited thereto. Unless otherwise specified, "%" and "parts" in the present Examples refer to "mass %" and "mass parts", respectively.

[0619] In addition, in a polymer compound, unless otherwise specified, the molecular weight is a weight average molecular weight (Mw), and the ratio of a structural unit is a molar percentage.

[0620] The weight average molecular weight (Mw) is a value measured as a polystyrene conversion value based on a gel permeation chromatography (GPC) method.

[0621] <X-ray diffraction pattern method based on CuKα rays>

[0622] The X-ray diffraction pattern measurement using CuKα rays was performed in accordance with Japanese Industrial Standards JIS K0131 (General Rules for X-ray Diffraction Analysis) within a diffraction angle (2θ) range of 3° to 35°.

[0623] The measurement conditions are as follows.

[0624] X-ray diffraction apparatus: RINT2100 manufactured by Rigaku Corporation

[0625] Sampling width: 0.02°

[0626] Scanning speed: 2.0° / min

[0627] Divergence slit: 1°

[0628] Divergence vertical limiting slit: 10mm

[0629] Scattering slit: 2°

[0630] Light receiving slit: 0.3mm

[0631] Tube ball: Cu

[0632] Tube voltage: 40kV

[0633] Tube current: 40mA

[0634] (A-ppb-1) was synthesized according to the following scheme. In the following structural formula, Et represents an ethyl group, and Ph represents a phenyl group.

[0635] [Chemical formula 51]

[0636]

[0637] <<Synthesis of Compound A>>

[0638] Compound a was synthesized according to the method described in Tetrahedron 62 (2006) 6018-6028.

[0639] <<Synthesis of Compound b>>

[0640] Compound b was synthesized using 7-ethyl-2-methyl-4-undecanol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material according to the method described in paragraph 0072 of Japanese Patent No. 6353060.

[0641] <<Synthesis of Compound C>>

[0642] Add compound b: 14.9 parts by mass, 50 parts by mass of tert-amyl alcohol, 14.3 parts by mass of sodium tert-pentoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) to the flask, add 10 parts by mass of compound a dropwise over 1 hour at an external temperature of 120°C, and stir for 4 hours. After the reaction, cool to an internal temperature of 60°C, add 100 parts by mass of methanol, 100 parts by mass of water, and 8 parts by mass of acetic acid, screen the precipitated crystals, and wash with 140 parts by mass of methanol. Add 100 parts by mass of methanol to the obtained crystals, heat and reflux for 30 minutes, cool to 30°C, and screen the crystals. By air drying the obtained crystals at 50°C, 10 parts by mass of compound c were obtained.

[0643] <<Synthesis of Compound d>>

[0644] Compound d was synthesized according to the method described in paragraph 0072 of Japanese Patent No. 6353060.

[0645] <<Synthesis of Compound e>>

[0646] Compound c: 7 parts by mass and compound d: 7.5 parts by mass were stirred in 140 parts by mass of toluene, 12 parts by mass of phosphorus oxychloride were added dropwise, and the mixture was heated under reflux for 3.5 hours. After the reaction was completed, the mixture was cooled to an internal temperature of 25°C, and 210 parts by mass of methanol were added dropwise over 60 minutes while maintaining the internal temperature below 30°C. After the addition was completed, the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were screened and washed with 140 parts by mass of methanol. 100 parts by mass of methanol were added to the obtained crystals, heated under reflux for 30 minutes, cooled to 30°C, and the crystals were screened. 6 parts by mass of compound e were obtained by air drying the obtained crystals at 50°C.

[0647] <<Synthesis of Compound f>>

[0648] 17 parts by mass of 2-aminoethyl diphenylborate was stirred in 120 parts by mass of 1,2-dichlorobenzene, and 18 parts by mass of titanium tetrachloride was added dropwise at an external temperature of 40°C over 10 minutes, and stirred for 30 minutes. 6 parts by mass of compound e were added, and the temperature was raised to an external temperature of 125°C and heated for 60 minutes. The mixture was cooled to an internal temperature of 30°C, and 120 parts by mass of methanol were added dropwise while maintaining the internal temperature below 30°C. After the addition, the mixture was stirred for 30 minutes, the crystals were screened, and washed with 60 parts by mass of methanol. 100 parts by mass of methanol were added to the obtained crystals, heated to reflux for 30 minutes, cooled to 30°C, and the crystals were screened. 6 parts by mass of compound f were obtained by air drying the obtained crystals at 50°C.

[0649] <Synthesis of A-ppb-1>

[0650] 5 parts by mass of compound f were stirred in 200 parts by mass of tetrahydrofuran, and 1.4 parts by mass of triethylamine were added dropwise. 0.47 parts by mass of terephthaloyl chloride was added dropwise at room temperature over 30 minutes, and stirred for 30 minutes. The temperature was raised to an external temperature of 75°C, and heated to reflux for 2 hours. The mixture was cooled to an internal temperature of 30°C, the crystals were screened, and washed with 100 parts by mass of tetrahydrofuran. 200 parts by mass of methanol were added to the obtained crystals, the mixture was heated to reflux for 1 hour, the mixture was cooled to 30°C, and the crystals were screened. 4 parts by mass of A-ppb-1 were obtained by air drying the obtained crystals at 50°C. Mass analysis based on MALDI TOF-MASS (time-of-flight mass spectrometry) and 1 As a result of H-NMR measurement, it was identified as a pigment [A-ppb-1].

[0651] ·MALDI TOF-MASS:Calc.for[M+H] + :2271.4found:2271.5

[0652] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.40(d, 4H), 7.00(d, 4H), 7.10(t, 4H), 7.16-7.44(m, 42H), 7.80( s, 2H), 7.82 (s, 2H) 8.22 (s, 2H), 8.30 (s, 2H), 8.49 (s, 4H), 9.00 (s, 2H), 9.05 (s, 2H)

[0653] ·λmax:882nm(CHCl 3 )

[0654] <Synthesis of A-ppb-2>

[0655] In the synthesis of compound A-ppb-1, compound A-ppb-2 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to 4,4'-diphenyldicarbonyl chloride. The identification data details are shown below.

[0656] ·MALDI TOF-MASS:Calc.for[M+H] + :2347.4found:2347.4

[0657] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.40(d, 4H), 7.00(d, 4H), 7.10(t, 4H), 7.16-7.44(m, 42H), 7.80(s, 2H), 7 .82(s, 2H), 7.90(d, 4H), 8.22(s, 2H), 8.30(s, 2H), 8.44(d, 4H), 9.00(s, 2H), 9.05(s, 2H),

[0658] ·λmax:882nm(CHCl 3 )

[0659] The X-ray diffraction pattern using CuKα rays was measured and found to have peaks at Bragg angles 2θ=5.7° and 6.4°.

[0660] <Synthesis of A-ppb-3>

[0661] In the synthesis of compound A-ppb-1, compound A-ppb-3 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to 4,4′-oxybis(benzoyl chloride). The identification data details are shown below.

[0662] ·MALDI TOF-MASS:Calc.for[M+H] + :2363.4found:2363.4

[0663] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.37(d, 4H), 6.97(d, 4H), 7.09(t, 4H), 7.16-7.44(m, 46H), 7.80(s , 2H), 7.81(s, 2H), 8.22(s, 2H), 8.29(s, 2H), 8.36(d, 4H), 8.99(s, 2H), 9.04(s, 2H),

[0664] ·λmax:882nm(CHCl 3 )

[0665] The X-ray diffraction pattern using CuKα rays was measured and found to have peaks at Bragg angles 2θ=7.7° and 9.6°.

[0666] <Synthesis of A-ppb-4>

[0667] In the synthesis of compound A-ppb-1, compound A-ppb-4 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to the following difunctional acid chloride 1.

[0668] [Chemical formula 52]

[0669]

[0670] The following shows the details of the identification data.

[0671] ·MALDI TOF-MASS:Calc.for[M+H] + :2371.4found:2371.5

[0672] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.37(d, 4H), 6.97(d, 4H), 7.09(t, 4H), 7.16-7.44(m, 42H), 7.77(d, 4H), 7 .80(s,2H),7.81(s,2H),8.22(s,2H),8.29(s,2H),8.33(d,4H),8.99(s,2H),9.04(s,2H),

[0673] ·λmax:882nm(CHCl 3 )

[0674] The X-ray diffraction pattern using CuKα rays was measured and found to have a peak at a Bragg angle of 2θ=6.3°.

[0675] <Synthesis of A-ppb-5>

[0676] Compound A-ppb-5 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to the following difunctional acid chloride 2.

[0677] [Chemical formula 53]

[0678]

[0679] The following shows the details of the identification data.

[0680] ·MALDI TOF-MASS:Calc.for[M+H] + :2415.4found:2415.5

[0681] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.38(d, 4H), 7.00(d, 4H), 7.09(t, 4H), 7.16-7.42(m, 42H), 7.78-7.82 (m, 8H), 7.88 (d, 4H), 8.22 (s, 2H), 8.30 (s, 2H), 8.42 (d, 4H), 9.00 (s, 2H), 9.05 (s, 2H),

[0682] <Synthesis of A-ppb-6>

[0683] Compound A-ppb-6 was synthesized by the same method as Compound A-ppb-1, except that terephthaloyl chloride was changed to fumaroyl chloride in the synthesis of Compound A-ppb-1.

[0684] The following shows the details of the identification data.

[0685] ·MALDI TOF-MASS:Calc.for[M+H] + :2221.4found:2221.5

[0686] · 1 H-NMR (CDCl 3 ): δ6.33(d, 4H), 6.38(d, 4H), 6.94(d, 4H), 7.09(t, 4H), 7.16-7.44(m, 44H), 7.80(s, 2H), 7.82(s, 2H), 8.22(s, 2H), 8.27(s, 2H), 9.00(s, 2H), 9.04(s, 2H)

[0687] ·λmax:882nm(CHCl 3 )

[0688] The X-ray diffraction pattern using CuKα rays was measured and found to have peaks at Bragg angles 2θ=10.0°, 11.5°, and 13.3°.

[0689] <Synthesis of A-ppb-7>

[0690] Compound A-ppb-7 was synthesized by the same method as Compound A-ppb-1, except that Compound a was changed to the following Compound a2 in the synthesis of Compound A-ppb-1.

[0691] [Chemical formula 54]

[0692]

[0693] The following shows the details of the identification data.

[0694] ·MALDI TOF-MASS:Calc.for[M+H] + :2415.4

[0695] Found: 2415.3

[0696] · 1 H-NMR (CDCl 3 ): δ6.25(d, 4H), 6.38(d, 4H), 7.00(d, 4H), 7.05(d, 4H), 7.18-7.42(m, 40H), 7.82(s, 2H), 7.83(s, 2H), 7.90(d, 4H), 8.26(s, 2H), 8.30(s, 2H), 8.44(d, 4H), 9.03(s, 2H), 9.04(s, 2H)

[0697] ·λmax:882nm(CHCl 3 )

[0698] <Synthesis of A-ppb-11>

[0699] Compound A-ppb-11 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to 2,5-furandiarylcarbonyl chloride.

[0700] The following shows the details of the identification data.

[0701] ·MALDI TOF-MASS:Calc.for[M+H] + :2261.4found:2261.4

[0702] · 1 H-NMR (CDCl 3): δ6.33(d, 4H), 6.38(d, 4H), 7.00(d, 4H), 7.09(t, 4H), 7.16-7.44(m, 42H), 7.59( s, 2H), 7.80 (s, 2H) 7.81 (s, 2H), 8.22 (s, 2H), 8.29 (s, 2H), 8.99 (s, 2H), 9.04 (s, 2H)

[0703] ·λmax:882nm(CHCl 3 )

[0704] <Synthesis of A-ppb-13>

[0705] Compound A-ppb-13 was synthesized by the same method as compound A-ppb-1, except that terephthaloyl chloride was changed to 1,3,5-benzenecarboxylic acid trichloride.

[0706] The following shows the details of the identification data.

[0707] ·MALDI TOF-MASS:Calc.for[M+H] + :3367.5 found:3367.4

[0708] · 1 H-NMR (CDCl 3 ): δ6.34(d, 6H), 6.44(d, 6H), 7.09(m, 12H), 7.16-7.46(m, 63H), 7.80( s, 6H), 8.22 (s, 3H), 8.33 (s, 3H), 9.00 (s, 3H), 9.09 (s, 3H), 9.49 (s, 3H)

[0709] ·λmax:882nm(CHCl 3 )

[0710] <Synthesis of A-ppb-16 to 22>

[0711] <Synthesis of A-ppb-16>

[0712] Compound A-ppb-16 was synthesized by the same method as that of Compound A-ppb-2, except that Compound d was changed to the following Compound d2.

[0713] [Chemical formula 55]

[0714]

[0715] The following shows the details of the identification data.

[0716] ·MALDI TOF-MASS:Calc.for[M+H] + :2210.6

[0717] Found: 2210.6

[0718] ·λmax:874nm(CHCl 3 )

[0719] <Synthesis of A-ppb-17>

[0720] Compound A-ppb-17 was synthesized by the same method as that of compound A-ppb-2, except that compound d was changed to the following compound d3.

[0721] [Chemical formula 56]

[0722]

[0723] The following shows the details of the identification data.

[0724] ·MALDI TOF-MASS:Calc.for[M+H] + :2387.4

[0725] Found: 2387.3

[0726] ·λmax:876nm(CHCl 3 )

[0727] <Synthesis of A-ppb-18>

[0728] Compound A-ppb-18 was synthesized by the same method as that of compound A-ppb-2, except that compound d was changed to the following compound d4.

[0729] [Chemical formula 57]

[0730]

[0731] The following shows the details of the identification data.

[0732] ·MALDI TOF-MASS:Calc.for[M+H] + :2699.0

[0733] Found: 2699.0

[0734] ·λmax:887nm(CHCl 3 )

[0735] <Synthesis of A-ppb-19>

[0736] Compound A-ppb-19 was synthesized by the same method as Compound A-ppb-1, except that Compound d was changed to the following Compound d5 in the synthesis of Compound A-ppb-1.

[0737] [Chemical formula 58]

[0738]

[0739] The following shows the details of the identification data.

[0740] ·MALDI TOF-MASS:Calc.for[M+H] + :1995.7

[0741] Found: 1995.6

[0742] ·λmax:814nm(CHCl 3 )

[0743] <Synthesis of A-ppb-21>

[0744] Compound A-ppb-21 was synthesized by the same method as Compound A-ppb-2, except that Compound d was changed to Compound d6 in the synthesis of Compound A-ppb-1.

[0745] [Chemical formula 59]

[0746]

[0747] The following shows the details of the identification data.

[0748] ·MALDI TOF-MASS:Calc.for[M+H] + :2019.6

[0749] Found: 2019.5

[0750] ·λmax:780nm(CHCl 3 )

[0751] <Synthesis of A-ppb-22>

[0752] Compound A-ppb-22 was synthesized by the same method as Compound A-ppb-2, except that Compound d was changed to Compound d7 in the synthesis of Compound A-ppb-1.

[0753] [Chemical formula 60]

[0754]

[0755] The following shows the details of the identification data.

[0756] ·MALDI TOF-MASS:Calc.for[M+H] + :1955.6

[0757] Found: 1955.5

[0758] ·λmax:740nm(CHCl 3 )

[0759] <Preparation of curable composition>

[0760] The raw materials described in the following Tables 1 to 4 were mixed, and the mixture was filtered using a nylon filter having a pore size of 0.45 μm (manufactured by NIHONPALL Corporation) to prepare a curable composition.

[0761] In addition, the dispersion liquid used was the dispersion liquid prepared as follows.

[0762] The pigments, derivatives, dispersants and solvent A of the types described in the dispersion liquid column of the following Tables 1 to 4 were mixed in the mass parts described in the dispersion liquid column of the following Tables 1 to 4, respectively, and 230 mass parts of zirconium oxide microbeads with a diameter of 0.3 mm were added, and a dispersion treatment was performed for 5 hours using a paint stirrer. The microbeads were separated by filtration to prepare a dispersion liquid.

[0763]

[0764]

[0765]

[0766]

[0767] The raw materials used for each curable composition are as follows.

[0768] Derivatives B-1 to B-31 are the same compounds as the above-mentioned B-1 to B-31.

[0769] Resin 1: CYCLOMER P (ACA) 230AA (acrylic polymer having acryloyl and carboxyl groups, manufactured by Daicel Corporation)

[0770] Resin 2: Copolymer of allyl methacrylate (AMA) and methacrylic acid (MAA) (composition ratio (mass ratio): AMA / MAA=80 / 20, Mw=15,000)

[0771] Resin 3: Resin with the following structure. (The values ​​attached to the main chain are molar ratios. Mw = 10,000, acid value = 69.2 mgKOH / g)

[0772] [Chemical formula 61]

[0773]

[0774] Resin 4: Resin having the following structure (acid value = 110 mgKOH / g, weight average molecular weight = 10,000). The numerical value attached to the main chain represents the molar ratio of the repeating unit.

[0775] [Chemical formula 62]

[0776]

[0777] Resin 5: Resin having the following structure (acid value = 184 mgKOH / g, weight average molecular weight = 9,700). The numerical value attached to the main chain represents the molar ratio of the repeating unit.

[0778] [Chemical formula 63]

[0779]

[0780] Curable compound 1: ARONIX M-350 (manufactured by TOAGOSEI CO., LTD.)

[0781] Curable compound 2: a compound having the following structure (M1)

[0782] Curable compound 3: A mixture of compounds of the following structure (M2) (containing 55 mol% to 63 mol% of the left-hand compound)

[0783] Curable compound 4: a compound having the following structure (M3)

[0784] Curable compound 5: a mixture of compounds of the following structure (M4) (the molar ratio of the left-hand compound to the right-hand compound is 7:3)

[0785] Curable compound 6: DENACOL EX-611 (manufactured by Nagase Chemtex Corporation)

[0786] [Chemical formula 64]

[0787]

[0788] Photopolymerization initiator 1: a compound having the following structure (F1)

[0789] Photopolymerization initiator 2: a compound having the following structure (F2)

[0790] Photopolymerization initiator 3: a compound having the following structure (F3)

[0791] Photopolymerization initiator 4: a compound having the following structure (F4)

[0792] Photopolymerization initiator 5: CPI-100P (manufactured by San-Apro Ltd.)

[0793] [Chemical formula 65]

[0794]

[0795] Ultraviolet absorber 1: UV-503 (manufactured by DAITO CHEMICAL CO., LTD.)

[0796] Ultraviolet absorber 2: a compound having the following structure (UV2)

[0797] [Chemical formula 66]

[0798]

[0799] Surfactant 1: Compound having the following structure (Mw=14,000, % indicating the ratio of the constituent repeating unit is mol %)

[0800] [Chemical formula 67]

[0801]

[0802] Surfactant 2: Phthalent FTX-218 (manufactured by NEOS COMANY LIMITED, fluorine-based surfactant)

[0803] Surfactant 3: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)

[0804] -Solvents-

[0805] Solvent 1: Propylene glycol methyl ether acetate (PGMEA)

[0806] Solvent 2: Cyclohexanone

[0807] Solvent 3: Butyl acetate

[0808] Solvent 4: Propylene glycol monomethyl ether

[0809] -Inhibitors-

[0810] Inhibitor 1: p-Methoxyphenol

[0811] Inhibitor 2: ADK STAB AO-80 (manufactured by ADEKA Corporation)

[0812] -Dispersant-

[0813] C1: Resin with the following structure. (The value attached to the main chain is the molar ratio, and the value attached to the side chain is the number of repeating units. Mw = 38,000, acid value = 99.1 mgKOH / g)

[0814] C2: Resin with the following structure. (The value attached to the main chain is the molar ratio, and the value attached to the side chain is the number of repeating units. Mw = 21,000, acid value = 36.0 mgKOH / g, amine value = 47.0 mgKOH / g)

[0815] C3: a block type resin having the following structure (amine value = 90 mgKOH / g, quaternary ammonium salt value = 30 mgKOH / g, weight average molecular weight = 9800). The numerical value attached to the main chain represents the molar ratio of the repeating unit.

[0816] C4: Resin with the following structure. (The value attached to the main chain is the molar ratio, and the value attached to the side chain is the number of repeating units. Mw = 22,900, acid value = 32.3 mgKOH / g, amine value = 45.0 mgKOH / g)

[0817] C5: Resin having the following structure (acid value = 87.0 mgKOH / g, weight average molecular weight = 18000). The numerical value attached to the main chain indicates the molar ratio of the repeating unit, and the numerical value attached to the side chain indicates the number of the repeating units.

[0818] C6: Resin having the following structure (acid value = 85.0 mgKOH / g, weight average molecular weight = 22000). The numerical value attached to the main chain indicates the molar ratio of the repeating unit, and the numerical value attached to the side chain indicates the number of the repeating units.

[0819] C7: Resin having the following structure (acid value = 43 mgKOH / g, weight average molecular weight = 9000). The numerical value attached to the side chain represents the molar ratio of the repeating unit.

[0820] [Chemical formula 68]

[0821]

[0822] [Chemical formula 69]

[0823]

[0824] [Chemical formula 70]

[0825]

[0826] Comparative Compound A to Comparative Compound C: pigments having the following structures.

[0827] [Chemical formula 71]

[0828]

[0829] <Measurement of PGMEA Solubility of Dye Dispersions Listed in Tables 1 to 4>

[0830] Under atmospheric pressure, about 100 mg of the dispersion of the pigments described in Tables 1 to 4 was added to 1 L of propylene glycol methyl ether acetate (PGMEA) at 25°C (the value of the pigments described in Tables 1 to 4 accurately weighed was set to X mg), and stirred for 30 minutes. Then, after standing for 5 minutes, the mixture was filtered, and the filtrate was dried under reduced pressure at 80°C for 2 hours and accurately weighed (the value of the filtrate accurately weighed was set to Y mg). The solubility of the pigments described in Tables 1 to 4 dissolved in propylene glycol methyl ether acetate was calculated by the following formula.

[0831] PGMEA solubility (mg / L) = XY

[0832] A: The solubility of PGMEA is less than 10 mg / L.

[0833] B: PGMEA solubility is 10 mg / L or more and less than 50 mg / L.

[0834] C: PGMEA solubility is 50 mg / L or more and 100 mg / L or less.

[0835] D: PGMEA solubility is greater than 100 mg / L.

[0836] The results are shown in Table 5 below.

[0837] [Table 5]

[0838]

[0839] <Preparation of Cured Film>

[0840] (Production example 1)

[0841] <<Method for producing a cured film using the curable composition of composition 1>>

[0842] Each composition described in Tables 1 to 4 was applied to a glass substrate (Corning Incorporated, "1737") by spin coating so that the film thickness after drying was 1.0 μm, and then heated for 120 seconds using a 100° C. hot plate (pre-baking). Next, an i-ray stepper exposure apparatus FPA-3000i5+ (Canon Inc.) was used at 500 mJ / cm 2 The whole surface was exposed. Then, a developer (CD-2060, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development at 23°C for 60 seconds, followed by rinsing with pure water and spin drying. In addition, a heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200°C to obtain a cured film.

[0843] <Evaluation of spectral characteristics>

[0844] The cured film obtained in the above was analyzed by using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 nm to 2,000 nm.

[0845] The maximum absorbance (Absλmax) at a wavelength of 650 nm to 2,000 nm was measured, and the “average absorbance at a wavelength of 400 nm to 550 nm” when the maximum absorbance was set to 1 was evaluated according to the following criteria.

[0846] The smaller the absorbance at a wavelength of 400 nm to 550 nm when the absorbance is 1, the steeper the spectral shape is, and the higher the transparency in the visible light region and the higher the colorability in the near infrared region are, so the obtained cured film can be said to have excellent spectral characteristics.

[0847] -Evaluation Criteria-

[0848] A: The average absorbance at wavelengths of 400nm to 550nm is less than 0.05.

[0849] B: The average absorbance at a wavelength of 400 nm to 550 nm is 0.05 or more and less than 0.1.

[0850] C: The average absorbance at a wavelength of 400 nm to 550 nm is 0.1 or more and less than 0.2.

[0851] D: The average absorbance at a wavelength of 400 nm to 550 nm is 0.2 or more.

[0852] <Evaluation of heat resistance>

[0853] The cured film obtained in the above was heated at 265° C. for 300 seconds using a hot plate. The transmittance of the film before and after heating for light of wavelength 400 to 2,000 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The transmittance change in the wavelength where the change in transmittance before and after heating is the largest in the range of wavelength 400 nm to 2,000 nm was calculated by the following formula, and the transmittance change was evaluated by the following benchmark. It can be said that the smaller the transmittance change, the better the heat resistance.

[0854] Transmittance change = |(transmittance after light irradiation - transmittance before light irradiation)|

[0855] -Evaluation Criteria-

[0856] A: The transmittance change is less than 3%.

[0857] B: The transmittance change is 3% or more and less than 5%.

[0858] C: The transmittance change is 5% or more and less than 10%.

[0859] D: The transmittance change is 10% or more.

[0860] <Evaluation of light resistance>

[0861] The obtained cured film was placed on a fading tester equipped with an ultra-xenon lamp (200,000 Lux) and irradiated with 200,000 Lux light for 75 hours without using an ultraviolet cutoff filter. Next, the light transmittance spectrum of the film after light irradiation was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The transmittance change in the wavelength with the largest change in transmittance before and after light irradiation within the wavelength range of 400nm to 2,000nm was calculated by the following formula, and the light resistance was evaluated by the following criteria.

[0862] Transmittance change = |(transmittance after light irradiation - transmittance before light irradiation)|

[0863] -Evaluation Criteria-

[0864] A: The transmittance change is less than 3%.

[0865] B: The transmittance change is 3% or more and less than 5%.

[0866] C: The transmittance change is 5% or more and less than 10%.

[0867] D: The transmittance change is 10% or more.

[0868] <Evaluation of dispersibility>

[0869] The average particle diameter of the pigment in the composition described in Tables 1 to 4 was measured by the following method to evaluate the dispersibility. In Comparative Example 2, since Comparative Compound 2 was dissolved in a solvent, the dispersibility was not evaluated.

[0870] The volume average particle size of the pigment in the composition was measured using a NANOTRAC UPA particle size analyzer (UPA-EX150, product name, manufactured by Nikkiso Co., Ltd.), and the dispersibility was evaluated according to the following criteria. It can be said that the smaller the volume average particle size of the pigment in the composition, the better the dispersibility.

[0871] -Evaluation Criteria-

[0872] A: The volume average particle size is 10 nm or more and 100 nm or less.

[0873] B: The volume average particle size is greater than 100 nm and less than 200 nm.

[0874] C: The volume average particle size is greater than 200 nm and less than 500 nm.

[0875] D: The volume average particle size is greater than 500 nm.

[0876] The evaluation results are summarized in Tables 6 to 9.

[0877] [Table 6]

[0878]

[0879] [Table 7]

[0880]

[0881] [Table 8]

[0882]

[0883] [Table 9]

[0884]

[0885] From the results described in Tables 6 to 9, it is understood that the films obtained from the curable compositions of Examples 1 to 68 of the present invention are superior in spectral characteristics to the curable compositions of Comparative Examples 1 to 3.

[0886] Furthermore, it was found that the curable compositions of Examples 1 to 68 of the present invention were also excellent in heat resistance and light resistance.

[0887] (Example 101 to Example 168)

[0888] Using the compositions of Examples 1 to 68, 2 μm square patterns (infrared cut filters) were formed by the following method. Solid-state imaging devices including the obtained infrared cut filters were produced as follows.

[0889] Using the curable compositions of Examples 1 to 68, patterns were produced by the following methods.

[0890] The curable composition was applied by spin coating so that the film thickness after film formation was 1.0 μm. Then, the film was heated at 100° C. for 2 minutes using a hot plate. Then, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1,000 mJ / cm 2 Exposure was performed through a mask with a 2 μm square dot pattern. Then, spin immersion development was performed for 60 seconds at 23°C using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed by spin spraying and further washed with pure water. Next, heating was performed at 200°C for 5 minutes using a hot plate, thereby forming a 2 μm square pattern (infrared cutoff filter).

[0891] Next, the Red composition was applied to the pattern of the infrared cut filter by spin coating so that the film thickness after film formation was 1.0 μm. Next, the film was heated at 100°C for 2 minutes using a hot plate. Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used at 1,000 mJ / cm 2 Exposure was performed through a mask with a 2 μm square dot pattern. Next, a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23°C for 60 seconds. Then, it was rinsed by spin spraying and further washed with pure water. Next, heating was performed at 200°C for 5 minutes using a hot plate, thereby patterning the Red composition on the pattern of the infrared cutoff filter. Similarly, the Green composition and the Blue composition were patterned in sequence to form red, green and blue coloring patterns (Bayer patterns).

[0892] In addition, the Bayer pattern refers to a pattern of a 2×2 array of color filter elements having 1 red element, 2 green elements, and 1 blue element, as disclosed in the specification of U.S. Patent No. 3,971,065, but in the present embodiment, a Bayer pattern of a 2×2 array of filter elements having 1 red element, 1 green element, 1 blue element, and 1 infrared transmission filter element is formed.

[0893] Next, the infrared transmission filter forming composition (the following composition 100 or composition 101) was applied to the patterned film by spin coating so that the film thickness after film formation was 2.0 μm. Next, the film was heated at 100° C. for 2 minutes using a hot plate. Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used at 1,000 mJ / cm 2 The mask of the Bayer pattern of 2 μm square was exposed. Then, a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23°C for 60 seconds. Then, it was rinsed by spin spraying and further washed with pure water. Next, it was heated at 200°C for 5 minutes using a hot plate, so that the infrared transmission filter was patterned in the blank part of the Bayer pattern of the infrared cutoff filter where the above-mentioned colored pattern was not formed. It was assembled in a solid-state imaging element according to these known methods.

[0894] The obtained solid-state imaging element was irradiated with infrared light by an infrared light emitting diode (infrared LED) under a low illumination environment (0.001 lux), and the image was read to evaluate the image performance. When any of the curable compositions obtained in Examples 1 to 68 was used, the image could be clearly recognized even in a low illumination environment.

[0895] The Red composition, the Green composition, the Blue composition, and the infrared transmission filter forming composition used for the above-mentioned patterning are as follows.

[0896] -Red composition-

[0897] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm to prepare a Red composition.

[0898] Red pigment dispersion: 51.7 parts by mass

[0899] Resin 4 (40 mass % PGMEA solution): 0.6 mass parts

[0900] Polymerizable compound 4: 0.6 parts by mass

[0901] Photopolymerization initiator 1: 0.3 parts by mass

[0902] Surfactant 1: 4.2 parts by mass

[0903] PGMEA: 42.6 parts by mass

[0904] -Green composition-

[0905] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm to prepare a Green composition.

[0906] Green pigment dispersion: 73.7 parts by mass

[0907] Resin 4 (40 mass % PGMEA solution): 0.3 mass parts

[0908] Polymerizable compound 1: 1.2 parts by mass

[0909] Photopolymerization initiator 1: 0.6 parts by mass

[0910] Surfactant 1: 4.2 parts by mass

[0911] Ultraviolet absorber (UV-503, manufactured by DAITO CHEMICAL CO., LTD.): 0.5 parts by mass

[0912] PGMEA: 19.5 parts by mass

[0913] -Blue composition-

[0914] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm to prepare a Blue composition.

[0915] Blue pigment dispersion: 44.9 parts by mass

[0916] Resin 4 (40 mass % PGMEA solution): 2.1 parts by mass

[0917] Polymerizable compound 1: 1.5 parts by mass

[0918] Polymerizable compound 4: 0.7 parts by mass

[0919] Photopolymerization initiator 1: 0.8 parts by mass

[0920] Surfactant 1: 4.2 parts by mass

[0921] PGMEA: 45.8 parts by mass

[0922] - Composition for forming infrared transmission filter-

[0923] The components in the following composition were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHONPALL LTD.) having a pore size of 0.45 μm to prepare a composition for forming an infrared transmission filter.

[0924] <Composition 100>

[0925] Pigment dispersion 1-1: 46.5 parts by mass

[0926] Pigment dispersion 1-2: 37.1 parts by mass

[0927] Polymerizable compound 5: 1.8 parts by mass

[0928] Resin 4: 1.1 parts by mass

[0929] Photopolymerization initiator 2: 0.9 parts by mass

[0930] Surfactant 1: 4.2 parts by mass

[0931] Inhibitor (p-methoxyphenol): 0.001 parts by mass

[0932] Silane coupling agent: 0.6 parts by mass

[0933] PGMEA: 7.8 parts by mass

[0934] <Composition 101>

[0935] Pigment dispersion 2-1: 1,000 parts by mass

[0936] Polymerizable compound (dipentatriol hexaacrylate): 50 parts by mass

[0937] Resin 4: 17 parts by mass

[0938] Photopolymerization initiator (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime)): 10 parts by mass

[0939] PGMEA: 179 parts by mass

[0940] Alkali-soluble polymer F-1: 17 parts by mass (solid content concentration: 35 parts by mass)

[0941] <Synthesis Example of Alkali-Soluble Polymer F-1>

[0942] In a reaction vessel, 14 parts by mass of benzyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of styrene and 20 parts by mass of methacrylic acid were dissolved in 200 parts by mass of propylene glycol methyl ether acetate, and 3 parts by mass of 2,2'-azobisisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were added. After nitrogen was purged in the reaction vessel, a solution containing an alkali-soluble polymer F-1 (solid content concentration 35% by mass) was obtained while stirring and bubbling nitrogen. The weight average molecular weight of the polymer converted to polystyrene was 9,700, the number average molecular weight was 5,700, and Mw / Mn was 1.70.

[0943] <Pigment dispersion 2-1>

[0944] 60 parts by mass of CI Pigment Black 32, 20 parts by mass of CI Pigment Blue 15:6, 20 parts by mass of CI Pigment Yellow 139, 80 parts by mass of SOLSPERSE 76500 manufactured by Lubrizol Japan Ltd. (solid content concentration 50% by mass), 120 parts by mass of a solution containing an alkali-soluble polymer F-1 (solid content concentration 35% by mass), and 700 parts by mass of propylene glycol methyl ether acetate were mixed and dispersed for 8 hours using a paint shaker to obtain a pigment dispersion 2-1.

[0945] The raw materials used in the Red composition, the Green composition, the Blue composition, and the infrared transmission filter forming composition are as follows.

[0946] Red pigment dispersion

[0947] A mixture consisting of 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH) and 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm) to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism was used to prepare a pigment dispersion at 2,000 kg / cm 3 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of . This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

[0948] Green pigment dispersion

[0949] A mixture consisting of 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH) and 83.1 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm) to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism was used to prepare a pigment dispersion at 2,000 kg / cm 3 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

[0950] ·Blue pigment dispersion

[0951] A mixture consisting of 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH) and 82.4 parts of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm) to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism was used to prepare a pigment dispersion at 2,000 kg / cm 3 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of . This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

[0952] Pigment dispersion 1-1

[0953] Pigment dispersion 1-1 was prepared by mixing and dispersing the mixed solution of the following components for 3 hours using zirconium oxide beads having a diameter of 0.3 mm with a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon Bee Chemical Co., Ltd.)).

[0954] Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by mass

[0955] Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 parts by mass

[0956] PGMEA: 79.1 parts by mass

[0957] Pigment dispersion 1-2

[0958] Pigment dispersion 1-2 was prepared by mixing and dispersing the mixed solution of the following components for 3 hours using zirconium oxide beads having a diameter of 0.3 mm with a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon Bee Chemical Co., Ltd.)).

[0959] Mixed pigment consisting of blue pigment (CI Pigment Blue 15:6) and violet pigment (CI Pigment Violet 23): 12.6 parts by mass

[0960] Resin (Disperbyk-111, manufactured by BYK Chemie): 2.0 parts by mass

[0961] Resin A: 3.3 parts by mass

[0962] Cyclohexanone: 31.2 parts by mass

[0963] PGMEA: 50.9 parts by mass

[0964] Details of the abbreviations used in the above components are shown below.

[0965] Resin A: The following structure (Mw = 14,000, the ratio in each structural unit is a molar ratio.)

[0966] [Chemical formula 72]

[0967]

[0968] Polymerizable compound 1: KAYARAD DPHA (a mixture of dipentatriol hexaacrylate and dipentatriol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0969] ·Polymerizable compound 4: The following structure

[0970] [Chemical formula 73]

[0971]

[0972] Polymerizable compound 5: the following structure (a mixture of the left-hand compound and the right-hand compound in a molar ratio of 7:3)

[0973] [Chemical formula 74]

[0974]

[0975] Resin 4: The following structure (acid value: 70 mgKOH / g, Mw=11,000, the ratio in each structural unit is a molar ratio.)

[0976] [Chemical formula 75]

[0977]

[0978] Photopolymerization initiator 1: IRGACURE-OXE01 (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime), manufactured by BASF)

[0979] Photopolymerization initiator 2: The following structure

[0980] [Chemical formula 76]

[0981]

[0982] Surfactant 1: 1 mass % PGMEA solution of the following mixture (Mw=14,000): In the following formula, % (62% and 38%) indicating the ratio of the structural unit is a molar ratio.

[0983] [Chemical formula 77]

[0984]

[0985] Silane coupling agent: a compound having the following structure: In the following structural formula, Et represents an ethyl group.

[0986] [Chemical formula 78]

[0987]

[0988] (Example 201)

[0989] The following composition was mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL Corporation) having a pore size of 0.45 μm, thereby preparing a pattern-forming composition of Example 201.

[0990] Curable composition of Example 1: 22.67 parts by mass

[0991] Pigment dispersion 2-1: 51.23 parts by mass

[0992] Using the pattern forming composition of Example 201, light resistance and heat resistance were evaluated in the same manner as in Example 1, and the same effects as in Example 1 were obtained. In addition, the cured film obtained using the pattern forming composition of Example 201 can block light with wavelengths in the visible region and transmit at least a portion of light with wavelengths in the near infrared region (near infrared rays).

[0993] (Example 202)

[0994] The following composition was mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL Corporation) having a pore size of 0.45 μm to prepare a pattern-forming composition of Example 202.

[0995] Curable composition of Example 1: 36.99 parts by mass

[0996] Pigment dispersion 1-1: 46.5 parts by mass

[0997] Pigment dispersion 1-2: 37.1 parts by mass

[0998] Using the pattern forming composition of Example 202, light resistance and heat resistance were evaluated in the same manner as in Example 1, and the same effects as in Example 1 were obtained. In addition, the cured film obtained using the pattern forming composition of Example 202 can block light with wavelengths in the visible region and transmit at least a portion of light with wavelengths in the near infrared region (near infrared rays).

[0999] (Example 301)

[1000] When the curable compositions of Examples 1 to 68 were used respectively and the substrates were changed to other substrates (the glass substrate was changed to a silicon wafer, and the silicon wafer was changed to a glass substrate), and evaluation was performed in the same manner as Example 101, the same effects as those of Examples 101 to 168 were obtained.

[1001] (Example 302)

[1002] When the pattern forming composition obtained in the above-mentioned Example 201 or Example 202 was used and the substrate was changed to other substrates (in the case of a glass substrate, it was changed to a silicon wafer, and in the case of a silicon wafer, it was changed to a glass substrate), and evaluation was performed in the same manner as in Example 101, the same effect as in Example 101 was obtained.

[1003] (Example 401)

[1004] As a result of preparing a pattern-forming composition in the same manner as in Example 201, except that the curable composition of Example 1 used in Example 201 was replaced with the curable composition of Examples 2 to 68, and evaluating light resistance and heat resistance in the same manner as in Example 1, the same effects as in Examples 2 to 68 were obtained. Furthermore, the cured film obtained using the pattern-forming composition of Example 401 was able to shield light of wavelengths in the visible region and transmit at least a portion of light of wavelengths in the near-infrared region (near-infrared rays).

[1005] (Example 402)

[1006] As a result of preparing a pattern forming composition in the same manner as in Example 202, except that the curable composition of Example 1 used in the above-mentioned Example 202 was replaced with the curable composition of Examples 2 to 68, and evaluating light resistance and heat resistance in the same manner as in Example 1, the same effects as in Examples 2 to 68 were obtained. Furthermore, the cured film obtained using the pattern forming composition of Example 402 can block light of wavelengths in the visible region and transmit at least a portion of light of wavelengths in the near infrared region (near infrared rays).

[1007] [Explanation of symbols]

[1008] 110: solid-state imaging element, 111: infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: planarization layer

[1009] In addition, the disclosed contents of Japanese Patent Application No. 2019-157412 filed on August 29, 2019 and Japanese Patent Application No. 2020-047017 filed on March 17, 2020 are incorporated in their entirety into this specification by reference.

[1010] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference in the same manner as if each individual document, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A composition comprising: At least one pigment selected from the group consisting of pigments represented by the following A-ppb-2 to A-ppb-4, A-ppb-6, A-ppb-16 to A-ppb-18, A-ppb-21, and A-ppb-22; organic solvents; and Curing compounds, The solubility of the pigment in propylene glycol methyl ether acetate at 25° C. is 100 mg / L or less, 。 2. The composition according to claim 1, in, The volume average particle size of at least one pigment selected from the pigments represented by A-ppb-2 to A-ppb-4, A-ppb-6, A-ppb-16 to A-ppb-18, A-ppb-21, and A-ppb-22 is 1 nm to 500 nm.

3. The composition according to claim 1, further comprising a pigment derivative.

4. The composition according to claim 1, in, The curable compound contains a polymerizable compound and further contains a photopolymerization initiator. The composition according to claim 1 , comprising an alkali-soluble resin. 6 . A film composed of the composition according to claim 1 or formed by curing the composition. 7 . A near infrared cut filter comprising the film according to claim 6 . The near infrared cut filter according to claim 7 , further comprising a glass substrate.

9. A method for forming a pattern, include: A step of forming a composition layer on a support using the composition according to any one of claims 1 to 5; and The step of patterning the composition layer by photolithography or dry etching. 10 . A laminate comprising the film according to claim 6 and a color filter containing a color colorant. 11 . A solid-state imaging element comprising the film according to claim 6 . 12 . An image display device comprising the film according to claim 6 . 13 . A camera module comprising the film according to claim 6 . 14 . An infrared sensor comprising the film according to claim 6 .

15. A pyrrolopyrrole compound selected from the group consisting of pigments represented by the following A-ppb-2 to A-ppb-4, A-ppb-6, A-ppb-16 to A-ppb-18, A-ppb-21, and A-ppb-22, 。

Images